CN103935955A - Rod-shaped material with surface having multiple properties and manufacturing method and application of Pickering emulsion thereof - Google Patents

Rod-shaped material with surface having multiple properties and manufacturing method and application of Pickering emulsion thereof Download PDF

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CN103935955A
CN103935955A CN201410099510.9A CN201410099510A CN103935955A CN 103935955 A CN103935955 A CN 103935955A CN 201410099510 A CN201410099510 A CN 201410099510A CN 103935955 A CN103935955 A CN 103935955A
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shaped
ball
bar
specially
nanometer
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周鹏
杨振忠
李婧
张成亮
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Abstract

The invention discloses a rod-shaped material with a surface having multiple properties and a manufacturing method and application of Pickering emulsion of the material. The material is composed of a nanorod and discs at the two ends of the nanorod, wherein the diameter of each disc is equal to the diameter of the two end faces of the nanorod, the material forming the nanorod is marked as the material B, the materials forming the discs at the two ends of the nanorod are different and are marked as the material A1 and the material A2 respectively, the material B is selected from at least one of an inorganic material and a metal material, and the material A1 and the material A2 are made of polymer. According to the rod-shaped material, a fiber array manufactured through a die plate method passes through an ultrathin section to obtain rod-shaped nano materials with the uniform size, and then the nano materials are combined with a Pickering emulsion protection-deprotection method to form the rod-shaped material. According to the method, the manufactured number of rod-shaped nano materials can be obviously increased, and the rod-shaped materials have the great potential in biological applications such as a superstructure with the functional surface and the complex assembly and amphiphilic molecular simulation.

Description

Surface has multiple character club-shaped material and Pickering emulsion preparation method and application
Technical field
The present invention relates to a kind of surface and there is multiple character club-shaped material and Pickering emulsion preparation method and application.
Background technology
At the beginning of last century, Pickering(J. Soc. Chem. Ind. 1910,91,2001-2021) find that tiny solid particle can be used as emulsion stabilizer, be called for short Pickering effect.Its possible mechanism is that particle accumulates in two kinds of immiscible liquid surfaces, forms fine and close individual layer and makes emulsion droplet stable, and this class emulsion is called as Pickering emulsion.
French scientist Pierre-Gilles De Genes in 1991 propose the concept of Janus particle first, and the research that from then on has a double properties particulate about surface has caused researcher's extensive concern.The chemical property of Janus particle is asymmetric gives this particle some important characteristics with physical arrangement is asymmetric, therefore, Janus particle is at emulsion-stabilizing (Angew.Chem. Int. Ed. 2008,47,711-714), optics, bio-sensing (Angew. Chem. Int. Ed. 2008,47,173-176), the field such as drug delivery and electronics has potential application prospect.Bar-shaped Janus material is due to particularity in shape, and in the application such as biology, has great potentiality, as simulates amphipathic biomolecule and pass into cell membrane.
Due to the incomplete symmetry of rod-like nano material, bring very large difficulty to its preparation, being difficult to find a kind of preparation method of versatility is that the club-shaped material of preparing is given Janus performance.At present, little about Janus club-shaped material preparation method's report, mainly contain these three kinds: one, utilize the way that microfluid is extruded to prepare bar-shaped Janus colloid (Sep. Pur. Technol. 2001,25,195-210).This colloidal solid size is too large, is difficult to be controlled in submicron-scale, and range of application has also been subject to restriction to a great extent; Two, utilize block copolymer phase disengagement method to prepare bar-shaped Janus colloid (Macromolecules. 2003,36,7894-7898).Janus rod yardstick prepared by this method is being within the scope of molecular scale, and yields poorly, and can not meet actual needs; Three, utilize the way of CNT electro-deposition to prepare bar-shaped Janus colloid, this method efficiency and output are very low, and cost is very high, are also difficult to practical requirement.Therefore, bar-shaped Janus material how to select a kind of simple method to prepare in a large number to possess clear and definite subregion is that researcher very pays close attention to and fail to obtain always the good problem solving, urgently further research.
Summary of the invention
The object of this invention is to provide a kind of surface and there is multiple character club-shaped material and Pickering emulsion preparation method and application.
The invention provides a kind of ball material for the preparation of club-shaped material, this ball material is made up of nanometer stick array section and medicine ball;
Wherein, the described medicine ball of described nanometer stick array section parcel;
Described nanometer stick array section is made up of nanometer rods and matrix; Described nanometer rods is dispersed in described matrix with array way.
In above-mentioned ball material, the material that forms described medicine ball is paraffin;
The material that forms described nanometer rods is selected from least one in inorganic material and metal material;
Wherein, described inorganic material is specially silica; Described metal material is specifically selected from least one in oxide and the simple substance of following element: gold, silver, platinum, iron, cobalt, nickel and rubidium;
The material that forms described matrix is PMMA.
The method of the described ball material of preparation provided by the invention, comprises the steps: that nanometer stick array section is placed in to the Pickering emulsion being made up of paraffin and water carries out emulsification pretreatment, obtains described ball material.
In said method, the mass ratio of described paraffin and water is 1:10-15;
Described nanometer stick array section is 1:5-10 with the mass ratio of paraffin;
In described emulsification pretreatment step, shearing rotating speed is 4000-6000rpm, and the time is 5-10 minute.
Bar-shaped A provided by the invention 1bA 2shaped material, is made up of nanometer rods and the disk that is positioned at described nanometer rods two ends;
And the diameter of described disk is identical with the diameter of two end faces of described nanometer rods;
Wherein, the material that forms described nanometer rods is designated as material B;
Described material B is selected from least one in inorganic material and metal material; Described inorganic material is specially silica; Described metal material is specifically selected from least one in oxide and the simple substance of following element: gold, silver, platinum, iron, cobalt, nickel and rubidium;
The material difference that forms described disk, is designated as respectively materials A 1and materials A 2;
Described materials A 1and A 2all be selected from least one in polystyrene and polyethylene glycol.
Wherein, described nanometer stick array section all can obtain according to the method preparation comprising the steps:
A, alumina formwork and octadecyl trichlorosilane alkane are refluxed and carries out, after hydrophobic treatments, being infiltrated in colloidal sol or electrolyte in solvent, obtain fiber array material;
B, step a gained fiber array material is embedded in polymer embedding matrix, removes after foraminous die plate, undertaken after secondary embedding by similar polymers embedding matrix, section, obtains described nanometer rods and cuts into slices.
In the step a of said method, the aperture of alumina formwork is 10-200nm, and hole depth is 10um-60um;
Solvent is selected from least one in toluene, ethanol and n-hexane;
The concentration of described octadecyl trichlorosilane alkane in reaction system is 1mM-100mM, is specially 10mM;
In described hydrophobic treatments, the time is 12-48 hour, is specially 12h;
In described step b, polymer embedding matrix is PMMA;
In described slicing step, the direction of section and the direction of fibre axis are perpendicular.
The bar-shaped A that the invention described above provides 1bA 2shaped material also can be the product obtaining according to following method preparation provided by the invention.
The bar-shaped A that the described material B of preparation provided by the invention is silica 1bA 2the method of shaped material, comprises the steps:
1) by aforementioned ball material provided by the invention in solvent a with CH 2=CH-C nh 2nsi-R 3room temperature is reacted, and adds after completion of the reaction SH-PEG to carry out Michael addition reaction in methyl alcohol again, obtains bar-shaped A 1type B material ball;
2) by bar-shaped step 1) gained A 1type B material ball is dissolved in n-hexane except deparaffnize, in described solvent a with CH 2=CH-C nh 2nsi-R 3room temperature is reacted, then in methyl alcohol, adds SH-PS to carry out Michael addition reaction, then removes after PMMA matrix with oxolane, and obtaining described material B is the bar-shaped A of silica 1bA 2shaped material;
Described CH 2=CH-C nh 2nsi-R 3in, be-OCH of R 3,-OCH 2cH 3,-Cl or-OCOCH 3;
Described CH 2=CH-C nh 2nsi-R 3be specially 3-(trimethoxy first is silica-based) propyl methacrylate;
N is the integer of 0-12.
In said method, described solvent aall be selected from least one in n-hexane and ethanol;
Described room temperature is carried out in reactions steps, and the time is 6-24 hour, is specially 12 hours;
In described Michael addition reaction step, temperature is room temperature, and the time is 1-10 hour, is specially 6 hours;
Described CH 2=CH-C nh 2nsi-R 3concentration in reaction system is 1-100mM, is specially 1-50mM, is more specifically 5mM;
Concentration in described SH-PS and SH-PEG reaction system is 1-100mM, is specially 1-50mM, is more specifically 5mM.
In addition, step 1) methyl alcohol used is Michael addition reaction solvent, again paraffin and embedding matrix methyl methacrylate is not had to dissolution simultaneously.
The bar-shaped A that the described material B of preparation provided by the invention is metal material 1bA 2the method of shaped material, comprises the steps:
1) ball material the invention described above being provided carries out complex coordination with SH-PEG and reacts in solvent b, obtains bar-shaped A 1type B material ball;
2) by bar-shaped step 1) gained A 1type B material ball is dissolved in oxolane except deparaffnize, carries out complex coordination react in oxolane with SH-PS, and obtaining described material B is the bar-shaped A of metal material 1bA 2shaped material.
In said method, described solvent b is all selected from least one in water, ethanol and oxolane;
In described complex coordination reactions steps, temperature is 15-50 DEG C; Time is 6-24 hour, is specifically 12 hours;
Described SH-PEG and the SH-PS concentration in reaction system is 1mM-100mM, is specially 1-50mM, is more specifically 5mM.
Above-mentioned two side's ratio juris as shown in Figure 1.
The invention provides a kind of method of preparing club-shaped material of protecting-go guard method to combine with ultrathin sectioning Pickering emulsion, the method can be used for preparing in a large number the A that material composition is different, surface has triple character, yardstick homogeneous 1bA 2type nano bar-shape material.
The method has the following advantages:
1, selected method step simple possible, reaction condition gentleness.
2, the method universality is strong, is applicable to metal, metal oxide, inorganic material, polymer etc., and the method is not only for the club-shaped material of single component, is suitable for equally composite material nanometer rod.
3, gained club-shaped material pattern, yardstick homogeneous, end face is smooth, experimental repeatability is good, yardstick controllability is strong, and the range scale of preparation to be clipped to um rank from nm level adjustable continuously.
Brief description of the drawings
Fig. 1 is the schematic diagram of the method.
Fig. 2 is the electromicroscopic photograph of embodiment 1-4 resulting materials; A, b, the corresponding embodiment 1 of c, d; The corresponding embodiment 2 of e, f; The corresponding embodiment 3 of g, h; The corresponding embodiment 4 of i, j.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
Following embodiment 1 nanometer stick array used section a is and is prepared as follows and obtains:
1) AAO template hydrophobically modified:
The AAO template that is 60um by aperture 200nm, hole depth ultrasonic 10min in ethanol, to remove surface debris dirt, after 40 DEG C of vacuum drying, the anhydrous toluene solution that is placed in concentration and is the octadecyl trichlorosilane alkane of 10mM refluxes more than 12h, use successively again dry toluene, after absolute ethyl alcohol repeatedly washs, be placed in 40 DEG C of vacuum drying ovens dry, obtain the AAO template of hydrophobically modified;
2) the AAO template of growth silicon dioxide fibre in duct:
The AAO template of step 1) gained hydrophobically modified is placed in to the ultrasonic 5min of silicon dioxide gel, leaves standstill 10 minutes, after making in the complete filler opening of colloidal sol, template is taken out from colloidal sol, strike off surperficial remaining colloidal sol, under room temperature, place 2h, make it carry out gel process.Be placed on again in 60 DEG C of baking ovens and place 1h, make silicon dioxide fibre gel more complete, obtain the AAO template of growth silicon dioxide fibre in duct.
Wherein, silicon dioxide gel obtains for being prepared as follows: by 4.6g ethanol and 1.08g0.3M HNO 3after solution mixes, then add 6.4g ethyl orthosilicate react 2 hours and obtain in room temperature.
3) embedding and section:
By step 2) the AAO template of growth silicon dioxide fibre is ground into the circular fragment that diameter is 2mm-3mm in gained duct, overlay in the glass tube of base plane sealing.Inject MMA prepolymer, make MMA prepolymer complete wetting embedding AAO lamination, more than 60 DEG C of polymerization 12h, to the complete polymerization of monomer.Take out embedded block, sand papering AAO embedded block sidewall, exposes AAO template, and it is placed in 70 DEG C of reagent and soaks more than 5 days, and AAO template is removed completely.Again this embedded block is dipped in to cyclic washing in intermediate water, ethanol, 40 DEG C of dried overnight.The embedded block being dried is placed in to the teflon hose of ￠ 2, add MMA prepolymer, logical nitrogen pressurization, 60 DEG C of polymerization 12h are above to the complete polymerization of PMMA, then embedded block is placed on ultramicrotome, ensure that fiber axis direction is perpendicular to slice direction, selection step-length is 400nm, use the section speed room temperature section of DiATOME 3mm diamond cutter with 0.3mm/s, obtain nanometer stick array section a, its electromicroscopic photograph is as Fig. 2 a.
Following embodiment 2 nanometer stick array section used b obtains for being prepared as follows:
1) AAO template hydrophobically modified:
The AAO template that is 60um by aperture 200nm, hole depth ultrasonic 10min in ethanol, to remove surface debris dirt, after 40 DEG C of vacuum drying, the anhydrous toluene solution that is placed in concentration and is the octadecyl trichlorosilane alkane of 10mM refluxes more than 12h, use successively again dry toluene, after absolute ethyl alcohol repeatedly washs, be placed in 40 DEG C of vacuum drying ovens dry, obtain the AAO template of hydrophobically modified;
2) preparation is scattered in the Au nano wire in alumina formwork:
Adopt constant potential two-probe method to the AAO template of step 1) gained hydrophobically modified is carried out to electro-deposition, the material of electric deposition device used is polytetrafluoroethylene (PTFE), and Pt silk is as to electrode; At alumina formwork back side evaporation last layer Pt, as working electrode; Electrolyte is made up of deionized water 15.0mL, four hydration gold chloride 1.0g, anhydrous sodium sulfite 1.05g, Triammonium citrate 1.2g, Cobalt monosulfate heptahydrate 0.01g, EDTA 0.9g and potassium hydroxide 0.1g; Au nanowire length, by sedimentation time control, is controlled current potential E=1.5V, after deposition 2h, takes out pellumina and repeatedly cleans with intermediate water, washes away remaining electrolyte, obtains being scattered in the Au nano wire that the length in alumina formwork is 20um;
B, embedding and section:
Step a gained alumina formwork is ground into the circular fragment of diameter 2mm-3mm, stacking in the glass tube of bottom for plane sealing of rule, (its preparation method is the MMA prepolymer that injection number-average molecular weight is 3000: the initator benzoyl peroxide (BPO) that the methacrylate of 4 mL (MMA) monomer is added to 0.04 g, obtain at 90 DEG C of oil bath polymerization 10 min), more than 60 DEG C of polymerization 12h become and have the solid entrapping of some strength piece to the complete polymerization of monomer.Take out after embedded block, the PMMA of its sidewall is struck off, template is exposed.Be placed in 70 DEG C of reagent and soak more than 5 days, alumina formwork is removed completely.Again this embedded block is dipped in to cyclic washing in intermediate water, ethanol, after 40 DEG C of vacuum drying, again be placed in teflon hose, add MMA prepolymer, 60 DEG C of polymerization 12h of logical nitrogen pressurization are above to the complete polymerization of PMMA, again embedded block is placed on ultramicrotome, ensure that fiber axis direction is perpendicular to slice direction, selection step-length is 400nm, use the section speed room temperature section of DiATOME 3mm diamond cutter with 0.3mm/s, obtain nanometer stick array section b, its electromicroscopic photograph as shown in Figure 2 e.
Following embodiment 3 nanometer stick array section used c obtains for being prepared as follows:
According to the preparation method of nanometer stick array section b, only electrolyte is replaced with by deionized water 40.0 mL, seven hydrations and close the electrolyte that the dilute sulfuric acid of ferrous sulfate 4.0g, ammonium sulfate 0.6g, magnesium sulfate 1.2g, antiacid hematic acid 0.04g, glycerine 80uL and concentration 1M forms, the dilute sulfuric acid of this 1M used for electrolyte regulates its pH value to 3;
And current potential E is replaced with to 2.5V, and obtaining being scattered in the Fe nano wire that the length in alumina formwork is 10um, its electromicroscopic photograph is as shown in Figure 2 g.
Following embodiment 4 nanometer stick array section used d obtains for being prepared as follows:
According to the preparation method of nanometer stick array section b, only electrolyte is replaced with to the electrolyte being formed by deionized water 25.0ml, six hydration nickel sulfate 5.26g, boric acid 0.75g and sodium sulphate 0.125g;
And current potential E is replaced with to 2.7V, and obtaining being scattered in the Ni nano wire that the length in alumina formwork is 15um, its electromicroscopic photograph is as shown in Fig. 2 i.
Embodiment 1
1) nanometer stick array is cut into slices a carries out the emulsification of Pickering particle:
First process section with organic solvent, improve after its hydrophilic and oleophilic character, the nanometer stick array Pickering emulsion that a paraffin that to be placed in by mass ratio be 1:10 and water forms of cutting into slices is carried out to high speed shear emulsification, at paraffin/aqueous systems high speed emulsification pretreatment, utilize the Pickering effect of section to form stable emulsion.By cooling the Pickering emulsion system obtaining, washing, obtains the paraffin ball that nanometer stick array section a wraps up, and is also ball material provided by the invention, and its electromicroscopic photograph is as Fig. 2 b;
This ball material is made up of silicon dioxide nano rod array slice and paraffin medicine ball; Wherein, silicon dioxide nano rod array slice parcel paraffin medicine ball; Silicon dioxide nano rod array slice is made up of silicon dioxide nano rod and matrix; Silicon dioxide nano rod length is 400nm, is dispersed in matrix PMMA with array way.
2) step 1) gained ball material is dissolved in ethanol and silane coupler 3-(trimethoxy first is silica-based) propyl methacrylate (the corresponding CH of 3-(trimethoxy first is silica-based) propyl methacrylate with the ratio of mass ratio 1:5 2=CH-C nh 2nsi-R 3middle n is 4, R 3for-OCH 3, the concentration in reaction system is 5mM) and be placed in room temperature reaction 2h on shaking table.This process repeats 3 times to strengthen modified effect, be placed in again afterwards unnecessary 3-(trimethoxy first the is silica-based) propyl methacrylate of filtering on gauze, be placed in again methyl alcohol add AIBN(account for methanol quality 1%) with SH-PEG(be 5mM in the concentration of reaction system) carry out Michael addition reaction 6 hours in room temperature, obtain A 1the bar-shaped A of termination branch PEG 1type B material ball;
3) by step 2) gained A 1the bar-shaped A of termination branch PEG 1type B material ball is dissolved in n-hexane except after deparaffnize, in ethanol, be placed in room temperature reaction 2h on shaking table with 3-(trimethoxy first is silica-based) propyl methacrylate (concentration of 3-(trimethoxy first is silica-based) propyl methacrylate in reaction system is 5mM), this process repeats 3 times to strengthen modified effect, be placed in again afterwards and on gauze, filter unnecessary 3-(trimethoxy first is silica-based) propyl methacrylate, be placed in again methyl alcohol add AIBN(account for methanol quality 1%) with SH-PS(be 5mM in the concentration of reaction system) carry out Michael addition reaction 6 hours in room temperature, react complete dry being placed on and in oxolane, remove PMMA matrix, obtain bar-shaped A provided by the invention 1bA 2shaped material, its electromicroscopic photograph is as shown in Fig. 2 c and d.
This material is made up of nanometer rods and the disk that is positioned at described nanometer rods two ends;
Wherein, the diameter of disk is identical with the diameter of two end faces of nanometer rods, is 200nm; The length of nanometer rods is 400nm;
The material that forms nanometer rods is designated as material B, is silica;
The material difference that forms the disk at two ends, is designated as respectively materials A 1and materials A 2;
Materials A 1for number-average molecular weight be 2000 PEG, materials A 2for the number-average molecular weight PS that is 10000.
Embodiment 2
1) step 1) is with embodiment 1 step 1);
Only nanometer stick array section a used step 1) is replaced with to nanometer stick array section b;
This ball material is made up of gold nano stick array section and paraffin medicine ball; Wherein, gold nano stick array section parcel paraffin medicine ball; Gold nano stick array section is made up of gold nanorods and matrix; Gold nanorods length is 400nm, is dispersed in matrix PMMA with array way.
2) by the paraffin ball of step 1) gained nanometer stick array section b parcel, in solvent b deionized water, the concentration in reaction system is 5mM with SH-PEG(SH-PEG) be placed in and on shaking table, carry out complex coordination in room temperature and react 6 hours, obtain bar-shaped A 1type B material ball;
3) by step 2) the bar-shaped A of gained 1type B material ball is dissolved in oxolane except deparaffnize, in deionized water, the concentration in reaction system is 5mM with SH-PS(SH-PS) be placed in and on shaking table, carry out complex coordination in room temperature and react 6 hours, react complete dry being placed in oxolane and remove PMMA matrix, obtain bar-shaped A provided by the invention 1bA 2shaped material, its electromicroscopic photograph is as shown in Fig. 2 f.
This material is made up of nanometer rods and the disk that is positioned at nanometer rods two ends;
Wherein, the diameter of disk is identical with the diameter of two end faces of nanometer rods, is 200nm; The length of nanometer rods is 400nm;
The material that forms nanometer rods is designated as material B, is gold;
The material difference that forms the disk at two ends, is designated as respectively materials A 1and materials A 2;
Materials A 1for number-average molecular weight be 2000 PEG, materials A 2for the number-average molecular weight PS that is 10000.
Embodiment 3
Preparation method, with embodiment 2, only replaces with nanometer stick array section c by nanometer stick array section a used, obtains bar-shaped A provided by the invention 1bA 2shaped material, its electromicroscopic photograph is as shown in Fig. 2 h.
This embodiment step 1) gained ball material is made up of the section of iron nanometer stick array and paraffin medicine ball; Wherein, iron nanometer stick array section parcel paraffin medicine ball; The section of iron nanometer stick array is made up of gold nanorods and matrix; Iron nanometer rods length is 400nm, is dispersed in matrix PMMA with array way.
The bar-shaped A of this embodiment step 3) gained 1bA 2shaped material is made up of nanometer rods and the disk that is positioned at nanometer rods two ends;
Wherein, the diameter of disk is identical with the diameter of two end faces of nanometer rods, is 200nm; The length of nanometer rods is 400nm;
The material that forms nanometer rods is designated as material B, is iron;
The material difference that forms the disk at two ends, is designated as respectively materials A 1and materials A 2;
Materials A 1for number-average molecular weight be 2000 PEG, materials A 2for the number-average molecular weight PS that is 10000.
Embodiment 4
Preparation method, with embodiment 2, only replaces with nanometer stick array section d by nanometer stick array section a used, obtains bar-shaped A provided by the invention 1bA 2shaped material, its electromicroscopic photograph is as shown in Fig. 2 j.
This embodiment step 1) gained ball material is made up of nanosized nickel rods array slice and paraffin medicine ball; Wherein, nanosized nickel rods array slice parcel paraffin medicine ball; Nanosized nickel rods array slice is made up of nanosized nickel rods and matrix; Nanosized nickel rods length is 400nm, is dispersed in matrix PMMA with array way.
The bar-shaped A of this embodiment step 3) gained 1bA 2shaped material is made up of nanometer rods and the disk that is positioned at nanometer rods two ends;
Wherein, the diameter of disk is identical with the diameter of two end faces of nanometer rods, is 200nm; The length of nanometer rods is 400nm;
The material that forms nanometer rods is designated as material B, is nickel;
The material difference that forms the disk at two ends, is designated as respectively materials A 1and materials A 2;
Materials A 1for number-average molecular weight be 2000 PEG, materials A 2for the number-average molecular weight PS that is 10000.

Claims (9)

1. a ball material, is made up of nanometer stick array section and medicine ball;
Wherein, the described medicine ball of described nanometer stick array section parcel;
Described nanometer stick array section is made up of nanometer rods and matrix; Described nanometer rods is dispersed in described matrix with array way.
2. ball material according to claim 1, is characterized in that: the material that forms described medicine ball is paraffin;
The material that forms described nanometer rods is selected from least one in inorganic material and metal material;
Wherein, described inorganic material is specially silica; Described metal material is specifically selected from least one in oxide and the simple substance of following element: gold, silver, platinum, iron, cobalt, nickel and rubidium;
The material that forms described matrix is PMMA.
3. prepare a method for claim 1 or 2 arbitrary described ball material, comprise the steps: that nanometer stick array section is placed in to the Pickering emulsion being made up of paraffin and water carries out emulsification pretreatment, obtains described ball material.
4. method according to claim 3, is characterized in that: the mass ratio of described paraffin and water is 1:10-15;
Described nanometer stick array section is 1:5-10 with the mass ratio of paraffin;
In described emulsification pretreatment step, shearing rotating speed is 4000-6000rpm, and the time is 5-10 minute.
5. a bar-shaped A 1bA 2shaped material, is made up of nanometer rods and the disk that is positioned at described nanometer rods two ends;
And the diameter of described disk is identical with the diameter of two end faces of described nanometer rods;
Wherein, the material that forms described nanometer rods is designated as material B;
Described material B is selected from least one in inorganic material and metal material; Described inorganic material is specially silica; Described metal material is specifically selected from least one in oxide and the simple substance of following element: gold, silver, platinum, iron, cobalt, nickel and rubidium;
The material difference that forms described disk, is designated as respectively materials A 1and materials A 2;
Described materials A 1and A 2all be selected from least one in polystyrene and polyethylene glycol.
6. prepare the bar-shaped A that material B is silica described in claim 5 for one kind 1bA 2the method of shaped material, comprises the steps:
1) by arbitrary claim 1 or 2 described ball material in solvent a with CH 2=CH-C nh 2nsi-R 3room temperature is reacted, and adds after completion of the reaction SH-PEG to carry out Michael addition reaction in methyl alcohol again, obtains bar-shaped A 1type B material ball;
2) by bar-shaped step 1) gained A 1type B material ball is dissolved in n-hexane except deparaffnize, in described solvent a with CH 2=CH-C nh 2nsi-R 3room temperature is reacted, then in methyl alcohol, adds SH-PS to carry out Michael addition reaction, then removes after PMMA matrix with oxolane, and obtaining described material B is the bar-shaped A of silica 1bA 2shaped material;
Described CH 2=CH-C nh 2nsi-R 3in, be-OCH of R 3,-OCH 2cH 3,-Cl or-OCOCH 3;
N is the integer of 0-12.
7. method according to claim 6, is characterized in that: described solvent a is all selected from least one in n-hexane and ethanol;
Described room temperature is carried out in reactions steps, and the time is 6-24 hour, is specially 12 hours;
In described Michael addition reaction step, temperature is room temperature, and the time is 1-10 hour, is specially 6 hours;
Described CH 2=CH-C nh 2nsi-R 3concentration in reaction system is 1-100mM, is specially 1-50mM, is more specifically 5mM;
Concentration in described SH-PS and SH-PEG reaction system is 1-100mM, is specially 1-50mM, is more specifically 5mM.
8. prepare the bar-shaped A that material B is metal material described in claim 5 for one kind 1bA 2the method of shaped material, comprises the steps:
1) arbitrary claim 1 or 2 described ball material is carried out to complex coordination with SH-PEG in solvent b and react, obtain bar-shaped A 1type B material ball;
2) by bar-shaped step 1) gained A 1type B material ball is dissolved in oxolane except deparaffnize, carries out complex coordination react in oxolane with SH-PS, and obtaining described material B is the bar-shaped A of metal material 1bA 2shaped material.
9. method according to claim 8, is characterized in that: described solvent b is all selected from least one in water, ethanol and oxolane;
In described complex coordination reactions steps, temperature is 15-50 DEG C; Time is 6-24 hour, is specifically 12 hours;
Described SH-PEG and the SH-PS concentration in reaction system is 1mM-100mM, is specially 1-50mM, is more specifically 5mM.
CN201410099510.9A 2014-03-18 2014-03-18 Rod-shaped material with surface having multiple properties and manufacturing method and application of Pickering emulsion thereof Pending CN103935955A (en)

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Application publication date: 20140723