CN100523286C - Preparation method of nano-grade capsule material based on composite mould plate technology - Google Patents
Preparation method of nano-grade capsule material based on composite mould plate technology Download PDFInfo
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- CN100523286C CN100523286C CNB2006100286752A CN200610028675A CN100523286C CN 100523286 C CN100523286 C CN 100523286C CN B2006100286752 A CNB2006100286752 A CN B2006100286752A CN 200610028675 A CN200610028675 A CN 200610028675A CN 100523286 C CN100523286 C CN 100523286C
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Abstract
This invention relates to a process of preparing capsule-like nanometer grade material. First prepare a kind of compound nanometer formwork; then use this formwork to pack material. The compound formwork is formed by the way of CVDP which is depositing PPX or derivate on the inner wall of AAO. And it is a porosity and hollow AAO/PPX formwork. Fill it by other material and seal the extremity, drop the AAO. This material can be used for catalyst transporting, drug releasing, coaxial cable and so on.
Description
Technical field
The invention belongs to nanometer and technical field of polymer materials, be specifically related to a kind of nano level material preparation method.
Background technology
Monodimension nanometer material is the focus of Recent study, and template is an effective technology of monodimension nanometer materials such as synthesis of nano line and nanotube, has good controllability.Template is that nano level arrives micron-sized porous material as template with the aperture normally, combined with electrochemical, the precipitator method, sol-gel method (C.R.Martin, Science, 1961) and vapour deposition process (K.Kim, J.Jin 1994,266 (23):, Nano Letters, 631) etc. 2001,1 (11): technology makes material atom or ion precipitation on the hole wall of template, forms required nanostructure.But in these methods, what have uses solvent, and adds additive, initiator etc., has certain toxicity, and the technology more complicated.
Summary of the invention
The objective of the invention is to propose the preparation method of a kind of safe and feasible and the simple nanometer materials of technology.Zhi Bei nano material can be applicable to the conveying of catalyzer, technical fields such as the slowly-releasing of medicine thus.
The preparation method of the nanometer materials that the present invention proposes, a kind of composite nano template of preparation utilizes this template nano material to be encapsulated (see figure 1) then earlier.Compound template is to utilize the method (W.F.Gorham of chemical vapor deposition polymerization (CVDP) in porous alumina (AAO) template, U.S.Pat.3,342,754.1967, Sept.19) at inwall formation of deposits polyparaphenylene dimethylene (PPX) the or derivatives thereof thin film layer of AAO.Shown in figure, after composite shuttering prepares, be the AAO/PPX template of a porous, hollow, fill other nano materials therein, end seals, and AAO is etched away again, and can obtain the nanometer materials by PPX or derivatives thereof parcel of similar capsule shape.The nanometer materials of this kind structure can be applied to the conveying of catalyzer, the slowly-releasing of medicine, research fields such as concentric cable.
Here, other nano materials of said filling can be some small molecule materials, as Disperse Red, catalyzer, biological enzyme etc.
The composite Nano template of using among the present invention is to adopt chemical vapor deposition polymerization (CVDP) method, and polymerization one deck forms phenylene dimethylene (PPX) or derivatives thereof microthin coating in porous alumina formwork (AAO), wherein:
Porous alumina formwork aperture≤100nm
Polyparaphenylene dimethylene and derivative coat-thickness thereof〉10nm, be generally less than 100nm
Described porous alumina (AAO) template is meant that matrix is aluminum oxide, has vesicular structure, and the template of aperture≤100nm.
Described polyparaphenylene dimethylene (PPX) and derivative thereof comprise that PPX or poly-(chloro-to the phenylene dimethylene), poly-(dichloro--to the phenylene dimethylene) wait one or more of the PPX derivative that replaced side group on the phenyl ring, from phenylene dimethylene dimer (DPX) (or derivatives thereof) employing chemical vapor deposition polymerization (CVDP) method is prepared.
Described phenylene dimethylene dimer (DPX) and derivative thereof are comprised that DPX and chloro-to phenylene dimethylene dimer, dichloro-are to having replaced the DPX derivative of side group on the phenyl ring such as phenylene dimethylene dimer.
Operation steps of the present invention is as follows:
(1) AAO preparation: with high purity aluminium foil disk process high temperature annealing, degreasing, deoxidation aluminium, electropolishing.Two-step anodization, perforate.Obtain the alumina wafer of the nano aperture of ordered arrangement.
(2) preparation of composite Nano template: on chemical vapor deposition polymerization device (as shown in Figure 2), with solid-state phenylene dimethylene dimer (or derivatives thereof) is distilled down at 120-180 ℃, control pressure is 100-150Pa; With the cracking of two side chain carbon carbon bonds, control pressure 60-80Pa generates the gasiform active intermediate under 600-700 ℃; Enter the sedimentary province under the ambient temperature then, the instaneous polymerization condensation is adsorbed on the AAO.
(3) add other small molecules (being other nano materials) in the above-mentioned composite shuttering for preparing, end-blocking etches away AAO with NaOH solution more then, obtains the small molecules nanometer materials by PPX or derivatives thereof parcel.
Among the present invention, the chemical vapor deposition means of use is connected to form by the road by distillation district, Pintsch process district, sedimentary province, cold-trap and pump, sees shown in Figure 2.Wherein, distillation district control pressure is 100-200Pa, and temperature is 100-200 ℃; Pintsch process district control pressure is 60-80Pa, and temperature is 600-700 ℃; Sedimentary province is room temperature, normal pressure.
Performance characterization method of the present invention is as follows:
(1) adopts the Quanta 200FEG field launch environment scanning electronic microscope observation AAO template, AAO/PPX composite shuttering of FEI Co. and the PPX behind the AAO partial etching managed.
(2) the H-800 type transmission electron microscope observation PPX nanotube of the Japanese Hitachi of employing company.
(3) effect after Red-1 200 also dyes is filled in the H-800 type transmission electron microscope observation of the Japanese Hitachi of employing company in the PPX nanotube.
The result shows, is used the method for composite shuttering that material is carried out the nano level packing by the present invention, makes the filling of the interior material of PPX pipe carry out more smoothly, the easier moulding of nanometer materials.Concrete advantage is as follows:
(1) the present invention accomplishes to add the requirement of other materials easily in nanotube.Because being macroscopic view, the composite shuttering that obtains goes up easy-operating AAO/PPX composite shuttering.The interpolation material in carbon nanotube powder that compares is much easier.
(2) the AAO template has following characteristics: 1. template used easy preparation, synthetic method is simple.2. can synthesize the very little tubular material of diameter.3. owing to pattern hole pore size unanimity, the nanometer materials of preparation have identical, the monodispersed structure in aperture equally.4. the nanotube and the nanofiber that form in pattern hole are separated from template easily.
(3) the present invention utilizes chemical vapor deposition polymerization (CVDP) method that polyparaphenylene dimethylene (PPX) is deposited on AAO inside as a kind of packaged material.Why select for use the method for PPX and CVDP to mainly contain following reason: 1. PPX and derivative thereof can coat multiple material, as metal or polymkeric substance; 2. need not solvent in the PPX polymerization process, need not additive and initiator, can reduce potential toxicity; 3. the thickness of the PPX layer of vapour deposition can accurately be controlled.4. PPX itself has a lot of premium propertiess, as excellent electric insulation performance and physical and mechanical properties, is insoluble in common solvent, and unreactiveness has good barrier performance etc.5. the PPX derivative can have the functional group of other functions, can change its surfactivity, and taking place to send out with other functional groups should.The relevant research of carrying out nano level material package with the composite shuttering method yet there are no report.
Description of drawings
The making of Figure 1A AO/PPX composite shuttering and the synoptic diagram that encapsulates other material.
Fig. 2 CVDP device synoptic diagram.
The SEM photo of Fig. 3 AAO template and the SEM photo of AAO/PPX composite shuttering.Wherein, (a) being the electron micrograph of AAO module, (b) is the electron micrograph of AAO/PPX composite shuttering.
Fig. 4 partial etching falls the SEM photo of PPX behind the AAO.
The TEM photo of Fig. 5 PPX pipe.
Fig. 6 fills the TEM photo after Disperse Red and the dyeing.
Number in the figure: 1 is the distillation district, and 2 is the Pintsch process district, and 3 is sedimentary province, and 4 is cold-trap, and 5 is pump.
Embodiment
Following examples are only for further specifying the present invention, are not violating under the purport of the present invention, and the present invention should be not limited to the content that following experimental example is specifically expressed.
Embodiment is raw materials used as follows:
Aluminium flake (99.99%), hundred million gold medals are ground in Beijing
To phenylene dimethylene dimer (N type, 99.0%), Fluka
Phosphoric acid, perchloric acid, Shanghai gold deer chemical reagent company limited
Red-1 200 (50%), Aldrich
(1) preparation of AAO and sign
The preparation of AAO: 99.99% aluminium flake is through high temperature annealing (500 ℃ of retort furnaces, 4-6 hour), degreasing (the ultrasonic 10-20 of aluminum chloride or acetone minute, distilled water flushing), deoxidation aluminium (10% NaOH, ultrasonic 10-20 minute), electropolishing (HCLO
4: dehydrated alcohol=1:4 volume ratio, 15V, electrolysis 3-5 minute) back cleans standby.30% H
3PO
1Under 40V voltage anodic oxidation 1-2 hour, removed after the zone of oxidation reoxidation 8-12 hour.Saturated HgCl
2Dissolve away aluminium base, 37 the degree H
3PO
4Middle reaming 25-35 minute, continue to be heated to 780-850 ℃, make alumina crystal.
The sign of AAO pattern: adopt the Quanta 200 FEG field launch environment scanning electronic microscope observation AAO templates of FEI Co., the aperture homogeneous is greatly about about 100nm.See Fig. 3 (a).
(2) utilize the CVDP method to prepare composite shuttering and sign thereof
Composite shuttering preparation: install as shown in Figure 2, the AAO template is placed in the deposition storehouse, add 20mg-50mg to phenylene dimethylene dimer (N type) in the distillation district, after vacuumizing, the distillation district is heated to 150 ℃, and cracking zone is heated to 680 ℃, and it is room temperature that sedimentary province is provided with temperature.
The sign of composite shuttering: adopt the Quanta 200 FEG field launch environment scanning electronic microscope observation composite shutterings of FEI Co., see Fig. 3 (b).
(3) with the sign of the AAO/PPX template behind the AAO partial etching
With the composite shuttering partial etching, adopt the Quanta 200 FEG field launch environment scanning electronic microscope observations of FEI Co. with 30%NaOH solution, obtain pattern as shown in Figure 4.
(4) pattern with PPX pipe after the complete etching of AAO characterizes
With 30%NaOH solution with the complete etching of AAO after, adopt the pattern of the H-800 type transmission electron microscope observation PPX pipe of Japanese Hitachi company, the result as shown in Figure 5.
(5) characterize with composite shuttering method parcel Disperse Red and to its pattern
On the composite shuttering of hollow, drip the Red-1 200 solution that is dissolved in methylene dichloride, treat that solvent evaporates is complete, with the complete etching of AAO, obtain red solution with 30%NaOH solution.With lead citrate to PPX/ Red-1 200 structure dyeing.Adopt the pattern of the H-800 type transmission electron microscope observation PPX pipe of Japanese Hitachi company, the result as shown in Figure 6.The Red-1 200 small molecules is comprised in the PPX tubular construction.
Embodiment is raw materials used as follows:
Aluminium flake (99.99%), hundred million gold medals are ground in Beijing
To phenylene dimethylene dimer (C type, 99.0%), Fluka
Phosphoric acid, perchloric acid, Shanghai gold deer chemical reagent company limited
Red-1 200 (50%), Aldrich
(1) preparation of AAO and sign
The preparation of AAO: 99.99% aluminium flake is through high temperature annealing (500 ℃ of retort furnaces, 6-7 hour), degreasing (ultrasonic 15 minutes of aluminum chloride or acetone, distilled water flushing), deoxidation aluminium (10% NaOH, ultrasonic 15 minutes), electropolishing (HCLO
4: dehydrated alcohol=1:4 volume ratio, 15V, electrolysis 3 minutes) back cleans standby.30% H
3PO
4Anodic oxidation is 1.5 hours under 40V voltage, and reoxidation is 10 hours after the removal zone of oxidation.Saturated HgCl
2Dissolve away aluminium base, 37 the degree H
3PO
4Middle reaming 30 minutes continues to be heated to 800 degree, makes alumina crystal.
The sign of AAO pattern: adopt the Quanta 200 FEG field launch environment scanning electronic microscope observation AAO templates of FEI Co., the aperture homogeneous is greatly about about 100nm.See Fig. 3 (a).
(2) utilize the CVDP method to prepare composite shuttering and sign thereof
Composite shuttering preparation: install as shown in Figure 2, the AAO template is placed in the deposition storehouse, add 20mg-50mg to phenylene dimethylene dimer (C type) in the distillation district, after vacuumizing, the distillation district is heated to 120 ℃, and cracking zone is heated to 600 ℃, and it is room temperature that sedimentary province is provided with temperature.
The sign of composite shuttering: adopt the Quanta 200 FEG field launch environment scanning electronic microscope observation composite shutterings of FEI Co., the amount of homodimer (DPX) can not cause deposition in various degree.Effect is as embodiment 1.
(3) with the sign of the AAO/PPX template behind the AAO partial etching
With the composite shuttering partial etching, adopt the Quanta 200 FEG field launch environment scanning electronic microscope observations of FEI Co. with 30%NaOH solution, effect is as embodiment 1.
(4) pattern with PPX pipe after the complete etching of AAO characterizes
With 30%NaOH solution with the complete etching of AAO after, adopt the pattern of the H-800 type transmission electron microscope observation PPX pipe of Japanese Hitachi company, effect is as embodiment 1.
(5) characterize with composite shuttering method parcel Disperse Red and to its pattern
On the composite shuttering of hollow, drip the Red-1 200 solution that is dissolved in methylene dichloride, treat that solvent evaporates is complete, with the complete etching of AAO, obtain red solution with 30%NaOH solution.With lead citrate to PPX/ Red-1 200 structure dyeing.Adopt the pattern of the H-800 type transmission electron microscope observation PPX pipe of Japanese Hitachi company, effect is as embodiment 1.The Red-1 200 small molecules is comprised in the PPX tubular construction.
Embodiment is raw materials used as follows:
Aluminium flake (99.99%), hundred million gold medals are ground in Beijing
To phenylene dimethylene dimer (D type, 99.0%), Fluka
Phosphoric acid, perchloric acid, Shanghai gold deer chemical reagent company limited
Red-1 200 (50%), Aldrich
(1) preparation of AAO and sign
The preparation of AAO: 99.99% aluminium flake is through high temperature annealing (500 ℃ of retort furnaces, 5 hours), degreasing (ultrasonic 20 minutes of aluminum chloride or acetone, distilled water flushing), deoxidation aluminium (10% NaOH, ultrasonic 10 minutes), electropolishing (HCLO
4: dehydrated alcohol=1:4 volume ratio, 15V, electrolysis 4 minutes) back cleans standby.30% hour
3PO
4Anodic oxidation is 2 hours under 40V voltage, and reoxidation is 12 hours after the removal zone of oxidation.Saturated HgCl
2Dissolve away aluminium base, 37 the degree H
3PO
4Middle reaming 40 minutes continues to be heated to 800 degree, makes alumina crystal.
The sign of AAO pattern: adopt the Quanta 200 FEG field launch environment scanning electronic microscope observation AAO templates of FEI Co., the aperture homogeneous is greatly about about 100nm.Effect is as embodiment 1.
(2) utilize the CVDP method to prepare composite shuttering and sign thereof
Composite shuttering preparation: install as shown in Figure 2, the AAO template is placed in the deposition storehouse, add 20mg-50mg to phenylene dimethylene dimer (N type) in the distillation district, after vacuumizing, the distillation district is heated to 180 ℃, and cracking zone is heated to 700 ℃, and it is room temperature that sedimentary province is provided with temperature.
The sign of composite shuttering: adopt the Quanta 200 FEG field launch environment scanning electronic microscope observation composite shutterings of FEI Co., the amount of homodimer (DPX) can not cause deposition in various degree.Effect is as embodiment 1.
(3) with the sign of the AAO/PPX template behind the AAO partial etching
With the composite shuttering partial etching, adopt the Quanta 200 FEG field launch environment scanning electronic microscope observations of FEI Co. with 30%NaOH solution, effect is as embodiment 1.
(4) pattern with PPX pipe after the complete etching of AAO characterizes
With 30%NaOH solution with the complete etching of AAO after, adopt the pattern of the H-800 type transmission electron microscope observation PPX pipe of Japanese Hitachi company, effect is as embodiment 1.
(5) characterize with composite shuttering method parcel Disperse Red and to its pattern
On the composite shuttering of hollow, drip the Red-1 200 solution that is dissolved in methylene dichloride, treat that solvent evaporates is complete, with the complete etching of AAO, obtain red solution with 30%NaOH solution.With lead citrate to PPX/ Red-1 200 structure dyeing.Adopt the pattern of the H-800 type transmission electron microscope observation PPX pipe of Japanese Hitachi company, effect is as embodiment 1.The Red-1 200 small molecules is comprised in the PPX tubular construction.
In the foregoing description, the parameter of each component raw material and consumption and preparation process only is the representative of choosing in order to describe invention.The adding of Red-1 200 is just in order to reach the effect of distinguishing easily under naked eyes or Electronic Speculum.Other small molecules also can encapsulate with the present invention, for example, and catalyzer, biological enzyme etc.
Claims (2)
1, a kind of preparation method of the nano-grade capsule material based on composite mould plate technology is characterized in that a kind of composite shuttering of preparation earlier, utilizes this template that nano material is encapsulated then, and concrete steps are as follows:
(1) adopt the chemical vapor deposition polymerization method at porous alumina formwork nano aperture inwall deposition polyparaphenylene dimethylene microthin coating, be prepared into composite shuttering, wherein, the aperture≤100nm of porous alumina formwork, polyparaphenylene dimethylene coat-thickness〉10nm;
(2) fill other nano materials in the nanoporous of composite shuttering, end seals, and porous alumina formwork is etched away again, and promptly gets the nanometer materials by polyparaphenylene dimethylene parcel of similar capsule shape; Other nano materials described here are small molecule material Disperse Red, catalyzer or biological enzyme.
2, preparation method according to claim 1 is characterized in that the step of described chemical vapor deposition polymerization is:
On the chemical vapor deposition polymerization device, with solid-state phenylene dimethylene dimer is distilled down at 120-180 ℃, control pressure is 100-150Pa; With the cracking of two side chain carbon carbon bonds, control pressure is 60-80Pa under 600-700 ℃, generates the gasiform active intermediate; Enter the sedimentary province under the ambient temperature then, the instaneous polymerization condensation is adsorbed on the inwall of porous alumina formwork aperture, obtains composite shuttering.
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| CN103041406B (en) * | 2013-01-16 | 2014-05-07 | 中国科学院理化技术研究所 | Method for preparing diagnosis and treatment-cooperated nano particles release system by template method |
| CN103041393B (en) * | 2013-01-16 | 2014-04-16 | 中国科学院理化技术研究所 | Preparation method of nano multi-medicine medicine carrying system for treating cancer |
| CN104959045B (en) * | 2015-06-16 | 2017-03-29 | 陕西科技大学 | A kind of method for preparing polyvinylidene fluoride nanometer array pore membrane |
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| US20030010971A1 (en) * | 2001-06-25 | 2003-01-16 | Zhibo Zhang | Methods of forming nano-scale electronic and optoelectronic devices using non-photolithographically defined nano-channel templates and devices formed thereby |
| CN1587438A (en) * | 2004-07-30 | 2005-03-02 | 中国科学院上海微系统与信息技术研究所 | Low temperature insert layer in gallium nitride film grown through hydride gas phase epitaxy |
| CN1737195A (en) * | 2005-07-29 | 2006-02-22 | 中国科学院上海微系统与信息技术研究所 | Metal inserting layer in the hydride gas phase epitaxial growth gallium nitride film and preparation method |
| US20060037477A1 (en) * | 2003-10-24 | 2006-02-23 | Lopez Gabriel P | Fabrication of an anisotropic super hydrophobic/hydrophilic nanoporous membranes |
| CN1790560A (en) * | 2005-12-22 | 2006-06-21 | 同济大学 | Soft magnetic composite particle for magnetorheological fluid and its preparing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030010971A1 (en) * | 2001-06-25 | 2003-01-16 | Zhibo Zhang | Methods of forming nano-scale electronic and optoelectronic devices using non-photolithographically defined nano-channel templates and devices formed thereby |
| US20060037477A1 (en) * | 2003-10-24 | 2006-02-23 | Lopez Gabriel P | Fabrication of an anisotropic super hydrophobic/hydrophilic nanoporous membranes |
| CN1587438A (en) * | 2004-07-30 | 2005-03-02 | 中国科学院上海微系统与信息技术研究所 | Low temperature insert layer in gallium nitride film grown through hydride gas phase epitaxy |
| CN1737195A (en) * | 2005-07-29 | 2006-02-22 | 中国科学院上海微系统与信息技术研究所 | Metal inserting layer in the hydride gas phase epitaxial growth gallium nitride film and preparation method |
| CN1790560A (en) * | 2005-12-22 | 2006-06-21 | 同济大学 | Soft magnetic composite particle for magnetorheological fluid and its preparing method |
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