CN100431956C - Process for preparing mesoporous silicon dioxide spiral coil - Google Patents
Process for preparing mesoporous silicon dioxide spiral coil Download PDFInfo
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- CN100431956C CN100431956C CNB2006100883081A CN200610088308A CN100431956C CN 100431956 C CN100431956 C CN 100431956C CN B2006100883081 A CNB2006100883081 A CN B2006100883081A CN 200610088308 A CN200610088308 A CN 200610088308A CN 100431956 C CN100431956 C CN 100431956C
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- ether
- silicon dioxide
- mesoporous silicon
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000001338 self-assembly Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 125000006353 oxyethylene group Chemical group 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 3
- 239000004593 Epoxy Substances 0.000 abstract 2
- 239000008121 dextrose Substances 0.000 abstract 2
- BJEYNNFDAPPGST-UHFFFAOYSA-N oxirene Chemical compound O1C=C1 BJEYNNFDAPPGST-UHFFFAOYSA-N 0.000 abstract 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 2
- 229960001866 silicon dioxide Drugs 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000008103 glucose Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229940024606 amino acid Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- -1 amino acid salts Chemical class 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000009416 shuttering Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Abstract
The present invention relates to a preparation method of a spiral pipe of mesoporous silicon dioxide. The present invention is characterized in that the water solution of dextrose of 100g * L<-1> is arranged at 160 to 190 DEG C for keeping for 3 to 6 hours to obtain the water solution of polymerized sugar; then, the water solution of the polymerized sugar, the tri-block high molecular polymer surfactant (with the average molecular weight of 5800) of poly oxene ether-poly epoxy propylene ether-poly oxene ether, and 2 mol * L<-1> of hydrochloric solution are mixed together, and tetraethyl orthosilicate is added; the optimal weight ratio of the reactants, namely, 100g * L<-1> of the water solution of the dextrose, the tri-block high molecular polymer surfactant (with the average molecular weight of 5800) of poly oxene ether-poly epoxy propylene ether-poly oxene ether, 2 mol * L<-1> of the hydrochloric solution and the tetraethyl orthosilicate, is 50: 1: 40: 2; after the tetraethyl orthosilicate is fully hydrolyzed, the reactants are arranged in a closed vessel and heated to 160 to 190 DEG C, and the heat is preserved for 24 hours; after separating, washing and drying, the product of the reaction is calcined for 6 to 8 hours at 550 to 650 DEG C at air atmosphere, and then the tri-stage self-assembly spiral pipe of the mesoporous silicon dioxide is obtained when the temperature drops to room temperature.
Description
One, technical field
The present invention relates to novel silicon dioxide spiral coil of a class and preparation method thereof, it belongs to the nano material preparation technical field
Two, background technology
At the synthetic artificially spirane structure material of Jie's sight aspect wide significance is arranged, not only because spirane structure and biological phenomena are so tight, and the spirane structure material also provides the performance more superior than common material.With regard to the carbon nanotube of spiral, early 1990s, the Motojima of Japan prepares the good helical carbon fiber of circulation ratio.Helical carbon fiber is except that excellent properties such as the thermotolerance that possesses common carbon fibers, chemical stability, electric heating conductivity, thermal expansivity and low density, also, be expected to become novel radio-radar absorber, little responsive energy absorber and Microspring and use because of its special spirane structure has typical chirality feature and good elasticity.
In recent years, the mesoporous SiO of micron order that forms for the basic comprising unit with the meso-hole structure
2Spiral tube is in the news successively.In general, the present mesoporous SiO of synthetic
2Spiral tube can be divided into two types: a kind of is that bigger product particle presents the helix structure, the macro morphology (micro-meter scale) that is product shows helix, and it constitutes elementary cell (mesoporous) and might not show orderly spirane structure, synthetic representative with seminars such as Ozin; Another kind is to constitute the mesoporous of macro morphology itself (nanoscale) also to show orderly spirane structure, work as the people such as Che of Nature in 2004 report, mesoporous pipeline shows consistent sense of rotation in its product, shows as the micron rifle bar with chirality on the macroscopic view; Stucky etc. also have similar report on NatureMaterials.
From the synthetic route, the synthetic method of these several typical mesoporous spiral tubes has nothing in common with each other, and is broadly divided into: (1) single template; (2) template adds physical action; (3) composite mould plate agent method; (4) soft or hard template.Wherein the mechanism [Che, S.et al.Nature2004,429,281] of composite shuttering has promptly been used in the work of Che seminar.
Mainly be by the charge effect between the adjusting template in the work of Che, thereby form spiral composite mould plate agent, detailed process is as follows: with the amino acid salts N-miristoyl-L-alanine sodium (C of 0.32g (1mmol)
14-L-AlaS) being dissolved in the 32g water under the room temperature, the back adds 1.4g (0.14mmol) 0.1molL
-1Hydrochloric acid soln makes a part of acidifying in the amino acid salts, produces a certain amount of free amino acid (C
14-L-AlaA).Above mixing solutions stirred after 1 hour, added the N-trimethoxysilylpropyl-N of 1.4g tetraethoxy (TEOS) and 0.20g in mixing solutions, N, N-trimethylammonium chloride (TMAPS).In above mixed system, the ammonium positively charged of TMAPS, and C
14-L-Alas and C
14Hydrophilic the base band negative electricity of-L-AlaA, two kinds of template are assembled by the interaction of positive and negative charge and are become the composite mould plate agent with spirane structure, again by controlling the hydrolytic action of TEOS, make silicon-dioxide be coated on template uniformly, roasting finally obtains having the micron bar of foraminous spiral tract structure after 6 hours under 650 ℃ of air atmospheres.Though can make the spiral micron bar of comparison homogeneous by this route, exist also that some is not enough: (1) synthesis material (as amino acid salts) costs an arm and a leg, common lab synthetic still can, but be unfavorable for large-scale preparation; (2) aperture of gained sample less (2 ~ 3nm), be unfavorable for that the later stage duct modifies; (3) the foraminous spiral tract structure in the sample is single, only has one-level duct (2 ~ 3nm's is mesoporous) to limit its range of application.
We are by cheap raw material glucose, triblock copolymer, success synthesized a micron spiral tube, its complex structure, synthesis material is easy, and good prospects for application is arranged.
Three, Fa Ming content
Purpose of the present invention; A kind of new preparation method is provided, prepares three grades of self-assembly mesoporous silicon dioxide spiral coils with it.One-level hole: mesoporous (10nm); Second hole: by the mesoporous solenoid coil (70nm) that constitutes for wall; The micron spiral tube that three grades of holes: by second hole---solenoid coil constitutes.It is expected to be applied in the aspects such as processing of complicated nanometer, micron devices.
Principle of the present invention is as follows: the extent of polymerization of at first controlling glucose, obtain this elementary template of bunching sugar, again under strong acidic condition, pass through interaction of hydrogen bond by polymer neutral surface active agent and bunching sugar, form senior template, add the silicon source therein, make its hydrolysis under given conditions, be coated on the template surface uniformly, roasting obtains three grades of mesoporous silicon dioxide spiral coils later on.
The object of the present invention is achieved like this: with 100gL
-1D/W place 160 ~ 190 ℃ to keep 3 ~ 6 hours down, obtain the bunching sugar aqueous solution; With bunching sugar aqueous solution and poly-oxyethylene ether-poly-propylene oxide ether-poly-oxyethylene ether three block macromolecular polymeric surfactants (molecular-weight average 5800) (writing a Chinese character in simplified form P123) and 2molL
-1Hydrochloric acid soln mixes mutually, adds tetraethoxy; 100gL
-1D/W, poly-oxyethylene ether-poly-propylene oxide ether-poly-oxyethylene ether three block macromolecular polymeric surfactants (molecular-weight average 5800), 2molL
-1Weight ratio between several reactants of hydrochloric acid soln and tetraethoxy is 40 ~ 60: 1: 30 ~ 50: 2 ~ 3; Treat that the abundant hydrolysis of tetraethoxy is placed in the encloses container, be heated to 160 ~ 190 ℃, be incubated 24 hours; Product is after separation, washing, drying, and 550 ~ 650 ℃ of roastings are 6 ~ 8 hours under air atmosphere, after reduce to room temperature and obtain three grades of self-assembly mesoporous silicon dioxide spiral coils.
With the situation among the embodiment 1 is example, and for ease of understanding, the composite mould plate agent forming process is seen accompanying drawing 1; The sign of products therefrom and structural simulation figure see accompanying drawing 2.
Preparation method's of the present invention advantage is:
1. use the precursor of glucose as the preparation of bunching sugar, its raw material is easy to get, and preparation process is simple, with segmented copolymer fine mutual effect is arranged under preparation condition, can form special composite mould plate agent.And the hydro-thermal glucose solution can also obtain little this byproduct of carbon ball, also can be used for nano material preparation;
2. by preparation process of the present invention, can prepare higher category, more complicated pore structure, for the processing of complicated nano-device provides possibility.
Four, description of drawings
Fig. 1: composite mould plate agent forms synoptic diagram.
Fig. 2: the inventive method prepares the characterization result and the structural simulation figure of product.(A) transmission electron microscope of gained sample (TEM) result, scale: 500nm.Wherein, inserting figure is the part amplification TEM figure and the Fast Fourier Transform (FFT) figure of spiral tube corner, scale among the figure: 20nm; (B) second hole---solenoidal transmission electron microscope results, scale: 100nm; (C) scanning electron microscope of gained sample (SEM) result, scale: 300nm; (D) mimic diagram of spiral tube.Wherein, inserting figure is the cross section structure synoptic diagram of second hole.
Five, embodiment
Preparation process is divided into two main phase:
1. the preparation of bunching sugar
5.0g glucose is dissolved in the 50ml water, and the back moves in the 80ml encloses container, is heated to 190 ℃, keeps 4 hours, reduces to room temperature, filter orange red bunching sugar soln.
2. the preparation of spiral tube
It is 2molL that the poly-oxyethylene ether of 1.0g-poly-propylene oxide ether-poly-oxyethylene ether triblock polymer tensio-active agent (molecular-weight average 5800) is dissolved in 40g concentration
-1Hydrochloric acid soln in, add the whole bunching sugar solns of gained (this moment, the pH value of solution value was about about 1) down at 40 ℃, stir and added 2.0g tetraethoxy (TEOS) in 1 hour later on, move in the encloses container after 24 hours in 40 ℃ of stirring reactions, be heated to 190 ℃ and kept filtration washing, dry air 24 hours, roasting is 6 hours in 550 ℃ of air atmospheres, reduces to room temperature and obtains three grades of self-assembly mesoporous silicon dioxide spiral coils.
The working sample porphyrize is after the ethanolic soln ultra-sonic dispersion is placed on the copper mesh observes.
Purposes of the present invention is: prepares three grades of self-assembly mesoporous silicon dioxide spiral coils with simple method, can be used for the processing of complicated nano-device, as; Little coil, nanometer spring etc.Also useful as catalysts carrier, the different active ingredient of load in different pore structures is expected to prepare novel catalytic material.
Claims (2)
1. the preparation method of a mesoporous silicon dioxide spiral coil is characterized in that: with 100gL
-1D/W place 160-190 ℃ to keep 3-6 hour down, obtain the bunching sugar aqueous solution; With bunching sugar aqueous solution and poly-oxyethylene ether-poly-propylene oxide ether-poly-oxyethylene ether three block macromolecular polymeric surfactant molecular-weight average 5800 and 2molL
-1Hydrochloric acid soln mixes mutually, adds tetraethoxy; 100gL
-1D/W, poly-oxyethylene ether-poly-propylene oxide ether-poly-oxyethylene ether three block macromolecular polymeric surfactant molecular-weight average 5800,2molL
-1Weight ratio between several reactants of hydrochloric acid soln and tetraethoxy is 40-60: 1: 30-50: 2-3; Treat that the abundant hydrolysis of tetraethoxy is placed in the encloses container, be heated to 160-190 ℃, be incubated 24 hours; Product after separation, washing, drying, under air atmosphere 550-650 ℃ roasting 6-8 hour, after reduce to room temperature and obtain three grades of self-assembly mesoporous silicon dioxide spiral coils.
2. according to the preparation method of the described mesoporous silicon dioxide spiral coil of claim 1, it is characterized in that 100gL
-1D/W, poly-oxyethylene ether-poly-propylene oxide ether-poly-oxyethylene ether three block macromolecular polymeric surfactant molecular-weight average 5800,2molL
-1Weight ratio is 50: 1: 40 between several reactants of hydrochloric acid soln and tetraethoxy: 2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100883081A CN100431956C (en) | 2006-07-10 | 2006-07-10 | Process for preparing mesoporous silicon dioxide spiral coil |
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|---|---|---|---|
| CNB2006100883081A CN100431956C (en) | 2006-07-10 | 2006-07-10 | Process for preparing mesoporous silicon dioxide spiral coil |
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| CN100431956C true CN100431956C (en) | 2008-11-12 |
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| CN110467775B (en) * | 2019-08-22 | 2022-03-08 | 苏州润佳工程塑料股份有限公司 | Polypropylene composite material of spiral tube containing silicon oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569632A (en) * | 2004-04-29 | 2005-01-26 | 上海交通大学 | silicon oxide mesoporous material having chiral structure and method for preparing same |
| CN1730390A (en) * | 2005-07-07 | 2006-02-08 | 上海交通大学 | Process for preparing monox mesoporous material with helical structure |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569632A (en) * | 2004-04-29 | 2005-01-26 | 上海交通大学 | silicon oxide mesoporous material having chiral structure and method for preparing same |
| CN1730390A (en) * | 2005-07-07 | 2006-02-08 | 上海交通大学 | Process for preparing monox mesoporous material with helical structure |
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