CN102530968A - Production method of spiral bi-thienyl silicon oxide nanometer material - Google Patents
Production method of spiral bi-thienyl silicon oxide nanometer material Download PDFInfo
- Publication number
- CN102530968A CN102530968A CN2012100053118A CN201210005311A CN102530968A CN 102530968 A CN102530968 A CN 102530968A CN 2012100053118 A CN2012100053118 A CN 2012100053118A CN 201210005311 A CN201210005311 A CN 201210005311A CN 102530968 A CN102530968 A CN 102530968A
- Authority
- CN
- China
- Prior art keywords
- spiral
- intermediate product
- bithiophene base
- monox nanometer
- bithiophene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a production method of a spiral bi-thienyl silicon oxide nanometer material, which comprises the following steps that: 1, Z-amino acid and alkylamine form amido linkage through condensation reaction, then a Z protecting group is removed, so an intermediate product A is obtained; 2, the intermediate product A is reacted with bromo acyl chloride to obtain an intermediate product B; 3, the intermediate product B is reacted with triethylamine to obtain an anionic surfactant C; and 4, the spiral bi-thienyl silicon oxide nanometer material is produced by using the anionic surfactant C as a template agent and bi-thienyl silsesquioxane as a silicon source. The production method has a simple process route, easily-obtained raw materials, short reaction time, convenience for operation and no pollution.
Description
Technical field
The invention belongs to field of nanometer material technology, particularly a kind of spiral bithiophene base monox nanometer preparation methods.
Background technology
Spirane structure is the most general a kind of shape of nature, and DNA and many microstructures that other is found in biomass cells have all adopted this structure.Big little of molecule to galaxy, unsymmetrical structure is found everywhere.In field of material preparation, scientists is utilized the chirality principle of transfer, has prepared the nanostructure of various chiralitys and spiral.Wherein, the mesoporous silicon dioxide nano fiber of single chiral and nanotube are the most successful examples.Usually, these nanostructures are that the self-assembly with chirality small molecules amphipathic compound is that the template preparation forms.These small molecules are generally the verivate of amino acid, glucose or SUV.They interact through hydrogen bond, π-π or hate the solvent association to form the 1-dimention nano fibrous texture of single chiral.But the report about spiral hybrid inorganic-organic monox nanometer material is also few.For the hybrid inorganic-organic silica material; Because the existence of organo-functional group; Make this type hybrid material on forming, have adjustability widely, and have good stability, thereby make this type hybrid material be widely used in surface-modifying agent, coating, catalyzer and mould material.
The hybrid inorganic-organic silicon oxide has inorganics and organic characteristic concurrently, also has the incomparable special performance of single inorganics and organism, has a good application prospect at aspects such as support of the catalyst, dielectric materials, luminescent material, metal-adsorbing materials.The monox nanometer material adopts sol-gel (Sol-gel) method to prepare usually; Its ultimate principle is: under certain conditions; Bridging organic sesqui siloxane presoma forms reticulated structure through complicated hydrolysis condensation reaction, obtains silica material through ageing and drying then.Through the different sol-gel technology of bridging silsesquioxane monomer, the change of selecting to contain different organic groups, selection hydrolytie polycondensation process condition, can make silica material with various structures.(publication number is one Chinese patent application: the preparation method who CN101638238) discloses the silica nano material that contains ordered mesoporous pore canals of a kind of pattern and controllable structure; This method is through regulating proportion of surfactant, and the source polycondensation obtains the silica nano material of different-shape through silicon; This method preparation technology is simple, and cost is low, and reaction conditions is gentle, and the material structure and the pattern of preparation are controlled.(publication number is one Chinese patent application: CN101514001) disclose a kind of bar-shaped ordered mesopore silicon dioxide nano material and preparation method thereof; This patent has bigger pore volume and specific surface area through the bar-shaped ordered mesopore silicon dioxide material of chemical surfactant preparation, and length-to-diameter ratio is controlled.One Chinese patent application (publication number: CN101024691) disclose a kind of polysilsesquioxane nanotube of self-assembled growth and the method for making of nano wire; This patent is solvent with water; Organic sesqui siloxane is the silicon source, and polymerization prepares nanotube and nano wire under certain temperature and pressure.And bithiophene base silicon oxide, the bithiophene base silicon oxide that especially has spirane structure does not appear in the newspapers at present as yet.
Summary of the invention
For overcoming deficiency of the prior art, the object of the present invention is to provide a kind of spiral bithiophene base monox nanometer preparation methods.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention realizes through following technical scheme:
The selection cats product is a template, prepares a kind of spiral bithiophene base monox nanometer material through the sol-gel method of transcribing, and may further comprise the steps:
(1) Z-amino acid and alkylamine are formed amido linkage through condensation reaction, slough the Z blocking group then, obtain intermediate product A, the structural formula general formula of said intermediate product A does
; In the formula; R is the amino acid side chain group; N is 1～17 arbitrary integer; Z blocking group in the said Z-amino acid is a benzyloxy, and amino acid is L-Xie Ansuan, D-Xie Ansuan, L-L-Ala, D-L-Ala, L-phenylalanine(Phe), D-phenylalanine(Phe), L-Isoleucine, D-Isoleucine, L-Methionin, D-Methionin, L-leucine or D-leucine; Said alkylamine is the primary amine of two to 18 carbon atoms.
Preferred alkylamine is tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine or stearylamine.
(2) the intermediate product A and the bromacyl chloride reaction that step (1) are obtained obtain intermediate product B; The structural formula general formula of said intermediate product B is
, and the general formula of said bromacyl chloride is
; In the formula, m is 2～10 arbitrary integer.
Preferred bromacyl chloride is bromoacetyl chloride, bromo propionyl chloro, bromobutanoylchloride, bromine valeryl chloride, bromine caproyl chloride.
(3) the intermediate product B and the triethylamine reaction that step (2) are obtained obtain cats product C, and the general structure of said cats product C is
.
(4) adopting cats product C is template; With bithiophene base silsesquioxane is the silicon source; Preparation spiral bithiophene base monox nanometer material, its general formula is
.
Preferably, said spiral bithiophene base monox nanometer material is 5,5 '-two (triethoxy is silica-based)-2,2 '-bithiophene, and its structural formula does.
Preferably, said spiral bithiophene base monox nanometer material is 4,4 '-two (triethoxy is silica-based)-2,2 '-bithiophene, and its structural formula does.
In the technique scheme; Step 1 is specially: with amino acid whose amount of substance is 1 standard part; Take by weighing 1 part of Z-amino acid and be dissolved in the ETHYLE ACETATE of 400-2000 mL, ice bath adds the dicyclohexyl carbon diamines (DCC) of 1-1.2 part down, stirs after 1-10 hour; The alkylamine of 1-1.2 part slowly is added in the mixed solution, reacted 24-72 hour.Add 5-20 mL Glacial acetic acid min. 99.5 and destroy DCC, stirred 1-3 hour.With the reaction mixture heat filtering, the filtrating crystallisation by cooling obtains white solid behind the suction filtration.It is dissolved in the ethanol of 100-1000 mL with the Pd/C of 5-10 g, feeds hydrogen reaction, do not have solid to separate out then to room temperature and react completely.Suction filtration is removed Pd/C, and the filtrating rotary evaporation removes and desolvates, with obtaining intermediate product A behind the sherwood oil recrystallization.
In the technique scheme, step 2 is specially: the amount of substance with intermediate product A is 1 standard part, and 1 part intermediate product A is dissolved in the CH that 100-1000 mL heavily steams
2Cl
2In, under the condition of ice bath, add triethylamine that heavily steams of 1.5-3 part and the bromacyl chloride of 1.1-1.5 part, reacted 1-10 hour.Carry out heat filtering after the reaction, the filtrating rotary evaporation removes and desolvates, with obtaining intermediate product B behind the absolute ethyl alcohol recrystallization.
In the technique scheme, step 3 is specially: the amount of substance with intermediate product B is 1 standard part, 1 part of intermediate product B is added in the triethylamine of 10.0-100.0 mL, is heated to 70-150 ° of C under the nitrogen protection, reacts 2-24 hour.Revolve the dried solid that is after reaction mixture is cooled to room temperature, with obtaining cats product C behind the ether recrystallization.
In the technique scheme; Step 4 is specially: the amount of substance with cats product C is 1 standard part; 1 part of C is dissolved in the NaOH solution of HCl solution or 1.6-4.0 mL 0.1-0.5 mol/L of 0.8-2.0 mL 1-3 mol/L; Add 1.8 ~ 3.6 parts of bithiophene base bridging silsesquioxanes, violent stirring to reaction mixture bleaches under the room temperature.Stop to stir, left standstill under the room temperature 1-3 days, 40-100 ℃ oil bath 3-6 days.The reaction mixture suction filtration is obtained white solid, it is joined in the HCl mixing solutions of 100mL methyl alcohol and 5 mL, 36 wt%, removed C in extracting 12-72 hour, obtain title product spiral bithiophene base monox nanometer material after the drying.
Compared with prior art, the present invention has following beneficial effect:
1) operational path of the present invention is simple, raw material cheaply is easy to get, the reaction times short, easy to operate, pollution-free;
2) the spiral bithiophene base monox nanometer material that obtains of the present invention is a kind of novel organic-inorganic hybrid nano material; The bithiophene group is combined in the nano material skeleton with chemical bonded refractory; And be the chirality accumulation, can be used for separating of asymmetric synthesis and chipal compounds.And the further functionalization of dipyridyl group, at aspects such as biology, medicine, electron devices potential use is arranged all.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention, understands technique means of the present invention in order can more to know, and can implement according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. detailed description.Embodiment of the present invention is provided by following examples and accompanying drawing thereof in detail.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 is embodiment one a SEM photo;
Fig. 2 is the TEM photo of embodiment one sample;
Fig. 3 is the x-ray diffractogram of powder (XRD) of embodiment one sample;
Fig. 4 is the nitrogen adsorption desorption isotherm of embodiment one sample;
Fig. 5 is the BJH pore size distribution curve of embodiment one sample.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Embodiment 1:
With
L-alanine type cats product is template preparation 4,4 '-bithiophene base silicon oxide.
(1)
L-18Ala6Et3Br's is synthetic
111.6g (0.5 mol) benzyloxy is protected
L-L-Ala (Z-
L-Ala) dissolving in the adding 400 mL ETHYLE ACETATE, ice-water bath adds 113.3 g (0.55 mol) DCC down, stirs 1.0 h.With ETHYLE ACETATE heating for dissolving 134.8 g (0.5 mol) NH
2(CH
2)
17CH
3, join after the cooling in the three-necked bottle, stir 2.0 h.Stir 1.5 h under the room temperature, oil bath is stirred 48.0 h down for 45 ℃, and 60 ℃ are stirred 3.0 h.Add 10.0 mL Glacial acetic acid min. 99.5 and continue to stir 1.0 h.With the reaction mixture filtered while hot, filtrating is cooled off in ice-water bath, collects solid behind the suction filtration and uses the n-propyl alcohol recrystallization, obtains intermediate product Z-
L-Ala-NH-C
18H
37
With 237.4 g (0.5 mol) Z-
L-Ala-NH-C
18H
37Join in the 1000 mL ethanol, heating for dissolving adds 5g Pd/C.Solution is heated to about 60 ℃, feeds hydrogen from three-necked bottle one side bottleneck, and opposite side connects liquid seal device and gets rid of hydrogen.After reacting 6.0 h, reaction finishes when cooling off no precipitate.Filter, filtrating is revolved the dried solid that is on Rotary Evaporators, with pouring in the ice-water bath refrigerative sherwood oil after the THF dissolving, separate out solid after suction filtration obtain intermediate product
L-Ala-NH-C
18H
37
With 34.1g (0.1 mol)
L-Ala-NH-C
18H
37Be dissolved in the CH that 400 mL heavily steamed
2Cl
2In, stir, add 5.0 mL and heavily steam triethylamine.Take by weighing 25.6 g (0.12 mol) Br (CH
2)
5COCl slowly adds with constant pressure funnel, stirring at room 5.0 h.The water washing soln, separatory, oil reservoir becomes solid through rotary evaporation.Use the absolute ethyl alcohol recrystallization, get intermediate product
L-18Ala6Br.
To heavily steam triethylamine 50.0 mL and 25.9 g (0.05 mol)
L-18Ala6Br puts into 100.0 mL three-necked bottles, feeds N fast
2Be heated to about 100 ℃, stir.After reacting 12.0 h, the rotation evaporate to dryness.Solid is dissolved in an amount of absolute ethyl alcohol, and rotary evaporation is removed residual thiophene.Solid is dissolved in the 10mL ethanol, is added drop-wise to dropper in the ether of 200 mL, stir, the frozen water cooling.Solid is separated out the back suction filtration and is obtained the target surface promoting agent
L-18Ala6Et3Br.
(2) 4, the preparation of 4 '-bithiophene base silicon oxide
With 50 mg (0.08 mmol)
L-18Ala6Et3Br is dissolved in the HCl solution of 1.0 mL, 2.4 mol/L, adds 100 mg (0.20 mmol) bithiophene base bridging silsesquioxane, and violent stirring to reaction mixture bleaches under the room temperature.Stop to stir, left standstill under the room temperature 1 day, 80 ℃ left standstill 4 days.The reaction mixture suction filtration is obtained white solid, it is joined in the HCl mixing solutions of 100mL methyl alcohol and 5 mL, 36 wt%, extracting was removed in 48 hours
L-18Ala6Et3Br obtains title product 4 after the drying at room temperature, 4 '-bithiophene base silicon oxide.
To shown in Figure 5, be respectively the SEM photo of present embodiment, the TEM photo of present embodiment sample, the x-ray diffractogram of powder (XRD) of present embodiment sample, the nitrogen adsorption desorption isotherm of present embodiment sample and the BJH pore size distribution curve of present embodiment sample referring to Fig. 1.
Embodiment 2:
With
D-alanine type cats product is template preparation 4,4 '-bithiophene base silicon oxide.
The preparation process is with embodiment 1, in step (1) with raw material Z-
L-Ala is changed to Z-
D-Ala keeps other condition constant.
Embodiment 3:
With
L-phenylglycine type cats product is template preparation 4,4 '-bithiophene base silicon oxide.
(1)
L-16Phg6Et3Br's is synthetic
142.6 g (0.5 mol) benzyloxy is protected
L-phenylglycine (Z-
L-Phg) dissolving in the adding 400 mL ETHYLE ACETATE, ice-water bath adds 113.3 g (0.55 mol) DCC down, stirs 1.0 h.With ETHYLE ACETATE heating for dissolving 120.7 g (0.5 mol) NH
2(CH
2)
15CH
3, join after the cooling in the three-necked bottle, stir 2.0 h.Stir 1.5 h under the room temperature, oil bath is stirred 48.0 h down for 45 ℃, and 60 ℃ are stirred 3.0 h.Add 11.0 mL Glacial acetic acid min. 99.5 and continue to stir 1.0 h.With the reaction mixture filtered while hot, filtrating is cooled off in ice-water bath, collects solid behind the suction filtration and uses the n-propyl alcohol recrystallization, obtains intermediate product Z-
L-Phg-NH-C
16H
37
In three-necked bottle, add 254.4 g (0.5 mol) Z-
L-Phg-NH-C
16H
37With 1000 mL ethanol, heating for dissolving, add 5 g Pd/C.Solution is heated to about 60 ℃, feeds hydrogen from three-necked bottle one side bottleneck, and opposite side connects liquid seal device and gets rid of hydrogen.After reacting 6.0 h, reaction finishes when cooling off no precipitate.Filter, filtrating is revolved the dried solid that is on Rotary Evaporators, with pouring in the ice-water bath refrigerative sherwood oil after the THF dissolving, separate out solid after suction filtration obtain intermediate product
L-Phg-NH-C
16H
37
With 37.5 g (0.1 mol)
L-Phg-NH-C
16H
37Be dissolved in the CH that 400 mL heavily steamed
2Cl
2In, stir, add 5.0 mL and heavily steam triethylamine.Take by weighing 25.6 g (0.12 mol) Br (CH
2)
5COCl slowly adds with constant pressure funnel, stirring at room 5.0 h.The water washing soln, separatory, oil reservoir becomes solid through rotary evaporation.Use the absolute ethyl alcohol recrystallization, get intermediate product
L-16Phg6Br.
To heavily steam triethylamine 50.0 mL and 27.6 g (0.05 mol)
L-16Phg6Br puts into 50.0 mL three-necked bottles, feeds N fast
2Be heated to about 100 ℃, stir.After reacting 12.0 h, the rotation evaporate to dryness.Solid is dissolved in an amount of absolute ethyl alcohol, and rotary evaporation is removed residual triethylamine.Solid is dissolved in the 10 mL ethanol, is added drop-wise in the 200 mL ether, stir, the frozen water cooling with dropper.Solid is separated out the back suction filtration and is obtained the target surface promoting agent
L-16Phg6Et3Br.
(2) 4, the preparation of 4 '-bithiophene base silicon oxide
With 50 mg (0.08 mmol)
L-16Phg6Et3Br is dissolved in the HCl solution of 1.0 mL, 2.4 mol/L, adds 100 mg (0.20 mmol) bithiophene base bridging silsesquioxane, and violent stirring to reaction mixture bleaches under the room temperature.Stop to stir, left standstill under the room temperature 1 day, 80 ℃ left standstill 4 days.The reaction mixture suction filtration is obtained white solid, it is joined in the HCl mixing solutions of 100 mL methyl alcohol and 5 mL, 36 wt%, extracting was removed in 48 hours
L-16Phg6Et3Br obtains title product 4 after the drying at room temperature, 4 '-bithiophene base silicon oxide.
Embodiment 4:
With
D-phenylglycine type cats product is template preparation 4,4 '-bithiophene base silicon oxide.
The preparation process is with embodiment 1, in step (1) with raw material Z-
L-Phg is changed to Z-
D-Phg keeps other condition constant.
Change the acidic conditions of preparation process (2) among embodiment 1 ~ embodiment 4 into alkaline condition, the HCl solution that is about to 1.0 mL, 2.4 mol/L changes the NaOH solution of 2.0 mL, 0.25 mol/L into, keeps other condition constant, repeated experiments.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within the scope of the present invention.
Claims (9)
1. spiral bithiophene base monox nanometer preparation methods is characterized in that, may further comprise the steps:
Step 1) forms amido linkage with Z-amino acid and alkylamine through condensation reaction, sloughs the Z blocking group then, obtains intermediate product A, and the structural formula general formula of said intermediate product A does
Step 2) said intermediate product A and bromacyl chloride reaction are obtained intermediate product B; The structural formula general formula of said intermediate product B is
, and the general formula of said bromacyl chloride is
;
Step 3) obtains cats product C with said intermediate product B and triethylamine reaction, and the general structure of said cats product C does;
It is template that step 4) adopts said cats product C, is the silicon source with bithiophene base silsesquioxane, preparation title product spiral bithiophene base monox nanometer material, and the general formula of said spiral bithiophene base monox nanometer material is:; In the general structure of the above-mentioned product that respectively reacts gained, n is 1～17 arbitrary integer, and m is 2～10 arbitrary integer.
2. spiral bithiophene base monox nanometer preparation methods according to claim 1, it is characterized in that: said alkylamine is tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine or stearylamine.
3. spiral bithiophene base monox nanometer preparation methods according to claim 1 is characterized in that: said bromacyl chloride is bromoacetyl chloride, bromo propionyl chloro, bromobutanoylchloride, bromine valeryl chlorine or bromine caproyl chloride.
4. spiral bithiophene base monox nanometer preparation methods according to claim 1 is characterized in that: said spiral bithiophene base monox nanometer material is 5,5 '-two (triethoxy is silica-based)-2,2 '-bithiophene, and its structural formula does.
5. spiral bithiophene base monox nanometer preparation methods according to claim 1 is characterized in that: said spiral bithiophene base monox nanometer material is 4,4 '-two (triethoxy is silica-based)-2,2 '-bithiophene, its structure be for.
6. spiral bithiophene base monox nanometer preparation methods according to claim 1; It is characterized in that the detailed process of step 1 is following: with amino acid whose amount of substance is 1 standard part, takes by weighing 1 part of Z-amino acid and is dissolved in the ETHYLE ACETATE of 400-2000 mL; Ice bath adds the dicyclohexyl carbon diamines of 1-1.2 part down; Stir after 1-10 hour, the alkylamine of 1-1.2 part slowly is added in the mixed solution, reacted 24-72 hour; Add 5-20 mL Glacial acetic acid min. 99.5 and destroy dicyclohexyl carbon diamines, stirred 1-3 hour; With the reaction mixture heat filtering, the filtrating crystallisation by cooling obtains white solid behind the suction filtration; It is dissolved in the ethanol of 100-1000 mL with the Pd/C of 5-10g, feeds hydrogen reaction, do not have solid to separate out then to room temperature and react completely; Suction filtration is removed Pd/C, and the filtrating rotary evaporation removes and desolvates, with obtaining intermediate product A behind the sherwood oil recrystallization.
7. spiral bithiophene base monox nanometer preparation methods according to claim 1; It is characterized in that; Step 2 detailed process is following: the amount of substance with intermediate product A is 1 standard part, and 1 part intermediate product A is dissolved in the CH that 100-1000 mL heavily steams
2Cl
2In, under the condition of ice bath, add triethylamine that heavily steams of 1.5-3 part and the bromacyl chloride of 1.1-1.5 part, reacted 1-10 hour; Carry out heat filtering after the reaction, the filtrating rotary evaporation removes and desolvates, with obtaining intermediate product B behind the absolute ethyl alcohol recrystallization.
8. according to the spiral bithiophene base monox nanometer preparation methods of claim 1; It is characterized in that; Step 3 detailed process is following: the amount of substance with intermediate product B is 1 standard part; 1 part of intermediate product B is added in the triethylamine of 10.0-100.0mL, be heated to 70-150 ℃ under the nitrogen protection, reacted 2-24 hour; Revolve the dried solid that is after reaction mixture is cooled to room temperature, with obtaining cats product C behind the ether recrystallization.
9. according to any described spiral bithiophene base monox nanometer preparation methods among the claim 1-8; It is characterized in that; Step 4 detailed process is following: the amount of substance with cats product C is 1 standard part; 1 part of C is dissolved in the NaOH solution of HCl solution or 1.6-4.0 mL 0.1-0.5 mol/L of 0.8-2.0 mL 1-3 mol/L, adds 1.8 ~ 3.6 parts of bithiophene base bridging silsesquioxanes, violent stirring to reaction mixture bleaches under the room temperature; Stop to stir, left standstill under the room temperature 1-3 days, 40-100 ℃ oil bath 3-6 days; The reaction mixture suction filtration is obtained white solid, it is joined in the HCl mixing solutions of 100mL methyl alcohol and 5 mL, 36 wt%, removed C in extracting 12-72 hour, obtain title product spiral bithiophene base monox nanometer material after the drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100053118A CN102530968A (en) | 2012-01-10 | 2012-01-10 | Production method of spiral bi-thienyl silicon oxide nanometer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100053118A CN102530968A (en) | 2012-01-10 | 2012-01-10 | Production method of spiral bi-thienyl silicon oxide nanometer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102530968A true CN102530968A (en) | 2012-07-04 |
Family
ID=46339189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100053118A Pending CN102530968A (en) | 2012-01-10 | 2012-01-10 | Production method of spiral bi-thienyl silicon oxide nanometer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102530968A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445253A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for synthesizing nanocrystalline MEL zeolite cluster |
| CN114276553A (en) * | 2020-12-31 | 2022-04-05 | 南京工业大学 | Monosaccharide functionalized organic nano soft ball and preparation method thereof |
| CN114345144A (en) * | 2021-12-30 | 2022-04-15 | 复旦大学 | Chiral CMS/AAO heterojunction membrane and preparation method thereof |
-
2012
- 2012-01-10 CN CN2012100053118A patent/CN102530968A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 《Chem. Commun.》 20110926 Baozong Li, et al Characterization of 4,4'-biphenylene-silicas and a chiral sensor for silicas 11495-11497 1-9 第47卷, * |
| BAOZONG LI, ET AL: "Characterization of 4,4’-biphenylene-silicas and a chiral sensor for silicas", 《CHEM. COMMUN.》 * |
| 裴仙风: "仿生孔材料的制备与性质研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445253A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Method for synthesizing nanocrystalline MEL zeolite cluster |
| CN104445253B (en) * | 2013-09-24 | 2016-08-24 | 中国石油化工股份有限公司 | The method of synthesizing nanocrystalline MEL zeolite cluster |
| CN114276553A (en) * | 2020-12-31 | 2022-04-05 | 南京工业大学 | Monosaccharide functionalized organic nano soft ball and preparation method thereof |
| CN114345144A (en) * | 2021-12-30 | 2022-04-15 | 复旦大学 | Chiral CMS/AAO heterojunction membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Fast and scalable synthesis of uniform zirconium-, hafnium-based metal–organic framework nanocrystals | |
| AU2009214118B2 (en) | Method for manufacturing mesoporous materials, materials so produced and use of mesoporous materials | |
| WO2011108649A1 (en) | Process for producing porous silica, and porous silica | |
| JP5060670B2 (en) | Silica-based chiral nanostructure and method for producing the same | |
| CN102909070B (en) | Load type chiral catalyst and preparation method thereof | |
| JP5958842B2 (en) | Method for producing chiral metal oxide structure, and chiral porous structure | |
| CN101475190B (en) | Preparation of periodic mesoporous organic silicon oxide material | |
| CN102530968A (en) | Production method of spiral bi-thienyl silicon oxide nanometer material | |
| Zhang et al. | High-efficiency grafting of halloysite nanotubes by using π-conjugated polyfluorenes via “click” chemistry | |
| JP2007137809A (en) | Fullerene derivative, method for producing fullerene derivative, nano-mesoscopic material and method for producing nano-mesoscopic material | |
| CN102874820A (en) | Method for preparing cellular silicon dioxide nanotubes | |
| CN101735633A (en) | Functionalized organic/inorganic hybridized asymmetric structure particle and synthesis method thereof | |
| CN1332963C (en) | Amino phenyl cage type sesqui siloxane and its preparing method | |
| Martín-Illán et al. | Evolution of covalent organic frameworks: from design to real-world applications | |
| CN110845484A (en) | Compound based on spirofluorene xanthene bilateral substituted carbazole, organic nanocrystal material, preparation method and application | |
| CN109053795A (en) | A kind of preparation method of more methacryloxy sesquialter silane | |
| CN105111233A (en) | Preparation method of octaphenyl silsesquioxane | |
| JP5377265B2 (en) | Polymer / tartaric acid crystalline nanocomposite and method for producing the same | |
| CN109880105B (en) | Preparation method of heteroatom doped ferrocene functionalized POSS-based hybrid porous polymer | |
| Wang et al. | Catalytic properties of dendron–OMS hybrids | |
| KR20110112682A (en) | Diurea-containing periodic mesoporous organosilica and method for making the same | |
| CN102532549A (en) | Method for preparing spiral bipyridine bridged polysilsesquioxanes nano-composite material | |
| CN104045800B (en) | Method for preparing spiral mesoporous phenolic resin nanofiber | |
| CN103030788A (en) | Conjugated polymer gelling agent poly(phenylene ethynylene) and preparation method thereof | |
| CN109970976B (en) | Tetraphenyl vinyl bridged polysilsesquioxane, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |