CN104355300A - Preparation method for amino-fullerene derivative - Google Patents
Preparation method for amino-fullerene derivative Download PDFInfo
- Publication number
- CN104355300A CN104355300A CN201410495019.8A CN201410495019A CN104355300A CN 104355300 A CN104355300 A CN 104355300A CN 201410495019 A CN201410495019 A CN 201410495019A CN 104355300 A CN104355300 A CN 104355300A
- Authority
- CN
- China
- Prior art keywords
- soccerballene
- amino
- halides
- dissolved
- fullerene derivate
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a preparation method for an amino-fullerene derivative. The preparation method comprises the following steps: (1) under the air atmosphere, dissolving a fullerene halide in an aromatic organic solvent, and dissolving an ammoniation reagent in DMSO (dimethyl sulfoxide), wherein the molar ratio of the fullerene halide to the ammoniation reagent is 1:(1-200); (2) adding a fullerene halide solution and an ammoniation reagent solution prepared in the step (1) in a reactor, and stirring for reaction at 20-150 DEG C for 0.1-10 days; (3) separating the liquid to take the dimethyl sulfoxide solution layer, adding in water, the volume of which is equivalent to 8-12 times of that of the dimethyl sulfoxide solution, as the precipitation solvent for dilution, carrying out centrifugal separation, washing the solid in water for 2-5 times, and carrying out vacuum drying at 40-60 DEG C to obtain a khaki solid, namely the amino-fullerene derivative. The preparation method has the advantages of being cheap and available for raw materials, simple in synthetic process, high in productive rate, environment-friendly and the like; the amount of amidogens introduced in is controllable, at most 48 amidogens can be simultaneously bonded in the fullerene structure, and the preparation method is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method of amino fullerene derivate, be specifically related to the preparation method of polyamino fullerene derivate.
Background technology
The development trend of current solid propelling agent is high-energy, high combustion speed, high strength, low sensitivity and recyclable recycling.When existing propellant formulation is constant, catalyzer or the oxygenant of seeking excellent performance are one of effective ways improving propellant burning property.Often adopt ammonium nitrate (AN) or ADN (ADN) as desirable oxygenant to develop low characteristic, low stain propelling agent at present, they have makes propelling agent have the advantages such as clean corrosion-free, the low price of high, the combustion gas of combustion speed; But the heteromorphism existed due to AN and ADN itself and extremely strong water absorbability, make their application in propelling agent be very limited; And AN energy is low, obtained propelling agent cannot obtain desirable specific impulse and high combustion speed, also limits its application in propelling agent.
In recent years, researchist finds that amino soccerballene can be used as intermediate, introduce ammonium nitrate and ADN etc. further in the structure and there is the molecule containing energy group, utilize the hydrophobicity of soccerballene to overcome the shortcomings such as the water absorbability of ammonium nitrate and ADN, be expected to replace ammonium nitrate and ADN and be applied in solid propellant.
At present, prior art synthesis prior art CN 200810115926.X discloses polyamino Fullerene and solid phase synthesis process thereof, this synthetic method by the Solid phase peptide synthesis resin of load amino and the toluene solution of soccerballene being obtained by reacting the Solid phase peptide synthesis resin of the amino soccerballene of load, then reacts obtained polyamino fullerene derivate C with lysate
60(NH
3)
n, n > 5; But the method has the shortcomings such as operation is loaded down with trivial details, production cost is high, meanwhile, utilizes the method also can only add 9 amino at most on fullerene structure.
Summary of the invention
Technical problem to be solved by this invention is, provide a kind of preparation method of amino fullerene derivate, the method has that starting material are cheap and easy to get, synthesis technique is simple, environmental protection, productive rate advantages of higher, and it is controlled to introduce amino number, simultaneously most multipotency adds 48 amino on fullerene structure.
The technical scheme that the present invention solves the employing of its technical problem is that the preparation method of amino fullerene derivate, comprises the following steps:
(1) in air atmosphere, be dissolved in aromatic organic solvents by soccerballene halides, be dissolved in by aminating agent in dimethyl sulfoxide (DMSO) (DMSO), wherein, the mol ratio of soccerballene halides and aminating agent is 1: 1 ~ 200;
(2) then by preparing soccerballene halides solution and aminating agent solution are put in reactor in step (1), under the condition of 20 ~ 150 DEG C, stirring reaction 0.1 ~ 10 day;
(3) then separatory, gets dimethyl sulphoxide solution layer, adds the water being equivalent to 8 ~ 12 times of dimethyl sulfoxide (DMSO) volumes and dilute as precipitation solvent, centrifugation, solid washed with water 2 ~ 5 times, after 40 ~ 60 DEG C of vacuum-dryings, obtain khaki color solid, be amino fullerene derivate.
Preferably, the preparation method of amino fullerene derivate, comprises the following steps:
(1) in air atmosphere, be dissolved in aromatic organic solvents by soccerballene halides, be dissolved in by aminating agent in dimethyl sulfoxide (DMSO) (DMSO), wherein, the mol ratio of soccerballene halides and aminating agent is 1: 100 ~ 150;
(2) then by preparing soccerballene halides solution and aminating agent solution are put in reactor in step (1), under the condition of 25 ~ 70 DEG C, stirring reaction 3 ~ 5 days;
(3) then separatory gets dimethyl sulphoxide solution layer, adds the water being equivalent to 10 times of dimethyl sulphoxide solution volumes and dilutes as precipitation solvent, centrifugation, solid washed with water 3 times, after 40 ~ 50 DEG C of vacuum-dryings, obtain khaki color solid, be amino fullerene derivate.
Further, in step (1), the described soccerballene halides ratio be dissolved in aromatic organic solvents is that the soccerballene halides of every 50mg is dissolved in the aromatic organic solvents of 15 ~ 35mL; The described aminating agent ratio be dissolved in dimethyl sulfoxide (DMSO) is that the aminating agent of every 50mg is dissolved in the dimethyl sulfoxide (DMSO) of 5 ~ 10mL.
Further, in step (1), described soccerballene halides is selected from soccerballene muriate (C
60cl
n, n=1-48) or soccerballene bromide (C
60br
n, n=1-48); Described aminating agent is selected from any one in azanol, ammoniacal liquor, trimethylammonium hydrazine iodide, amino-1,2, the 4-triazole of 4-, mercaptan ammonia, sulfinyl amine, potassium phthalimide; Described aromatic organic solvents is selected from any one in dimethylbenzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, orthodichlorobenzene.
Further, described precipitation solvent is distilled water.
Preparation method of the present invention utilizes soccerballene halides and aminating agent to be obtained by reacting polyamino fullerene derivate, there is the advantages such as starting material are cheap and easy to get, synthesis technique is simple, aftertreatment distilled water has environmental protection as precipitation solvent, the feature that productive rate is high; And it is controlled to introduce amino number, simultaneously most multipotency adds 48 amino on fullerene structure, is applicable to suitability for industrialized production.
Amino fullerene derivate prepared by the present invention is due to-the NH containing some amount in structure
2group, can be introduced containing energy group by this group, be a kind of desirable intermediate, have good development potentiality and market outlook in the aerospace such as explosive, propelling agent and priming system and national defence on fullerene ball.
Accompanying drawing explanation
Fig. 1 is with C
60br
24for raw material obtains C
60(NH
2)
24infrared spectrogram.
Fig. 2 is with C
60cl
24for raw material obtains C
60(NH
2)
24infrared spectrogram.
Embodiment
Contribute to understanding the present invention by following embodiment, but the content of invention is not by the restriction of this embodiment.
Embodiment 1: amino soccerballene C
60(NH
2)
24preparation
Amino for 1.26g 4--1,2,4-triazole (15mmol) is dissolved in 20mI dimethyl sulfoxide (DMSO) (DMSO), then joins 100mI and be dissolved with 0.26gC
60br
24(0.1mmol) in xylene solution, stirring reaction 5 days under 70 DEG C of conditions, separatory obtains DMSO layer solution, then add 200mI distilled water, have solid to separate out, centrifugation, solid 50mI washes 3 times, obtains the amino soccerballene C of faint yellow solid after 45 DEG C of vacuum-dryings to constant weight
60(NH
2)
2496.3mg, productive rate is 88.3%, product C
60(NH
2)
24infrared spectra is shown in Fig. 1.Product C
60(NH
2)
24ultimate analysis calculated value: C 65.22%, H 4.35%, N 30.43%; Measured value: C 65.14%, H 4.36%, N 30.50%.
Embodiment 2: amino soccerballene C
60(NH
2)
24preparation
2.02g trimethylammonium hydrazine iodide (10mmol) is dissolved in 40mI dimethyl sulfoxide (DMSO) (DMSO) solution, then joins 100mI and be dissolved with 0.16g C
60cl
24xylene solution in, stirring reaction 3 days under 25 DEG C of conditions, separatory obtains DMSO layer solution, then adds 400mI distilled water, has solid to separate out, centrifugation, and solid 50mI washes 3 times, after 45 DEG C of vacuum-dryings to constant weight the amino soccerballene C of faint yellow solid
60(NH
2)
2492.5mg, productive rate is 84.8%, product C
60(NH
2)
24infrared spectra is shown in Fig. 2.Product C
60(NH
2)
24ultimate analysis calculated value: C 65.22%, H 4.35%, N 30.43%; Measured value: C 65.16%, H 4.35%.N 30.49%.
Embodiment 3: amino soccerballene C
60(NH
2)
48preparation
Amino for 1.68g 4--1,2,4-triazole (20mmol) is dissolved in 20mI dimethyl sulfoxide (DMSO) (DMSO), then joins 100mI and be dissolved with 0.45gC
60br
48(0.1mmol) in xylene solution, stirring reaction 8 days under 70 DEG C of conditions, separatory obtains DMSO layer solution, then add 200mI distilled water, have solid to separate out, centrifugation, solid 50mI washes 3 times, obtains the amino soccerballene C of faint yellow solid after 45 DEG C of vacuum-dryings to constant weight
60(NH
2)
48132.3mg, productive rate is 88.9%.Product C
60(NH
2)
48ultimate analysis calculated value: C48.39%, H 6.45%, N 45.16%; Measured value: C 48.44%, H 6.36%, N 45.20%.
Embodiment 4: amino soccerballene C
60(NH
2)
12preparation
Amino for 0.84g 4--1,2,4-triazole (10mmol) is dissolved in 15mI dimethyl sulfoxide (DMSO) (DMSO), then joins 100mI and be dissolved with 0.17g C
60br
12(0.1mmol) in xylene solution, stirring reaction 4 days under 70 DEG C of conditions, separatory obtains DMSO layer solution, then add 200mI distilled water, have solid to separate out, centrifugation, solid 50mI washes 3 times, obtains the amino soccerballene C of faint yellow solid after 45 DEG C of vacuum-dryings to constant weight
60(NH
2)
2488.2mg, productive rate is 96.7%.Product C
60(NH
2)
24ultimate analysis calculated value: C78.95%, H 2.63%, N 18.42%; Measured value: C 78.88%, H 2.65%, N 18.47%.
Claims (8)
1. the preparation method of amino fullerene derivate, is characterized in that, comprises the following steps:
(1) in air atmosphere, soccerballene halides is dissolved in aromatic organic solvents, for subsequent use; Aminating agent is dissolved in dimethyl sulfoxide (DMSO), for subsequent use; Wherein, the mol ratio of soccerballene halides and aminating agent is 1: 1 ~ 200;
(2) then soccerballene halides organic solution for subsequent use in step (1) and aminating agent solution are put in reactor, under the condition of 20 ~ 150 DEG C, stirring reaction 0.1 ~ 10 day;
(3) then separatory gets dimethyl sulphoxide solution layer, adds the water being equivalent to 8 ~ 12 times of dimethyl sulphoxide solution volumes and dilutes as precipitation solvent, centrifugation, solid washed with water 2 ~ 5 times, after 40 ~ 60 DEG C of vacuum-dryings, obtain khaki color solid, obtain amino fullerene derivate.
2. amino fullerene derivate according to claim 1, is characterized in that, comprise the following steps:
(1) in air atmosphere, just soccerballene halides is dissolved in aromatic organic solvents, is dissolved in by aminating agent in dimethyl sulfoxide (DMSO), and wherein, the mol ratio of soccerballene halides and aminating agent is 1: 100 ~ 150;
(2) then by preparing soccerballene halides solution and aminating agent solution are put in reactor in step (1), under the condition of 25 ~ 70 DEG C, stirring reaction 3 ~ 8 days;
(3) then separatory gets dimethyl sulphoxide solution layer, adds the water being equivalent to 10 times of dimethyl sulphoxide solution volumes and dilutes as precipitation solvent, centrifugation, solid washed with water 3 times, after 40 ~ 50 DEG C of vacuum-dryings, obtain khaki color solid, obtain amino fullerene derivate.
3. amino fullerene derivate according to claim 1 and 2, it is characterized in that, in step (1), the described soccerballene halides ratio be dissolved in aromatic organic solvents is that the soccerballene halides of every 50mg is dissolved in the aromatic organic solvents of 15 ~ 35mL; The described aminating agent ratio be dissolved in dimethyl sulfoxide (DMSO) is that the aminating agent of every 50mg is dissolved in the dimethyl sulfoxide (DMSO) of 5 ~ 10mL.
4. amino fullerene derivate according to claim 1 and 2, is characterized in that, in step (1), described soccerballene halides is selected from soccerballene muriate (C
60cl
n, n=1-48) or soccerballene bromide (C
60br
n, n=1-48); Described aminating agent is selected from any one in azanol, ammoniacal liquor, trimethylammonium hydrazine iodide, amino-1,2, the 4-triazole of 4-, mercaptan ammonia, sulfinyl amine, potassium phthalimide; Described aromatic organic solvents is selected from any one in dimethylbenzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, orthodichlorobenzene.
5. amino fullerene derivate according to claim 3, is characterized in that, in step (1), described soccerballene halides is selected from soccerballene muriate (C
60cl
n, n=1-48) or soccerballene bromide (C
60br
n, n=1-48); Described aminating agent is selected from any one in azanol, ammoniacal liquor, trimethylammonium hydrazine iodide, amino-1,2, the 4-triazole of 4-, mercaptan ammonia, sulfinyl amine, potassium phthalimide; Described aromatic organic solvents is selected from any one in dimethylbenzene, o-Xylol, p-Xylol, m-xylene, chlorobenzene, orthodichlorobenzene.
6. amino fullerene derivate according to claim 1 and 2, is characterized in that, in step (3), described precipitation solvent is distilled water.
7. amino fullerene derivate according to claim 3, is characterized in that, in step (3), described precipitation solvent is distilled water.
8. amino fullerene derivate according to claim 4, is characterized in that, in step (3), described precipitation solvent is distilled water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410495019.8A CN104355300B (en) | 2014-09-23 | 2014-09-23 | The preparation method of amino fullerene derivate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410495019.8A CN104355300B (en) | 2014-09-23 | 2014-09-23 | The preparation method of amino fullerene derivate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104355300A true CN104355300A (en) | 2015-02-18 |
| CN104355300B CN104355300B (en) | 2016-08-17 |
Family
ID=52522645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410495019.8A Expired - Fee Related CN104355300B (en) | 2014-09-23 | 2014-09-23 | The preparation method of amino fullerene derivate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104355300B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041241A (en) * | 2019-05-10 | 2019-07-23 | 西南科技大学 | Fullerene amino benzenes derivates and its preparation method and application |
| CN110734049A (en) * | 2019-11-25 | 2020-01-31 | 江西省科学院应用化学研究所 | method for preparing nitrogen-doped carbon material with high specific surface area by using potassium phthalimide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418079A (en) * | 2008-11-27 | 2009-04-29 | 同济大学 | Method for preparing polyimide lubrication film containing fullerene additives |
| CN102898542A (en) * | 2012-10-23 | 2013-01-30 | 郑州大学 | Water-soluble fullerene and application thereof |
| CN103316341A (en) * | 2013-06-26 | 2013-09-25 | 郑州大学 | Fullerene-nanogold composite material as well as preparation method and application thereof |
-
2014
- 2014-09-23 CN CN201410495019.8A patent/CN104355300B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418079A (en) * | 2008-11-27 | 2009-04-29 | 同济大学 | Method for preparing polyimide lubrication film containing fullerene additives |
| CN102898542A (en) * | 2012-10-23 | 2013-01-30 | 郑州大学 | Water-soluble fullerene and application thereof |
| CN103316341A (en) * | 2013-06-26 | 2013-09-25 | 郑州大学 | Fullerene-nanogold composite material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIANGQING HU ET AL.: "Amination of [60]Fullerene by Ammonia and by Primary and Secondary Aliphatic Amines—Preparation of Amino[60] fullerene Peroxides", 《CHEM.EUR.J.》, vol. 13, 31 October 2006 (2006-10-31), pages 1129 - 1141 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041241A (en) * | 2019-05-10 | 2019-07-23 | 西南科技大学 | Fullerene amino benzenes derivates and its preparation method and application |
| CN110041241B (en) * | 2019-05-10 | 2022-04-01 | 西南科技大学 | Fullerene aniline derivative and preparation method and application thereof |
| CN110734049A (en) * | 2019-11-25 | 2020-01-31 | 江西省科学院应用化学研究所 | method for preparing nitrogen-doped carbon material with high specific surface area by using potassium phthalimide |
| CN110734049B (en) * | 2019-11-25 | 2022-08-19 | 江西省科学院应用化学研究所 | Method for preparing nitrogen-doped carbon material with high specific surface area by using potassium phthalimide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104355300B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104355300A (en) | Preparation method for amino-fullerene derivative | |
| CN104341319B (en) | A kind of synthesis technique of 2 cyano 4 nitro 6 bromo aniline | |
| Li et al. | Direct oxidative nitration of aromatic sulfonamides under mild conditions | |
| Lancaster et al. | Aromatic nitrations in ionic liquids: the importance of cation choice | |
| CN105418458A (en) | Synthetic process of 2-cyano-4-nitroaniline | |
| Shi et al. | Tetraphenylethene-decorated functional polybenzoxazines: post-polymerization synthesis via benzoxazine–isocyanide chemistry and application in probing and catalyst fields | |
| 赵廷兴 et al. | Up-sizing 50 Grams-scale Synthesis Technology of Dihydroxylammonium 5, 5′-Bistetrazole-1, 1′-diolate (TKX-50) | |
| CN110483572B (en) | Trinuclear gold alkynyl urea complex with tetrahedral oxyanion recognition function and preparation method thereof | |
| CN105859582A (en) | New technology for separating nitride in production of 2-cyano-4-nitroaniline | |
| Dhiman et al. | Glycoluril derived cucurbituril analogues and the emergence of the most recent example: tiarauril | |
| CN112552520B (en) | Two-dimensional energy-containing CMOFs material containing nitro nitrogen-rich heterocyclic anions and preparation method thereof | |
| CN107445886B (en) | Preparation method of high-purity 3-bromo-9-phenylcarbazole | |
| CN103342646A (en) | High-selectivity synthesis method of 4-nitro-ortho-xylene | |
| CN105693641A (en) | Preparation method of triazine ultraviolet absorbent | |
| CN112111060A (en) | Porous organic framework material, preparation method thereof and application of porous organic framework material in selective separation of perrhenate | |
| CN103880708B (en) | A kind of improvement process for catalytic synthesis of propane dinitrile | |
| CN104028253B (en) | A kind of gold nano grain-polysaccharide bonded silica gel stationary phase and preparation method thereof | |
| CN109111351B (en) | Synthesis method of asymmetric 9-alkoxy phenanthrene dimer | |
| CN109012639A (en) | Chitosan silicon based composite material of molybdenum trace and preparation method thereof and the application in recycling rhenium | |
| CN105111101B (en) | Method for preparing N-cyanoethyl-N-ethoxylaniline by using ionic liquid | |
| CN106824141B (en) | Preparation method of cyclodextrin chromatographic stationary phase | |
| Yao et al. | Synthesis, characterization, thermal analyses, and spectroscopic properties of novel naphthyl-functionalized imidazolium ionic liquids | |
| Yu et al. | Synthesis and anion recognition of acetate ions using pyrrole-⍺-carboxaldehyde 2, 4-dinitrophenyl hydrazone | |
| CN104974321B (en) | A kind of methyl-etherified melamine resin and preparation method thereof | |
| KR102573598B1 (en) | Method of pretreating metal-phthalocyanine-based colorant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20190923 |