CN111498832A - Preparation process of high-purity fullerol - Google Patents
Preparation process of high-purity fullerol Download PDFInfo
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- CN111498832A CN111498832A CN202010215591.XA CN202010215591A CN111498832A CN 111498832 A CN111498832 A CN 111498832A CN 202010215591 A CN202010215591 A CN 202010215591A CN 111498832 A CN111498832 A CN 111498832A
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention discloses the technical field of fullerene materials, and particularly relates to a preparation process of high-purity fullerol, which comprises the following steps of 1: purifying the polystyrene divinylbenzene resin to remove unmodified fullerene; step 2: purifying brominated polystyrene-amine-acrylamide resin, and collecting fullerol with different hydroxyl groups; the method for preparing the high-purity fullerol by utilizing the chromatography has the following advantages: 1) the method is simple and only needs two steps of purification; 2) the solvent consumption is less, and is greatly reduced compared with the multi-step liquid-liquid extraction solvent consumption; 3) the purity is high and is more than 95 percent; 4) can distinguish fullerene substituted by different hydroxyl groups, particularly collect the fullerene alcohol with 20-25 hydroxyl groups, and has the characteristics of good water solubility and good free radical removing effect. The method can selectively purify the fullerol from the fullerene derivative product with high efficiency, has the characteristics of high product purity, high efficiency, solvent saving and simple method, and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of fullerene materials, in particular to a preparation process of high-purity fullerol.
Background
Fullerene is a hollow molecule composed entirely of carbon, and is in the shape of a sphere, ellipsoid, column or tube. The fullerene has super-strong permeability due to the nanometer size; it has super strong oxidation resistance and can eliminate free radicals; and a perfect symmetrical structure and an ultra-stable performance are known as 'nanometer prince', and the fullerene has wide application in a plurality of fields, and the fullerene family represented by C60 opens up a new research direction in physics, chemistry and material science by the unique shape and good properties of the fullerene family. Like benzene, which is very common in organic chemistry, fullerenes, represented by C60, form the basis of a rich and varied class of organic compounds. Many unusual properties of new fullerene materials can have many practical applications in modern technologies and industries, including lubricants, catalysts, abrasives, cosmetics, high strength carbon fibers, semiconductors, nonlinear optical devices, superconducting materials, photoconductors, organic solar high energy cells, fuels, sensors, molecular devices, and for medical imaging and therapy.
C60 and its derivatives are the most studied and used fullerenes because C60 is the relatively most readily available, most easily purified, and least expensive species in the fullerene family. In particular, the cosmetic effects of fullerenes are mainly: resisting aging, removing wrinkle, whitening skin, removing speckle, inhibiting acne, and shrinking follicular orifice. Since fullerenes dissolve poorly in most solvents, they are typically dissolved with an aromatic solvent, such as toluene, chlorobenzene, or a non-aromatic solvent, carbon disulfide.
Fullerol is a derivative of fullerene, and is obtained by chemically introducing hydroxyl groups into fullerene carbons. The synthesis reaction of the fullerol is generally an acid method, a bromination method and the like, and after the synthesis is finished, the fullerol product with certain purity is obtained by multiple liquid-liquid extraction with water, acetone, tetrahydrofuran or benzene. The conventional liquid-liquid extraction method has the problems of complicated operation steps and high solvent consumption on one hand, and has the problems of relatively low purity of the extracted fullerol on the other hand, and the conventional liquid-liquid extraction method cannot distinguish the fullerol products with different hydroxyl numbers, thereby bringing great troubles to the quality control and the using effect of the fullerol.
The purpose of introducing hydroxyl groups into fullerene is to improve the water solubility of fullerene, but the fullerene has better water solubility only when the number of hydroxyl groups reaches more than 20. In practical application, the fullerene alcohol needs to maintain the stability of O60 and increase the solubility of fullerene, and most importantly, the biological safety is guaranteed in biological application, so that the development of a green and environment-friendly method with high biological safety is of great significance.
Disclosure of Invention
The invention aims to provide a preparation process of high-purity fullerol by a two-step preparation chromatography, which has the characteristics of simple method, less solvent consumption, high fullerol purity and controllable hydroxyl number, and overcomes the defects of complicated operation steps, large solvent consumption and uncontrollable hydroxyl number in the traditional fullerol purification process.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation process of high-purity fullerol comprises the following steps:
step 1: purifying the polystyrene divinylbenzene resin to remove unmodified fullerene;
step 2: purifying the brominated polystyrene-acrylamide resin, and collecting the fullerol with different hydroxyl groups.
Preferably, the particle size of the polystyrene divinylbenzene resin is 200-400 mu m, and the specific surface area is 600-750 m2/g。
Preferably, the elution solvent for purifying the polystyrene divinyl benzene resin in the step 1 is one of toluene, xylene, dichlorotoluene and dimethyl sulfoxide.
Preferably, the elution solvent for purifying the polystyrene divinyl benzene resin in the step 1 is toluene.
Preferably, the collection time for purifying the polystyrene divinylbenzene resin in the step 1 is 1 to 4 times of the column volume.
Preferably, the particle size of the brominated polystyrene-acrylamide resin is 50-250 mu m, and the specific surface area is 400-700 m2/g。
Preferably, the elution solvent for purifying the brominated polystyrene amine-acrylamide resin in the step 2 is one of methanol, ethanol, acetonitrile, isopropanol, toluene, xylene and water.
Preferably, the elution solvent for the purification of the brominated polystyrene amine-acrylamide resin in the step 2 is isopropanol.
Preferably, the collection time for purifying the brominated polystyrene amine-acrylamide resin in the step 2 is 3-6 times of the column volume.
Preferably, the collection time for purifying the brominated polystyrene amine-acrylamide resin in the step 2 is 3.5 to 4 times of the column volume.
The invention has the beneficial effects that: a preparation process of high-purity fullerol, which utilizes chromatography to prepare high-purity fullerol, has the following advantages:
1) the method is simple and only needs two steps of purification;
2) the solvent consumption is less, and is greatly reduced compared with the multi-step liquid-liquid extraction solvent consumption;
3) the purity is high and is more than 95 percent;
4) can distinguish fullerene substituted by different hydroxyl groups, particularly collect the fullerene alcohol with 20-25 hydroxyl groups, and has the characteristics of good water solubility and good free radical removing effect.
The method can selectively purify the fullerol from the fullerene derivative product with high efficiency, has the characteristics of high product purity, high efficiency, solvent saving and simple method, and is easy to realize industrial production.
Drawings
FIG. 1 is a chromatogram of the polystyrene divinylbenzene resin purification in the examples;
FIG. 2 is a purification chromatogram of a brominated polystyrene amine-acrylamide resin in an example;
fig. 3 is a purity chromatogram of fullerol prepared in the example, with a purity of 96.81%.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example (b):
crude preparation: polystyrene divinylbenzene resin purification
The instrument comprises the following steps: suzhou convergent chromatography HT100 series preparative chromatography;
a chromatographic column: 26mm ID x460 mm; 226g of synthetic resin was charged;
the sample loading amount is that the fullerene derivative product is dissolved by toluene, the concentration is 50mg/m L, and the sample loading amount is 500m L;
mobile phase: xylene;
collecting: 4.2-12.8 min of fraction; and (3) post-treatment: rotary steaming and drying;
the purification chromatogram is shown in FIG. 1, and the time periods for collecting the fractions are shown in the figure.
Refining: purification of brominated polystyrene-acrylamide resin
The instrument comprises the following steps: suzhou convergent chromatography HT100 series preparative chromatography;
a chromatographic column: 26mm ID x460 mm; 226g of synthetic resin was charged;
the sample loading amount is that the fullerene derivative product is dissolved by methanol, the concentration is 200mg/m L, and the sample loading amount is 100m L;
mobile phase: isopropanol/water 8: 2;
collecting: fraction of 18.2-23.1 min; and (3) post-treatment: rotary steaming and drying;
the purification chromatogram is shown in FIG. 2, and the time periods for collecting the fractions are shown in the figure.
The target components were collected for analysis and the purity chromatogram was shown in FIG. 3, normalized by the product after integration, with a purity of 96.81%.
Crude preparation: comparison of purification Processes with different macroporous resins (see Table 1)
The instrument comprises the following steps: suzhou convergent chromatography HT100 series preparative chromatography;
a chromatographic column: 26mm ID x460 mm; filling 180-230 g of synthetic resin;
the sample loading amount is that the fullerene derivative product is dissolved by toluene, the concentration is 50mg/m L, and the sample loading amount is 500m L;
mobile phase: xylene;
collecting the fraction, and rotary evaporating for drying.
Refining: comparison of purification of different resins (see Table 2)
The instrument comprises the following steps: suzhou convergent chromatography HT100 series preparative chromatography;
a chromatographic column: 26mm ID x460 mm; filling 180-240 g of synthetic resin;
the sample loading amount is that the fullerene derivative product is dissolved by methanol, the concentration is 200mg/m L, and the sample loading amount is 100m L;
mobile phase: isopropanol/water 8: 2;
collecting the fraction, and rotary evaporating for drying.
TABLE 1 comparison of crude different macroporous resin purification processes
TABLE 2 comparison of crude different resin purification processes
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation process of high-purity fullerol is characterized in that: the preparation process comprises the following steps:
step 1: purifying the polystyrene divinylbenzene resin to remove unmodified fullerene;
step 2: purifying the brominated polystyrene-acrylamide resin, and collecting the fullerol with different hydroxyl groups.
2. The process according to claim 1, wherein the reaction is carried out in the presence of a solvent, and wherein:the particle size of the polystyrene divinylbenzene resin is 200-400 mu m, and the specific surface area is 600-750 m2/g。
3. The process according to claim 1, wherein the reaction is carried out in the presence of a solvent, and wherein: the elution solvent for purifying the polystyrene divinylbenzene resin in the step 1 is one of toluene, xylene, dichlorotoluene or dimethyl sulfoxide.
4. The process according to claim 3, wherein the reaction is carried out in the presence of a solvent, and wherein: the elution solvent for purifying the polystyrene divinylbenzene resin in the step 1 is toluene.
5. The process according to claim 1, wherein the reaction is carried out in the presence of a solvent, and wherein: the collection time of the polystyrene divinylbenzene resin purification in the step 1 is 1-4 times of the column volume.
6. The process according to claim 1, wherein the reaction is carried out in the presence of a solvent, and wherein: the particle size of the brominated polystyrene-amine-acrylamide resin is 50-250 mu m, and the specific surface area is 400-700 m2/g。
7. The process according to claim 1, wherein the reaction is carried out in the presence of a solvent, and wherein: the elution solvent for purifying the brominated polystyrene amine-acrylamide resin in the step 2 is one of methanol, ethanol, acetonitrile, isopropanol, toluene, xylene or water.
8. The process according to claim 7, wherein the reaction is carried out in the presence of a solvent, and wherein: in the step 2, the elution solvent for purifying the brominated polystyrene-acrylamide resin is isopropanol.
9. The process according to claim 1, wherein the reaction is carried out in the presence of a solvent, and wherein: and (3) collecting the purified brominated polystyrene amine-acrylamide resin in the step (2) for 3-6 times of column volume.
10. The process according to claim 9, wherein the step of preparing the high purity fullerol comprises: and (3) in the step 2, the collection time of the purification of the brominated polystyrene amine-acrylamide resin is 3.5-4 times of the column volume.
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| CN202010215591.XA CN111498832A (en) | 2020-03-24 | 2020-03-24 | Preparation process of high-purity fullerol |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013181002A (en) * | 2012-03-02 | 2013-09-12 | Osaka Univ | Fullerene derivative, process for producing the same and resin composition using the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013181002A (en) * | 2012-03-02 | 2013-09-12 | Osaka Univ | Fullerene derivative, process for producing the same and resin composition using the same |
Non-Patent Citations (2)
| Title |
|---|
| 胡长伟: "《纳米材料的生态毒性效应与环境释放风险》", 28 February 2015, 山东人民出版社 * |
| 贾红兵等: "《高分子材料》", 30 November 2009, 南京大学出版社 * |
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