CN111547706A - Method for removing fullerene solvent residue - Google Patents
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- CN111547706A CN111547706A CN202010392667.6A CN202010392667A CN111547706A CN 111547706 A CN111547706 A CN 111547706A CN 202010392667 A CN202010392667 A CN 202010392667A CN 111547706 A CN111547706 A CN 111547706A
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Abstract
The invention relates to a method for removing fullerene solvent residue by a grinding and crystal transformation method, which comprises the following steps: adding the fullerene crude product containing solvent residues into a sand mill, adding zirconia beads, adding ethanol, grinding, filtering the ethanol to obtain fullerene solid powder, adding the fullerene powder into the sand mill, adding the zirconia beads, adding purified water, grinding, filtering the water to obtain fullerene solid powder, and drying to obtain the fullerene finished product.
Description
Technical Field
The invention belongs to the field of chemical pharmacy, and particularly relates to a method for removing fullerene solvent residue by a grinding and crystal transformation method.
Background
Fullerene (Fullerene) is the third allotrope found in elemental carbon. Any substance consisting of carbon, in a spherical, ellipsoidal, or tubular structure, can be called a fullerene, which refers to a class of substances. Fullerenes are similar in structure to graphite, but the structure of graphite has only six-membered rings, whereas there may be five-membered rings in fullerenes. In the laser vaporization graphite experiment of Kroto et al at Rice university in USA in 1985, the first discovery was that the cluster containing 60 carbon atoms is named C60 and the cluster containing 70 carbon atoms is named C70, and C60 and C70 both have cage structures and can be regarded as three-dimensional aromatic compounds in physical and chemical properties, and the molecular stereo configuration belongs to the symmetry of D5h point group. The spherical structure is formed by 20 regular hexagons and 12 regular pentagons in C60, and 60 vertexes are totally occupied by 60 carbon atoms respectively, and the three homomorphs of carbon are proved to belong to a third allotrope of carbon and are named as Fullerene (Fullerene). The C60 has a haze of about 50%, and due to special structure and properties, the C60 has excellent performances in the aspects of superconductivity, magnetism, optics, catalysis, materials, biology and the like, and is widely applied. In particular, Kratschmer and Huffman et al prepared gram-level C60 since 1990, so that the application research of C60 is more comprehensive and active, and preliminary research shows that the fullerene compound has unique effects in resisting HIV, inhibiting enzyme activity, cutting DNA, performing photodynamic therapy and the like. In 7 months of 2018, the first domestic ton-level fullerene production line created by inner Mongolia carbon valley technology Co., Ltd is put into production in the inner Mongolia call and Haote city formally. A method for preparing fullerene. Mainly include an arc method, a thermal evaporation method, a combustion method, a chemical vapor deposition method, and the like.
The preparation and purification of fullerene mainly comprises that the product is more or less with organic solvent residue in organic solvent, at present, the method for removing the fullerene organic solvent residue mainly adopts supercritical carbon dioxide extraction method, heating vacuum drying or ultrasonic method, which can only remove the solvent adsorbed on the surface and can not remove the solvent residue in the fullerene crystal. In addition, fullerene is in a conjugated polyene organic compound, the fullerene is active in chemical property, oxidation and cyclization addition reaction of double bonds 2+2 between fullerene spheres are easy to occur, and impurities such as fullerene oxide and a dimmer are increased by removing solvent residues by a heating or ultrasonic method, so that the quality standard of new drug research cannot be met. The fullerene is a spherical rigid molecule, a solvent is included in gaps between spheres when rigid spheres of the fullerene are stacked in a crystallization process, the solvent is difficult to remove by a common method when entering fullerene lattices, and at present, the solvent residues purchased from the U.S. and Japan are seriously exceeded after detection, so that the quality standard of drug research cannot be achieved.
A paper of mechanical grinding combined with solid-state crystal transformation for researching the diversification of the solid-state forms of the drugs discloses a mechanical grinding and solid-state crystal transformation method, the paper researches the solid-state diversification of a plurality of drugs, discusses the influence of grinding conditions on the solid-state transformation of the drugs, and investigates the differences of the stability, the solubility, the dissolution rate and the like of each solid-state form. In addition, recent studies have found that grinding a polymorph of a drug mold may cause a crystal transformation, which may greatly affect the bioavailability and therapeutic effects of the finally obtained preparation.
Through research, the invention finds a method for removing the solvent residue in the fullerene crystal, and simultaneously finds a stable, safe and high-purity fullerene new crystal form, thereby achieving the technical effect of killing two birds with one stone.
The method adopts a grinding method to remove the residual solvent of the fullerene, the fullerene particles are broken, cold welded and then broken in the grinding process, the fullerene particles become thin, the crystal lattice is disturbed, the solvent molecules in the fullerene crystal lattice are separated from the crystal lattice and are replaced by ethanol or water, and finally, the residual solvent meets the quality standard of new drug research.
Disclosure of Invention
The invention aims to provide a method for removing solvent residues in fullerene, in particular to a method for removing the solvent residues in the fullerene by grinding.
The method has simple process, the prepared fullerene product has the characteristics of high purity, high content and the like, and the solvent residue meets the quality standard of new drug research and is suitable for industrial production.
The method for removing the solvent residue in the fullerene comprises the following steps:
1) adding the fullerene crude product containing solvent residues into grinding equipment, and respectively adding grinding beads and ethanol for grinding;
2) filtering ethanol to obtain fullerene solid powder;
3) adding the fullerene solid powder into grinding equipment, adding grinding beads and purified water, and grinding;
4) filtering water to obtain fullerene solid powder;
5) vacuum drying to obtain fullerene finished product.
Preferably, the method for removing the solvent residue from the fullerene comprises the following steps:
1) adding the fullerene crude product containing solvent residues into grinding equipment, adding grinding beads, adding ethanol, setting the rotation speed of the grinding equipment at 1000-;
2) filtering the ethanol to obtain fullerene solid powder;
3) adding the fullerene powder into grinding equipment, adding grinding beads, adding purified water, setting the grinding equipment at the rotation speed of 1000-;
4) filtering the water to obtain fullerene solid powder;
5) vacuum drying to obtain fullerene finished product;
wherein, the fullerene in the step 1) includes but is not limited to: hollow fullerenes, metallic fullerenes, and derivatives thereof.
The hollow fullerene includes but is not limited to: c60, C70 and their derivatives C60 hydroxyfullerene, C70 hydroxyfullerene, C60 carboxylic ester, C70 carboxylic ester, C60 amino fullerene, C70 amino fullerene,
among these, metallofullerenes include, but are not limited to: gd @ C82 and derivatives thereof, Gd @ C82 hydroxyfullerene, and the like, without being limited to these fullerenes and derivatives thereof;
the fullerene solvent residue includes but is not limited to: benzene, toluene, o-xylene, m-xylene, p-xylene, o-dichlorobenzene, dichloromethane, methanol, n-hexane, cyclohexane, diethyl ether, petroleum ether, etc.;
the grinding device includes but is not limited to: grinders, sand mills;
the grinding beads include, but are not limited to: silicon carbide, silicon nitride, zirconium oxide;
the ethanol is absolute ethanol or ethanol water solution;
the rotating speed of the sand mill and the grinding and crystal transformation time can be adjusted according to specific conditions;
step 1), 3) the rotation speed of the sand mill and the grinding and crystal transformation time can be adjusted according to specific conditions, preferably the rotation speed is set to 2000-3000 r/min, and the time is 1-3 hours;
the vacuum drying temperature and time in the step 5) can be adjusted optionally according to specific conditions, and the vacuum drying is preferably carried out for 4 to 8 hours at the temperature of between 50 and 70 ℃.
Most preferably, the method for removing the solvent residue from the fullerene comprises the following steps:
1) weighing 10 g of a fullerene C60 crude product containing o-xylene and 1000ml of absolute ethyl alcohol, adding into a sand mill, and adding zirconia beads with the diameter of 0.1 mm;
2) setting the rotation speed of the sand mill at 2500rpm for 2 hours, and filtering with a 0.22 mu m filter membrane after grinding;
3) adding the solid into a sand mill, adding 1500ml of purified water, and adding 0.1mm of zirconia beads;
4) setting the rotation speed of the sand mill at 2500rpm for 1 hour, and filtering with a 0.22 μm filter membrane after grinding to obtain wet fullerene C60;
5) vacuum drying at 60 deg.C for 6 hr to obtain fullerene C70.
It is another object of the present invention to provide a novel crystal of fullerene.
The novel fullerene crystal is obtained by the grinding and crystal transformation method.
The novel fullerene crystal has the following physical and chemical properties: the hollow fullerene and the derivatives thereof and the metal fullerene are converted into brown amorphous powder from black crystals, the particle size is changed from 86 microns to 0.6 micron, and the dissolution rate and the bioavailability can be improved when the hollow fullerene and the derivatives thereof and the metal fullerene are used as medicines.
According to one embodiment, the novel fullerene crystal is prepared by the following method:
1) weighing 10 g of a fullerene C60 crude product containing o-xylene and 1000ml of absolute ethyl alcohol, adding into a sand mill, and adding zirconia beads with the diameter of 0.1 mm;
2) setting the rotation speed of the sand mill at 2500rpm for 2 hours, and filtering with a 0.22 mu m filter membrane after grinding;
3) adding the solid into a sand mill, adding 1500ml of purified water, and adding 0.1mm of zirconia beads;
4) setting the rotation speed of the sand mill at 2500rpm for 1 hour, and filtering with a 0.22 μm filter membrane after grinding to obtain wet fullerene C60;
5) vacuum drying at 60 deg.C for 6 hr to obtain fullerene C70.
In order to detect the fullerene content and the fullerene purity, the invention also provides a method for detecting the solvent residue in the fullerene, which comprises the following steps:
1. apparatus and equipment therefor
Shimadzu gas chromatograph; a headspace autosampler; a one hundred thousand mettler electronic balance;
2. required reagents and drugs
O-dichlorobenzene is chromatographically pure;
3. measurement method
Accurately weighing 100mg of the product, accurately weighing, placing in a 20ml headspace bottle, accurately adding 1, 2-dichlorobenzene, sealing, shaking up to obtain a test sample, accurately weighing another mixed solution containing 21.7 μ g of ethanol, 8.9 μ g of toluene, and 21.7 μ g of o-xylene, M-xylene, p-xylene and ethylbenzene by using 1, 2-dichlorobenzene, quantitatively diluting to obtain a reference sample solution, placing in a 10ml headspace bottle, sealing, measuring by using a solvent residue measuring method (0861 second method in the four-part general rules of the 2015 edition of Chinese pharmacopoeia), and using polyethylene glycol (PEG-20M) (or with similar polarity) as a capillary column chromatographic column of a stationary solution; the initial column temperature was 40 ℃, held for 2 minutes, ramped at a rate of 5 ℃ per minute to 100 ℃, held for 2 minutes, then ramped at a rate of 50 ℃ per minute to 200 ℃, held for 5 minutes; the injection inlet temperature is 200 ℃, the detector temperature is 250 ℃, the headspace bottle equilibrium temperature is 100 ℃, and the equilibrium time is 30 minutes; and (4) taking a headspace sample of the reference solution, recording a chromatogram, and calculating according to an external standard method.
Compared with the prior art, the method for removing the solvent residue in the fullerene has the following advantages:
1. simple operation process and low cost, and is suitable for the industrial production of fullerene.
2. The fullerene product prepared by the method has high purity and content, has no solvent residue, and meets the quality standard of new drug research.
In the invention, the crude fullerene C60 containing o-xylene is obtained from the following sources:
recrystallizing the mixture of the fullerene C60 and the fullerene C70 by o-xylene to obtain a wet fullerene C60 crude product, and drying in vacuum to obtain a fullerene C60 crude product.
In the invention, the toluene-containing fullerene C60 crude product is obtained from the following sources:
and recrystallizing a mixture of the fullerene C60 and the fullerene C70 by toluene to obtain a fullerene C60 wet crude product, and drying in vacuum to obtain a fullerene C60 crude product.
By the method, the hollow fullerene and the derivatives thereof and the metal fullerene are converted into brown amorphous powder from black crystals, the particle size is changed from 86 micrometers to 0.6 micrometer, and the dissolution rate and the bioavailability can be improved when the hollow fullerene and the derivatives thereof and the metal fullerene are used as medicines for development.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not to be construed as limiting the invention thereto.
Example 1
Weighing 10 g of crude fullerene C60 containing o-xylene and 1000ml of absolute ethyl alcohol, adding into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 2 hours, filtering with a 0.22 mu m filter membrane after grinding, adding the solid into the sand mill, adding 1500ml of purified water, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 1 hour, filtering with a 0.22 mu m filter membrane after grinding to obtain a fullerene C60 wet product, drying under vacuum at 60 ℃ for 6 hours to obtain a fullerene C60 finished product, detecting solvent residues by using a headspace gas chromatography, and detecting no o-xylene.
The residual content of o-xylene in the crude fullerene C60 of this example was determined to be 0.82% by headspace gas chromatography.
After removal by the method, the o-xylene residue in the finished fullerene C60 product is detected by headspace gas chromatography to be lower than the detection limit and is not detected.
Example 2
Weighing 10 g of crude fullerene C70 containing o-xylene and 1000ml of absolute ethyl alcohol, adding into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 3 hours, filtering with a 0.22 mu m filter membrane after grinding, adding the solid into the sand mill, adding 2000ml of purified water, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 2 hours, filtering with a 0.22 mu m filter membrane after grinding to obtain a fullerene C70 wet product, drying in vacuum at 60 ℃ for 6 hours to obtain a fullerene C70 finished product, detecting solvent residues by using a headspace gas chromatography, and detecting no o-xylene.
The residual content of o-xylene in the crude fullerene C70 of this example was determined to be 0.86% by headspace gas chromatography.
After removal by the method, the o-xylene residue in the finished fullerene C70 product is detected by headspace gas chromatography to be lower than the detection limit and is not detected.
Example 3
Weighing 100mg of crude metal fullerene Gd @ C82 containing toluene and 500ml of absolute ethyl alcohol, adding the crude metal fullerene Gd @ C82 containing toluene and 500ml of absolute ethyl alcohol into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to be 2500rpm for 1.5 hours, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished, adding the solid into the sand mill, adding 500ml of purified water, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to be 2500rpm for 1 hour, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished to obtain a wet metal fullerene Gd @ C82 product, performing vacuum drying at 60 ℃ for 4 hours to obtain a finished metal fullerene Gd @ C82 product, and detecting solvent residue by using a headspace gas chromatography and detecting no toluene.
The content of residual toluene in the crude metal fullerene Gd @ C82 product of the example was 0.93% by headspace gas chromatography.
After the removal by the method, the toluene residue in the finished product of the metal fullerene Gd @ C82 is detected to be lower than the detection limit by headspace gas chromatography and is not detected.
Example 4
Weighing 10 g of toluene-containing fullerene C60 crude product and 2000ml of anhydrous ethanol, adding the crude product and 2000ml of anhydrous ethanol into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to 2500rpm for 2.5 hours, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished, adding the solid into the sand mill, adding 2500ml of purified water, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to 2500rpm for 1.5 hours, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished to obtain a fullerene C60 wet product, performing vacuum drying at 60 ℃ for 6 hours to obtain a fullerene C60 finished product, detecting the solvent residue by using a headspace gas chromatography, and detecting no toluene.
The residual content of toluene in the crude fullerene C60 of this example was 0.82% as determined by headspace gas chromatography.
After removal by the method, the toluene residue in the finished fullerene C60 product is detected by headspace gas chromatography to be lower than the detection limit and is not detected.
Example 5
Weighing 10 g of toluene-containing fullerene C70 crude product and 2000ml of anhydrous ethanol, adding the crude product and 2000ml of anhydrous ethanol into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 3 hours, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished, adding the solid into the sand mill, adding 4000ml of purified water, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 1.5 hours, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished to obtain a fullerene C70 wet product, performing vacuum drying at 60 ℃ for 6 hours to obtain a fullerene C70 finished product, detecting the solvent residue by using a headspace gas chromatography, and detecting no toluene.
The residual content of toluene in the crude fullerene C70 of this example was 0.86% as determined by headspace gas chromatography.
After removal by the method, the toluene residue in the finished fullerene C70 product is detected by headspace gas chromatography to be lower than the detection limit and is not detected.
Example 6
Weighing 100mg of crude metal fullerene Gd @ C82 containing o-xylene and 1000ml of absolute ethyl alcohol, adding the crude metal fullerene Gd @ C82 containing o-xylene and 1000ml of absolute ethyl alcohol into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to be 2500rpm for 2 hours, filtering the crude metal fullerene Gd @ C82 containing o-xylene with a 0.22 mu m filter membrane after grinding, adding 500ml of purified water into the sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to be 2500rpm for 1.5 hours, filtering the crude metal fullerene Gd @ C8932 containing o-xylene with the 0.22 mu m filter membrane after grinding to obtain a wet metal fullerene Gd @ C82 product, drying the wet metal fullerene Gd @ C82 containing o-xylene in vacuum at 60 ℃ for 4 hours to obtain a finished metal fullerene Gd.
The crude metal fullerene Gd @ C82 product of the example has a residual content of o-xylene of 0.93% as determined by headspace gas chromatography.
After the removal by the method, the o-xylene residue in the finished product of the metal fullerene Gd @ C82 is detected to be lower than the detection limit by headspace gas chromatography and is not detected.
Example 7
Weighing 10 g of toluene-containing hydroxyfullerene crude product and 1500ml of anhydrous ethanol, adding the mixture into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 2 hours, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished, adding the solid into the sand mill, adding 200ml of purified water, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill at 2500rpm for 1 hour, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished to obtain a hydroxyfullerene wet product, drying the hydroxyfullerene finished product for 5 hours in vacuum at 60 ℃, detecting the solvent residue by headspace gas chromatography, and detecting no toluene.
The residual content of toluene in the crude hydroxyfullerene of this example was 0.87% by headspace gas chromatography.
After removal by the method, the toluene residue in the hydroxyl fullerene finished product is detected by headspace gas chromatography to be lower than the detection limit and is not detected.
Test example 1, control experiment
Compared with the product produced by the international well-known fullerene manufacturer, the fullerene solvent residue prepared by the method is obviously superior to that of the fullerene manufacturer in the United states and Japan.
| Fullerene C60 manufacturer | SES corporation of America | Mitsubishi, Japan | Example 1 product |
| Toluene residue (%) | 0.83 | 0.78 | 0 |
Test example 2 screening test
In the research process, the inventor compares and screens various methods, and unexpectedly finds that the grinding and crystal transformation method has obviously better effect on removing the solvent residue than other methods.
1) Screening zirconium oxide grinding beads, grinding at the rotating speed of a sand mill of 2500 rpm:
2) screening by a sand mill at a rotating speed, and grinding under the condition of 0.1mm of zirconia beads:
| rotational speed (rpm) | 500 | 1500 | 2500 |
| O-xylene residue (%) | 0.18 | 0.02 | 0 |
。
Claims (10)
1. A method for removing fullerene solvent residue is characterized by comprising the following steps:
1) adding the fullerene crude product containing solvent residues into grinding equipment, and respectively adding grinding beads and ethanol for grinding;
2) filtering ethanol to obtain fullerene solid powder;
3) adding the fullerene solid powder into grinding equipment, adding grinding beads and purified water, and grinding;
4) filtering water to obtain fullerene solid powder;
5) vacuum drying to obtain fullerene finished product.
2. The method of claim 1, comprising the steps of:
1) adding the fullerene crude product containing solvent residues into grinding equipment, adding grinding beads, adding ethanol, setting the rotation speed of the grinding equipment at 1000-;
2) filtering the ethanol to obtain fullerene solid powder;
3) adding the fullerene powder into grinding equipment, adding grinding beads, adding purified water, setting the grinding equipment at the rotation speed of 1000-;
4) filtering the water to obtain fullerene solid powder;
5) vacuum drying to obtain fullerene finished product.
3. The method of claim 1,
wherein, the fullerene in the step 1) includes but is not limited to: hollow fullerenes, metallic fullerenes, and derivatives thereof,
the hollow fullerene includes but is not limited to: c60, C70 and their derivatives C60 hydroxyfullerene, C70 hydroxyfullerene, C60 carboxylic ester, C70 carboxylic ester, C60 amino fullerene, C70 amino fullerene,
among these, metallofullerenes include, but are not limited to: gd @ C82 and derivatives thereof Gd @ C82 hydroxyfullerene, and the like, without being limited to these fullerenes and derivatives thereof.
4. The method of claim 1,
the fullerene solvent residue includes but is not limited to: benzene, toluene, o-xylene, m-xylene, p-xylene, o-dichlorobenzene, dichloromethane, methanol, n-hexane, cyclohexane, diethyl ether, petroleum ether, etc.
5. The method of claim 1,
the grinding device includes but is not limited to: a grinding machine and a sand mill,
the grinding beads include, but are not limited to: silicon carbide, silicon nitride, zirconia.
6. The method of claim 1,
the ethanol is absolute ethanol or ethanol water solution;
the rotation speed of the sand mill and the grinding and crystal transformation time in the steps 1) and 3) can be adjusted according to specific conditions, and preferably, the rotation speed is set to 2000-3000 r/min for 1-3 hours.
7. The method of claim 1,
the vacuum drying temperature and time in the step 5) can be adjusted optionally according to specific conditions, and the vacuum drying is preferably carried out for 4 to 8 hours at the temperature of between 50 and 70 ℃.
8. The method of claim 1, comprising the steps of:
weighing 10 g of crude fullerene C60 containing o-xylene and 1000ml of absolute ethyl alcohol, adding the crude fullerene C60 containing o-xylene and 1000ml of absolute ethyl alcohol into a sand mill, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to be 2500rpm for 2 hours, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished, adding the solid into the sand mill, adding 1500ml of purified water, adding 0.1mm of zirconia beads, setting the rotation speed of the sand mill to be 2500rpm for 1 hour, filtering the mixture by using a 0.22 mu m filter membrane after the grinding is finished to obtain a fullerene C60 wet product, and performing vacuum drying at 60 ℃ for 6 hours to obtain a fullerene C60 finished product.
9. A novel fullerene crystal produced by the method according to claim 1.
10. The novel fullerene crystal according to claim 9, wherein the novel fullerene crystal is brown amorphous powder having a particle size of 86 μm to 0.6. mu.m.
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