CN1116260C - Process for preparing Cy(OH)n - Google Patents
Process for preparing Cy(OH)n Download PDFInfo
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- CN1116260C CN1116260C CN 01109496 CN01109496A CN1116260C CN 1116260 C CN1116260 C CN 1116260C CN 01109496 CN01109496 CN 01109496 CN 01109496 A CN01109496 A CN 01109496A CN 1116260 C CN1116260 C CN 1116260C
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Abstract
The present invention relates to a new method for preparing fullerenol Cy(OH)n, which comprises: solid-phase grinding fullerene halide and strong alkali carry out reaction, and then fullerenol is separated from the neutral water solution of the solid-phase grinding fullerene halide and the strong alkali by methanol. The method of the present invention has the advantages of simplicity, high efficiency, high yield, no byproduct, stable structural composition and performance of the fullerenol, and the water solution of the fullerenol can be stably preserved for more than 5 years; the fullerenol can be widely used for the fields of biology, medicine, the synthesis of high molecular materials, the synthesis of organic functional materials, etc.
Description
The invention relates to a novel method for preparing fullerol, in particular to a novel method for preparing the fullerol by solid-phase grinding.
Fullerol Cy(OH)nThe molecular structure has multiple electron releasing groups, but retains the parent fullerene CyA conjugated system of pi-bonds formed by conjugated double bonds of (A) to (B) to (C)y(OH)nThe molecular structure of the polymer has an electron affinity group and an allylhydroxyl group, and the structural characteristics of the polymer make the polymer have extremely high solubility in water, so that the polymer is possibly used as a free radical scavenger or a water-soluble antioxidant in a biological system and is attracted attention. Various methods for producing fullerol have been proposed so far. As early as 1992 Abdul n, et al Tetrahedron lett, 1992, 32 (47): 7097 the first example reports heating of solid C mixed with excess KOH under vacuum60/C70The fullerene toluene solution gradually fades the color of the solution to be colorless to generate C60(OH)nA fullerene alcohol precipitate. Li J et al, J. chem. soc. chem. commun.1993, 23: 1784 reports on the use of tetrabutylammonium hydroxide (TBAH) as a phase transfer catalyst for catalyzing C60The phase transfer reaction between the fullerene toluene solution and the concentrated NaOH aqueous solution directly leads C in the toluene solution60Conversion of fullerene to C60(OH)nAn aqueous solution of fullerol, wherein n is 24-26. Huang L.Y. et al 1992-1996 were described in J.chem.Soc.chem.Commun, 1992, 22: 1791; j.am.chem.soc., 1993, 115 (13): 5453; chem., 1994, 59 (4): 3960; j.am.chem.soc., 1992, 114 (26): 10154; tetrahedron, 1996, 52 (14): 4963; US5,117,248, US5,294,732, report the synthesis of fullerol using an acid route. Such as C60Fullerene and oleum (H)2SO4) At 55 ℃ N2Then hydrolyzed with NaOH aqueous solution at room temperature to generate C with n-10-1260(OH)nA fullerol; or with C60Fullerene toluene solution and HNO3/NaNO3System for carrying outReaction to form C-60(NO2)nIntermediate is hydrolyzed by NaOH aqueous solution to generate C60(OH)nThe reaction formula is as follows: n is 16 at maximum;
sunday, et al, in the "chemical journal of higher school" 1996; 17: 19 above reports C60Fuller (F)Reflux reaction of alkene with potassium metal in toluene, C60Complete conversion to insoluble KnC60Then hydrolyzed to form C60(OH)nA dark brown aqueous solution of (a).
In the above-mentioned methods for preparing fullerol, C is obtained by different preparation methods60(OH)nThe number n of hydroxyl groups in the molecule is different, and n varies from 10 to 26; moreover, the preparation method has complicated steps, side reactions, byproducts, reaction time control and other problems, which all lead to C60(OH)nUncertainty in structural composition, unstable performance, and C60(OH)nAre greatly limited in various applications.
The invention aims to overcome the problems in the preparation method of the fullerol, and provides a simple and efficient preparation method of the fullerol C with stable molecular structure composition and performance through research and research of the inventor and long-term practicey(OH)nIn particular to a novel method for preparing fullerol by solid-phase grinding.
The invention provides a method for preparing fullerol Cy(OH)nThe method comprises the following steps:
1. the reaction of fullerene halides (CyXn) with strong bases such as NaOH or KOH is carried out at temperatures<100 ℃.
2. Dissolving the reaction product in the step 1 by using water, neutralizing the reaction product by using hydrochloric acid until the pH value is approximately equal to 7, and separating the product of the fullerol Cy (OH) n by using methanol.
In the method for preparing the fullerol, the general formula of the fullerene halide in the step 1 is CyXn, wherein C represents carbon atoms, Y is an even number (integer number) from more than or equal to 60 to less than or equal to 540, such as 60, 70, 76, 78, 82, 84, 88, 90, 92, 96, 100, 104 and the like; preferably 60, 70, 76, 78, 82, 84; more preferably 60, 70. n is an even number from 2 to 72, such as 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 … … 72; preferably 10, 12, 14, 16, 18, 20, 22, 24; more preferably 10, 16, 20, 24, and n is generally expressed as an average in CyXn. X is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), preferably Cl.
A specific example of CyXn is C60Fn、C60Cln、C60Brn、C100Cln、C60ln、C60/C70Fn、C60/C70Cln、C60/C70In、C60/C70Brn、C76Cln、C84Cln、C90Brn、C100Cln, etc., e.g. C60F18、C60F36、C60F48、C60F70、C60Cl8、C60Cl10、C60Cl12、C60Cl16、C60Cl20、C60Cl22、C60Cl24、C60Cl28、C60Cl34，C60Br18、C60Br22、C60Br34，C60l2、C60I4，C60/C70Cl10、C60/C70Cl18、C60/C70Cl20、C60/C70Cl22、C60/C70Cl24、C60/C70Br10、C60/C70Br16、C60/C70Br18、C60/C70Br22、C60/C70Br24，C60/C70I2、C60/C70I4Etc., wherein C is preferred60Cl12、C60Cl14、C60Cl18、C60Cl20、C60Cl22、C60Cl24、C60/C70Cl18、C60/C70Cl20、C60/C70Cl22、C60/C70Cl24、C60/C70Br18、C60/C70Br22、C60/C70Br20、C60/C70Br24And the like.
The strong base is NaOH or KOH, etc., preferably NaOH.
The reaction of the fullerene halide with a base, such as NaOH, may be carried out in any manner,
for example, liquid-liquid reaction, liquid-solid reaction or solid-phase reaction, preferably solid-phase grinding. The reaction temperature may be in a wide range without any limitation, for example, in the range of 0 ℃ to 90 ℃, preferably room temperature. The reaction environment is not particularly limited and may be in air or an inert gas such as nitrogen, preferably nitrogen, so that the influence of impurities on the reaction can be avoided. If solid phase grinding is adopted to prepare the fullerol, the grinding time is determined by the amount of the reaction materials and the grinding operation, generally 0.5-5 hours, until the reaction is completed, and the conversion rate and the yield are both over 90 percent. The solid-phase grinding reaction can be carried out in a glass mortar, corundum mortar, agate mortar, and if the preparation amount is large, it can be carried out in a mechanical grinding machine, for example, in a ball mill. In order to prevent the powder from splashing during the grinding, a proper amount of water such as water may be added to be 1 to 10% by mass of the reaction mass.
In solid phase grinding chemistry, the halogen atom, e.g., Cl atom, in the CyXn molecule is exchanged with the hydroxyl (OH) group in the base, e.g., NaOH molecule. Cy such as C due to spherical symmetry60The molecule has a plurality of, e.g., 30, conjugated pi bonds and has an extremely strong electron affinityAnd electronegativity, the activation energy required for the exchange reaction is small, very similar to acid-base neutralization. Generation of Cy (OH)nWith NaX, e.g. C60(OH)nThe aqueous solution of the paste is a dark brown paste of NaCl, and the aqueous solution is a dark red transparent solution (n is 18-24), and is stable for more than 5 years for a long time. Cy (OH)nThe number n of hydroxyl groups in the molecule is determined by the reactant CyClnThe number n of halogen atoms such as chlorine atoms in the molecule is determined, and by controlling the number n of different halogen atoms such as chlorine atoms, a fullerene Cy (OH) having a number n of hydroxyl groups different from that of the corresponding fullerene can be producednOn average, n is an even number from 2 to 72, preferably an even number from 6 to 24, for example, n is 6, 8, 10, 12, 14, 16, 18, 20, 22, 24. Efficient solid phase grinding reaction, CyXn being e.g. C60ClnCan be made intoPartial conversion to Cy (OH)nSuch as C60(OH) n, without side reactions and by-products. To the ground reaction product Cy(OH)nDissolving the black paste with NaCl in water, neutralizing with HCl to pH 7, adding methanol, and adding methanoly(OH)nFrom its aqueous solution, NaCl was completely separated.
The fullerene halide being different with the starting material of the reaction, e.g. C60/C70ClnMixture, C60Cln、C70Cln、C76Cln、C84Cln、C100Cln、C60BrnEtc. can prepare the corresponding C60(OH)n、C60/C70(OH)n、C70(OH)n、C76(OH)n、C84(OH)n、C100(OH) n, etc., wherein n may have an even number average of 2 to 72, preferably n is 6 to 34. Follow-up determination of reactants, e.g. C, in practice by infrared spectroscopy60ClnThe characteristic C-Cl stretching vibration of the molecule is 847-887cm-1Whether the twogroups of absorption peaks nearby disappear or not determines the progress of the grinding chemical reaction. Typically 847cm was observed after 0.5h of grinding-1、887cm-1The nearby absorption peak had disappeared completely, and the reaction product C60(OH)nThe characteristic absorption peaks of (A) are: 3426cm-1Nearby O-H bond vibration peak, 1617cm-1Nearby C ═ Cn double bond stretching vibration peak, 1396cm-1Bending vibration peak in nearby O-H bond surface, 1092cm-1Nearby C-O11Peak of key expansion and contraction vibration, and 473cm-1Nearby absorption peaks. Purified C60(OH)nN is 18-24, which1H-NMR measurement results show that the chemical shift of 24 hydroxyl protons only shows a single peak by using DMSO-d6 as a solvent: 3.53X 10-6Quite similar to the data of the literature. C prepared in different ways60(OH)nThe comparison of the relative absorption peak intensities of the infrared absorption spectra of the molecules shows that the relative intensities among the peaks of the infrared absorption spectra of the fullerol prepared by the solid phase grinding method are obviously different from those of the fullerol prepared by the method reported in the literature. The n-20-24C prepared by the method60(OH)n1617cm of infrared absorption spectrum of molecule representing C ═ C double bond-1The nearby peaks are relatively obviously weakened, and the other three absorption peaks respectively represent OH and C-O absorption peaks and are relatively obviously enhanced. This measurement demonstrates that C is produced by the method of the present invention60(OH)nThe number of hydroxyl groups on the molecule is higher than in other methods.
The method for preparing the fullerol provided by the invention is characterized by comprising the followingsteps:
1. simple process, high efficiency and high yield.
2. Adapting to wide surface and obtaining serial fullerol.
3. The molecular structure and composition of the fullerol are determined, the performance of the fullerol is stable, and the aqueous solution of the fullerol can be stable for more than 5 years.
4. No side reaction, no side product, no need of solvent and low cost.
The method can provide reliable fullerol of various products for further application research of biology, medicine, high polymer material synthesis, organic functional material synthesis, fullerene water solution chemical research and the like of the fullerol.
The invention will be further illustrated by the following examples, without limiting the scope of the invention to the examples listed.
Example 1
99.9% of C was weighed60ClnAnd n-22-24, about 30mg (equivalent to 2X 10) of ginger-yellow powder-5mol), was mixed with 200mg of solid, granular NaOH (commercially available analytical reagent) and placed in N2The milling was carried out under an atmosphere at room temperature for about 0.5 hours and the reaction product was a dark brown paste. Sampling and measuring the infrared absorption spectrum. If it is marked C60ClnCharacteristic absorption peak of 847cm-1，887cm-1Has completely disappeared to show that C60ClnHas been totally converted into C60(OH)nAnd n is 22-24. Otherwise, continuously grinding to C60ClnAnd (4) complete conversion. The reaction product was dissolved in about 10ml of distilled water to give a reddish brown color C60(OH)nAqueous solution, neutralized to pH about 7 with hydrochloric acid of appropriate concentration, and then treated with C8-10 ml of methanol60(OH)nSeparating from water, centrifuging, removing supernatant, dissolving with 3-5ml distilled water, dissolving C with 3-5ml methanol60(OH)nAnd separating out until all NaCl is separated out. The product was dried under vacuum at 80 ℃ and charged with N2The product is preserved or prepared into water solution for preservation, and the yield is more than 90 percent.
Example 2
Weighing C60Cln/C70ClnMixed, n-22-24, ginger-yellow powder in appearance (wherein C60/C70In a mass ratio of between 100 and 70/0 and 30), about 30mg of NaOH in solid granular form (commercially available analytical reagent) was mixed with 200mg of NaOH in N2The milling was carried out under an atmosphere at room temperature for about 0.5 hours and the reaction product was a dark brown paste. Sampling and determining the infrared absorption spectrum, if labeled C60Cln/C70ClnCharacteristic absorption peak of 847cm-1，887cm-1Has completely disappeared to show that C60Cln/C70ClnHas been completely converted to generate C-60(OH)n/C70(OH)nAnd n is 22-24. Otherwise, continuously grinding to C60Cln/C70ClnAnd (4) complete conversion. The reaction product was dissolved in about 10ml of distilled water to give a reddish brown color C60(OH)n/C70(OH)nAqueous solution, neutralized to pH about 7 with hydrochloric acid of appropriate concentration, and then treated with C8-10 ml of methanol60(OH)n/C-70(OH)nCompletely separating out from water, centrifuging, removing supernatant, dissolving with 3-5ml distilled water,then adding 3-5ml of methanol to the mixture to obtain C60(OH)n/C70(OH)nAnd separating out until all NaCl is separated out. The product was dried under vacuum at 80 ℃ and charged with N2The product is preserved or prepared into water solution for preservation, and the yield is more than 90 percent.
Example 3
Weighing C60Cln/C70ClnMixed, n-12-14 (average n-14), earthy yellow powder in appearance, about 30mg (equivalent to 2 × 10)-5mol) was mixed with 145mg of solid, granular NaOH (commercially available analytical reagent) and placed in N2The reaction product was a dark brown paste when ground at room temperature in an atmosphere for about 0.5 h. Sampling and determining the infrared absorption spectrum, if labeled C60Cln/C70ClnCharacteristic absorption band 847cm of the mixture-1，887cm-1Has completely disappeared to show that C60Cln/C70ClnHas been completely converted into C60(OH)n/C-70(OH)nAnd n is 12-14. Otherwise, continuously grinding to C60Cln/C70ClnAll conversion to C60(OH)n/C70(OH)n. The reaction product is dissolved in about 10ml of distilled water as a brownish yellow (yellowish) aqueous solution, neutralized to a pH of about 7 with hydrochloric acid of an appropriate concentration, and C is neutralized with 8 to 10ml of methanol60(OH)n/C70(OH)nSeparating from water, centrifuging, removing supernatant, dissolving precipitate with 3-5ml distilled water, dissolving C with 3-5ml methanol60(OH)n/C70(OH)nAnd separating out until all NaCl is separated out. The product was dried under vacuum at 80 ℃ and charged with N2Storing or preparing into water solution for storage. The yield is more than 90%.
Example 4
Weighing C60Cln/C100ClnMixed sample, n-20-24, in ginger yellow powder appearance (mixed sample C)100/C60Mass ratio<1%), about 30mg was mixed with 200mg of solid granular NaOH (commercially available analytical reagent) and placed in N2The milling was carried out under an atmosphere at room temperature for about 0.5 hours and the reaction product was a dark brown paste. Sampling and determining the infrared absorption spectrum, if labeled C60Cln/C100ClnCharacteristic absorption peak of 847cm-1，887cm-1Has completely disappeared to show that C60Cln/C100ClnAnd n is 22-24 after complete conversion. Otherwise, continuously grinding to C60Cln/C100ClnComplete conversion to C60(OH)n/C100(OH)n. The reaction product was dissolved in about 10ml of distilled water to give a reddish brown color C60(OH)n/C100(OH)nAqueous solution, neutralized to pH about 7 with hydrochloric acid of appropriate concentration, and then treated with C8-10 ml of methanol60(OH)n/C100(OH)nSeparating from water, centrifuging, removing supernatant, dissolving with 3-5ml distilled water, dissolving C with 3-5ml methanol60(OH)n/C100(OH)nAnd separating out until all NaCl is separated out. The product was dried under vacuum at 80 ℃ and charged with N2The product is preserved or prepared into water solution for preservation, and the yield is more than 90 percent.
Claims (7)
1. A method of producing fullerol, the method comprising the steps of:
(1) reacting the fullerene halide with a strong base selected from sodium hydroxide or potassium hydroxide;
(2) dissolving the reaction product obtained in step 1 in water, and neutralizing with hydrochloric acid until the pH value is close to
And 7, separating the fullerol from the methanol.
2. A process for the preparation of fullerol according to claim 1 characterised in that the fullerene halide is CyXn, where C represents a carbon atom, y is an even number from 60 to 540, n is an even number from 2 to 72 and X is F, Cl, Br, I.
3. A method of preparing fullerol according to claim 1, characterised in that the fullerene halide is C60Cln、C60/C70Cln、C76Cln、C84Cln、C100Cln. Where n is an even number from 6 to 34.
4. A method of producing fullerol according to claim 1, characterised in that the fullerol is C60(OH)n、C60(OH)n/C70(OH)n、C76(OH)n、C84(OH)n、C100(OH)n. Where n is an even number from 6 to 34.
5. A process for producing fullerol according to any one of claims 1 to 4, characterised in that the fullerene halide is subjected to solid phase milling reaction with a strong base selected from sodium hydroxide or potassium hydroxidein nitrogen or air at 0-90 ℃ for 0.5-5 hours.
6. A process for producing fullerol according to any one of claims 1 to 4, characterised in that the milling reaction is carried out at room temperature under nitrogen.
7. A process for producing fullerol according to claim 1, characterised in that the fullerol is separated multiple times with methanol.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296054C (en) * | 2004-05-14 | 2007-01-24 | 中国科学院上海应用物理研究所 | Application of fuller alcohol as ramification of C60 in nourishing hair |
| CN1312031C (en) * | 2004-09-03 | 2007-04-25 | 中国科学院化学研究所 | Method for synthesizing gadolinium metal fullerol using ultrasonic wave |
| CN102849717B (en) * | 2012-09-12 | 2014-12-10 | 深圳市通产丽星股份有限公司 | Fullerol and preparation method thereof |
| CN103086344B (en) * | 2012-12-27 | 2014-12-17 | 深圳市通产丽星股份有限公司 | Equipment for producing fullerol |
| CN104030898A (en) * | 2014-05-17 | 2014-09-10 | 青岛科技大学 | Amphipathic fullerene derivative and preparation method thereof |
| CN104555977B (en) * | 2014-12-11 | 2017-01-18 | 河南农业大学 | Preparation method of fullerol |
| KR20190142930A (en) * | 2018-06-19 | 2019-12-30 | 삼성전자주식회사 | Hydroxyl fullerene dispersion and method of preparing the same and polishing slurry including the same and method of manufacturing semiconductor device |
| KR20200010806A (en) | 2018-07-23 | 2020-01-31 | 삼성전자주식회사 | Polishing slurry and method of manufacturing the same and method of manufacturing semiconductor device |
| CN112592481A (en) * | 2020-12-14 | 2021-04-02 | 苏州经贸职业技术学院 | Method for modifying polyaniline polymer |
| CN115246639B (en) * | 2021-04-28 | 2024-02-06 | 广州汇材科技有限公司 | Green macro preparation method of fullerol |
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