1

RUS
FULLERENE  AND  LIFE PHENOMENON


SYNTHESIS OF FULLERENOL C60(OH)24 OUT OF GLYCERINE
Decline of the classic fullerenol era
The fullerenol C60(OH)24 doesn't contains any sodium


Kozeev A.
Senior Researcher
Scientific and Technical Centre NANOCLASTER
Nizhny Tagil, Russian Federation

Web-site: 
www.nanoclaster.ru

ABSTRACT
Existing methods of synthesis of fullerenols C60(OH)n (polyhydroxylated fullerenes) cannot have prospects for industrial use, primarily because of high cost of the fullerenol, produced by classic methods (electroarc or plasma method). Cost of the fullerenol (polyhydroxylated fullerene) in the process of synthesis is increased by a factor of tens in comparison with the cost of fullerene itself, and today cost of fullerenol C60(OH)n in the world market is 2000-2500 USD/g, which makes it economically unviable. But it has the biggest prospect in such area as pharmacology. Besides, the fullerenol, produced by classic method, will always contain some potassium or sodium hydroxides. Scientific and Technical Centre Nanocluster (STC Nanocluster) has developed an alternative, fully chemical method of production of fullerenol C60(OH)n, based on catalytic hyperaromatization and hypercyclization of products of glycerine dehydration with formation of carbon nanoclusters with closed structure, in the result of which fullerenol C60(OH)24 is produced. Industrial cost price of fullerenol, synthesized out of glycerine, does not exceed 2000-2500 USD/kg. The reason of this low cost price of fullerenol, synthesized out of glycerine, is that the synthesis includes only glycerine, and scanty amount of catalyst  0,02-0,05% of the glycerine mass. Cost of glycerine in Russia, even produced in Germany, is about 0,90 Euro/kg (less than 1 USD). The fullerenol, produced by this method, does not contain hydroxides of alkaline metals.
Fullerenol C
60(OH)24, produced of glycerine, under its appearance, physical-chemical  and chemical  properties, is analogous to fullerenol Cx(OH)n, produced by classic methods: by means of hydroxylation of fullerene by sodium hydroxide, or by means of alkali hydrolysis of fullerene bromide.

SYNTHESIS
The synthesis is based on catalytic dehydration of glycerine. The glycerine, placed in a retort connected with refrigerator, is heated over inoculum catalyst to the temperature of 220-250 degrees (Fig 1). After 20-25 minutes, the distillation of water vapor begins. The quantity of the catalyst is 0.02-0.05%. Such a minimum quantity of the catalyst is reasoned by the fact that with the production of first synthesis products, the process transits to the auto-catalytic mode. In such a way, the initial catalyst is only an inoculum for the start of the dehydration process in the auto-catalytic mode. For example, for the process of dehydration of 200 ml (252 g) of glycerine, only 50-100 mg of catalyst is needed. Form 200 ml of glycerin, 63 g of dehydration product can be obtained using the catalytic dehydration method (see
Fig 2).

Catalytic dehydration of Glycerine  

Catalytic dehydration
Fig 1
Before dehydrationAfter dehydration is over

Product of dehydration of glycerin
Ground product of of dehydration of glycerin
Fig 2
Product of dehydration of glycerin
200 ml (252 g)

Product weight is 63 g

Fig 3
Ground product of dehydration of glycerin

Synthesis mechanism of fullerenols C60(OH)n  out of Glycerine

Stage 1
Stage 1

Stage 2
Stage 2

Stage 3
Stage 3

Stage 4
Stage 4

In the product of glycerine dehydration (see
Fig 2 and Fig 3), along with fullerenols 60()n (n = 2-24), compounds with not loop-closed into sphere structures are contained, in particular, C9H12(OH)9, C36H36(OH)36, C36H12(OH)30, C36H6(OH)24, and other (see Scheme Synthesis mechanism of fullerenols C60(OH)n out of Glycerine), which are intermediate products of synthesis. A large part of those uncompletely fullereneized intermediate products are loop-closed into spherical structures with the nucleus of fullerene by the reaction of catalytic hypercyclization. The product obtained in result of the catalytic hypercyclization is a large-crystals product of black color (see Fig 4), and in the crushed form it is a small-crystals product of brown color (see Fig 5). In appearance, the product of the glycerine dehydration stage and the product of the cyclization stage look similar. But by their chemical composition they are different. The cyclization stage product does not contain compounds with not loop-closed into sphere structures, in particular, C9H12(OH)9, C36H36(OH)36, C36H12(OH)30, C36H6(OH)24, and is free from side-components. The cyclization stage products is nothing else but a mixture of fullerenols 60()12 (85-90%) and 60()24 (10-12%) with a little admixture of fullerenol 60()2 (1-2%) with common formula 60()n.
The solvability of the mixture of fullerenols 60()n in water is insignificant: 2-3 mg/l, because of the predomination therein of fullerenol 60()12  (85-90%), which is practically insoluble in water. The color of the solution of fullerenol 60()n in water is bright-yellow (see
Fig 6). But this solvability is also reasoned not by the fullerenol 60()12, but by the fullerenol 60()24 (10-12%). The fullerenol 60()24 can be extracted from the mixture by distilled water in a Soxhlet-type apparatus. The solvability of the fullerenol 60()24 in water is 40-50 mg/l. The color of the solution of the fullerenol 60()24 in water is yellow (see Fig
7).
From 51 g of fullerenol
60()n (the product of the catalytic cyclization) obtained from 200 ml of glycerine, about 5 g of fullerenol 60()24 can be extracted using water in the Soxhlet-type apparatus. In such a way, from 1.0 l of glycerin, about 25 g of the fullerenol 60()24 can be produced.

Product of cycling stage
Ground product of cycling stage
Fig 4
Product of cyclization stage
  
Product weight is 501 g 
Fig 5
Ground product of cyclization stage

Solution of fullerenol 60()n in water
Solution of fullerenol 60()24 in water
Fig 6
Solution of fullerenol 60()n in water

Soluble 2-3 mg/l
Fig 7
Solution of fullerenol 60()24 in water
Soluble 40-50 mg/l

Solution of fullerenol in ethyl alcohol
Solution of fullerenol in DMFA
Fig 8
Solution of fullerenol
60()24 in ethyl alcohol
Fig 9
Solution of fullerenol
60()24 in DMFA
 

         Analysis of dehydroxylated fullerenol sample mass spectrum

Sample of fullerenol C60(OH)24 was exposed to high-temperature heating in hydrogen atmosphere. As a result, there was a defucylized (dehydroxylation) of fullerenol to fullerene-containing mixture, in which absolute, under its value, peak (Base Peak) was the peak with m/z  equal to 720. In case of z equal to 1, this corresponds to molecular weight of fullerene C60 equal to 720 AMU. Thereby, we can highly assert that the center of this fullerenol is really fullerene C60.

 

Mass-spectrum of dehydroxylated fullerenol C60(OH)n - 2013

Fig 10
Mass spectrum of dehydroxylated fullerenol C60(OH)n - 2013

 

From the fullerenol 60()24 sample, IR spectral data was collected (see Fig 11). For comparison, Fig 12 shows IR spectral data from the literature (J. Braz. Chem. Soc. vol.17 no.6 So Paulo Sept./Oct. 2006). As it can be seen from the comparative analysis of those spectra, main characteristics of spectra are the same.

 

IR spectra of a fullerenols C60

IR spectrum of fullerenol C60(OH)24
synthesized out of glycerine, produced by STC "Nanocluster"


Synthesis of C60(OH)18-20
 in aqueous alkaline solution under O2-atmosphere

J. Braz. Chem. Soc. vol.17 no.6 So Paulo Sept./Oct. 2006
IR spectrum of fullerenol C60(OH)24

IR spectrum of a fullerol synthesis
Fig 11
IR spectra of a fullerenol C60
produced by Institute of Organic Synthesis Ural Division of RAS

IR spectra is the property of the STC STC NANOCLUSTER


Fig 12
Results and Discussion

Figure 2 shows the IR spectrum of a fullerol synthesis. The spectrum is dominated by a broad band at 3380 cm-1due to the stretching mode of the OH groups, as well as other peaks at 1600 cm-1 (C=C), 1390 cm-1 (C-OH) and 1055 cm-1 (C-O). All these bands have been reported before for the compound as belonging to the fullerol molecules.21-25

In such a way, the self-cost of fullerenol 60()24 synthesized from glycerine is 3 orders of magnitude lower than the self-cost of classic  fullerenol produced from fullerene 60. More to that, fullerenol 60()24, synthesized from glycerine does not contain sodium ions. The fullerenol C60(OH)24 doesn't contains any sodium.

Hydroxylation of Low Hydroxylated Fullerenol C60(OH)12
to Mild Hydroxylated Fullerenol C60(OH)24


Almost all companies producing fullerenol 60(OH)24 or selling it actually offer not fullerenol 60(OH)24, but its sodium salt 60(OH)24-n(ONa)n.
That is reasoned by the fact that all technologies for production of classic fullerenol are connected with the use of sodium (or sometimes potassium) hydroxide, and it is very difficult to remove sodium ions from the fullerenol. By contrast to classic fullerenols, fullerenol 60(OH)24 synthesized from glycerine is a genuine fullerenol and does not contain sodium ions.
The classic fullerenol, being by its nature a sodium salt 60(OH)24-n(ONa)n of fullerenol, is not soluble in spirits, in DMF (dimethylformamide), and in DMSO (dimethylsulphoxide). 
By contrast, fullerenol 60(OH)24 produced from glycerine, being genuine fullerenol, is soluble in spirits, in DMF and DMSO (see Fig 8 and Fig 9).
Although the main direct final product of the synthesis from glycerine is low hydroxylated fullerenol 60()12 (85-90%), there are methods which allow to transform low hydroxylated fullerenol 60()12 into mild hydroxylated fullerenol 60()24. One of such methods is described in the article Water-Solubl Single-Nano Carbon Particles: Fullerenol and Its Derivatives,  Ken Kokubo,  Division of Applied Chemistry, Graduate School of Engineering, Osaka University Japan http://cdn.intechopen.com/pdfs-wm/36889.pdf.

The mild hydroxylated fullerenol 60()24 is a fine-crystalline product of brown color which is insignificantly soluble in water, 40-50 mg/l, forming a pale- yellow solution (see Fig 6).
At Scientific Research Center "Nanocluster" own technology for production of mild hydroxylated fullerenol from low hydroxylated fullerenol synthesized from glycerine has been developed. However, in reality, because of the use in this technology of sodium hydroxide NaOH, the final product is not fullerenol 60()24 itself, but its sodium salt 60(OH)24-n(ONa)n.
Sodium salt 60(OH)24-n(ONa)n in crushed form is a fine-crystalline product of brown color which is easily soluble in water, 40-50 g/l, forming, depending of the concentration, solutions of yellow to brown color (see Fig
13). The solubility in water of the sodium salt of fullerenol 60(OH)24-n(ONa)n is 1000 times greater than the solubility of the fullerenol 60()24 itself. But sodium salt of fullerenol is soluble neither in spirits nor in DMF or DMSO.

CONCLUSIONS

The quantity of sodium salt 60(OH)24-n(ONa)n which can be produced from 200 mg of glycerine is 36-38 g which is equivalent to 180-190 g sodium salt 60(OH)24-n(ONa)n from 1.0 l of glycerine.

Solutions of sodium salt of fullerenol 60()24-n(ONa)n in water
Fig 13
Solutions of sodium salt of fullerenol 60()24-n(ONa)n in water
depending on the concentration

Fullerenol C60(OH)24 and its sodium salt 60(OH)24-n(ONa)n can be used in:  

Pharmaceutics and cosmetology
    Antiviral medicine without cytotoxicity;
    Antioxidants, comparable to fullerenes under their effectiveness;
    Wound and burn healing medicine.

Materials science
    Modifiers of polymers, resins, glues, paint-and-lacquer and other materials;
    Modifiers of materials on base of silicate binding agents, including concretes;
    Component of electrolytes for metal galvanic coatings;
    Component of ultra-hard composite materials with metal matrix.

Agroindustry plant cultivation and animal husbandry
    Plant growth stimulants;
    Antiviral and antimycotic agents;
    Preparations, which increase stability of crops by complex nonspecific action;
    Additives to fodders, which increase resistibility of agricultural animals and birds to different diseases, and which do not accumulate in their organism.

In particular:

a) as modifier of epoxy-filled composites:
b) as antiviral medicine of broad spectrum, without cytotoxicity.
c) as microbicids with anti-HIV activity, without cytotoxicity:
1. Dissertation (26.11.2010): Microbicids with anti-HIV activity,  Gilyazova A.V. Gamaleya Institute of immunology, Moscow. Section 6. Research of cytotoxicity, antiviral activity and virucidal effect of addition compounds of carbon nanoclusters, p.18. Fullerenol corresponds to sample no.3.
2. Water Soluble Carbon Nanoclusters as Microbicides with Anti-HIV Activity. A. Gilyazova, G. Kornilaeva, A. Ponomarev, V. Chereshnev, E. Karamov http://figovsky.borfig.com/sita/12_34.aspx
3. Water Soluble Carbon Nanoclusters as Microbicides with Anti-HIV Activity. A. Gilyazova, G. Kornilaeva, A. Ponomarev, V. Chereshnev, E. Karamov. Scientific Israel, Technological Advantages http://www.sita-journal.com/files/4_v.12,%20No.3,4,2010.pdf
d) as a component of cosmetic preparations, which have antioxidant properties.
e) as a component of electrolytes for electrochemical deposition of nanostructured carbon film.  
   

Patents issued for fullerenol:
Russian patent 
No. 2497751 and German patent DE102012103579A1
    

 RU 2497751




The invention can be used in production of modifiers of epoxy-filled composites, microbicids with anti-HIV activity without cytotoxicity, antioxidant additives to makeup preparations. Fullerenol C60 is produced by catalytic dehydration of glycerine during heating. As a catalyst one can use fullerene, fullerenol and other organic and mineral compounds. It is an autocatalytic reaction, and the catalyst is necessary only for "launching" of the synthesis. Hereafter, the produced fullerenol catalyzes synthesis of fullerenol by itself. Thats why the amount of catalyst for launching of the reaction is scanty, 0,02-0,05% of the  glycerine mass.

FULLERENOL C60 AND METHOD OF ITS PRODUCTION OF GLYCERINE

AUTHOR'S PUBLICATIONS

1. Kozeev E.A., Kozeev A.A.  Patent  RU  No. 2497751, 12.28.2011.  FULLERENOL C60 AND METHOD OF ITS PRODUCTION FROM GLYCERINE. http://www1.fips.ru/Archive/PAT/2013FULL/2013.11.10/DOC/RUNWC2/000/000/002/497/751/DOCUMENT.PDF
2. Kozeev E.A., Kozeev A.A.  German patent  DE102012103579A1, 2013.06.20. Fullerenol C60 und Verfahren zu dessen Herstellung aus Glyzerin.
3. T.A. Nizina,  counsellor of RAACS, technical PhD, professor; A.N. Ponomarev, candidate of technical science, professor, STC of "Applied Nanotechnologies" Ltd., St. Petersburg;  S.N. Kislyakov, postgraduate student of Mordovsky state university; A.A. Kozeev, scientific officer of  STC of "Applied Nanotechnologies" Ltd., St. Petersburg.  Results of the research of epoxy compositions, modified by soluble addition compounds of carbon nanoclusters.
4. Endoprosthesis: nanocarbon coating. Electrochemical deposition of nanocarbon film on current-carrying materials http://www.nanochemlab.ru/
5. Kozeyev A.A. Deposizione  elettrochimica  di  film  Nanocarbon  su  materiali  conduttivi. Italian Science Review. 2014; 10(19). PP. 221-223. Available at URL: http://www.ias-journal.org/archive/2014/october/Kozeyev.pdf


E-mail: alex.kozeev@yandex.ru  or   info@nanoclaster.ru
Web-site: www.nanoclaster.ru