The way to obtain 1-(n-propyl)-2-minihaloes - fullerene
(57) Abstract:Describes a new method to produce 1-(n-propyl)-2-minihaloes( fullerenes, wherein the toluene solution of fullerene C60interacts with excess ethereal solution of n-propylaniline (n-PrMgBr) or n-propylaniline (n-PrMgCl), taken in a molar ratio of C60: n-PrgHal =1:(50-150), in the presence of zirconatetitanate (Cp2ZrCl2as the catalyst, taken in the amount of 1-3 mol.% in relation to n-PrMgHal, in an argon atmosphere under normal conditions within 8-12 hours New magnesium-containing fullerenes can find application in thin organic and ORGANOMETALLIC synthesis. table 1. The invention relates to methods for new magyarkanizsa compounds, specifically, to a method for producing 1-(n - propyl)-2-minihaloes  fullerenes General formula (1):
< / BR>where n = 1-6, C60- new allotropic modification of carbon;
Hal = Br, Cl.Magnesium-containing fullerenes can find application in thin organic and ORGANOMETALLIC synthesis, and products functionalization of (1) are of interest as physiologically active substances, extraction agents, absorbents, additives, shotacon the USSR. The series of chem., 1983, page 218) 1,2-carbamazipine - olefins using diethylamine (Et2Mg) in the presence of catalytic amounts Cp2ZrCl2at room temperature in air, leading to 1-ethyl-2-magnesium-containing alkaram scheme:
< / BR>By a known method cannot be obtained 1-(n-propyl)-2-minihaloes  fullerenes (1).The known method (, U. M. Dzhemilev, O. S. Vostrikova, P. M. Sultanov, A., Kukovinets, L. M. Khalilov. Izvestiya an SSSR. The series of chem., 1984, No. 9, page 2053) 1,2-carbamazipine polyene hydrocarbons, in particular, 1,4 E,9-decatriene using diethylamine (Et2Mg) in the presence of catalytic amounts Cp2ZrCl2under mild conditions in ethereal solvents. Carbamazipine is solely on the terminal double bonds, with internal disubstituted double bond in the reaction is not involved.< / BR>The known method does not allow to obtain 1-(n-propyl)-2-minihaloes fullerenes (1).Thus, to date, the literature contains no information on the synthesis of 1-(n-propyl)-2-minihaloes fullerenes.We propose a new method (synthesis of 1-(n-propyl)-2-magnesium-halogen bonds fullerenes.The method consists in the(n-PrMgBr) or n-propylaniline (n-PrMgCl), taken in a molar ratio of C60: n-PrMgHal = 1 : (50-150), preferably 1:100, in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in an amount of 1 to 3 mol.% in relation to PrMgHal, preferably 2 mol.%, in an argon atmosphere at room temperature (22-23oC) and normal pressure for 8 to 12 hours, preferably 10 hours. Output 1-(n-propyl)-2 - minihaloesfullerenes (1) 76-92%. Output alkyl Mg-containing fullerenes (1) was determined by the products of hydrolysis. The reaction proceeds according to the scheme
< / BR>n = 1 - 6, Hal = Br, Cl
n-Propylaniline (n-PrMgHal) take in excess relative to the fullerene C60with the purpose of introducing into the molecule of fullerene greatest number of n-sawn and holodnognutyh groups. The reduction in the number of n-PrMgHal relative to C60leads to some reduction of the yield of the target products, as well as lower input to the fullerene molecule n-sawn and minigallery groups. Changing the ratio of initial reagents in the direction of increasing the content of n-PrMgHal relative to C60does not lead to a significant increase in the yield of carmagnani fullerene molecules (1).The conduct of a specified reaction in the presence of a catalyst Cp2ZrCl2more than 3 mol.%2 less than 1 mol.% reduces output 1-(n-propyl)-2-minihaloes fullerenes, possibly associated with some decrease in the catalytically active sites in the reaction mass. Experiments were performed at room temperature. At higher temperatures, for example 60oC, no significant increase of the yield of the target products, at a lower temperature, for example 0oC, decreases the reaction rate. Carbamazipine fullerene carried out in toluene solution, as it is the best solvent for fullerene. The original n-propylaniline synthesized in the ether, because it is the best solvent for Grignard reagents.Significant differences of the proposed method:
The proposed method is based on using as initial reagents n-propylaniline (n-PrMgBr or n-PrMgCl) and fullerene C60the reaction proceeds in a mixture of aromatic (toluene) and ether solvent. In the known method are used determine (Et2Mg) and acyclic triene (1,4 E,9-decatriene).The proposed method, in contrast to the known, allows to obtain 1-(n-propyl)-2-minihaloes -fullerene (1), the synthesis of which are not described in literature.The way peaslake in the atmosphere of argon at room temperature was placed 0.05 mmol of fullerene C60, 40 ml dry toluene, 5 mmol n-PrMgBr (0.95 M ether solution) in 20 ml of ether and the catalyst Cp2ZrCl2in the amount of 0.1 mmol (2 mol. % relative to n-PrMgHal), stirred for 10 hours at room temperature (22-23oC). Get 1-(n-propyl)-2 - mineraloid[C60]-fullerenes General formula (1) with the number n-sawn and minigallery fragments from 1 to 6 with a total yield of 84%. Exit (1) was determined by the products of hydrolysis (2):
< / BR>n = 1 - 6.The spectral characteristics of 1-(n-propyl)-2-hydro[C60]- fullerenes (2): the Range of the MRP , M. D.): 0,95 t (CH3, 'J C-H = 7 Hz), 1.29 - 1.50 m (CH2, sawn), 3.70 - 4.05 m (CH, fullerene). The mass spectrum of negative ions n-propylsilane fullerenes (2) consists of the following mass lines: 764 (n-Pr1C60H1), 808 (n-Pr2C60H2), 852 (n-Pr3C60H3), 896 (n-Pr4C60H4), 940 (n-Pr5C60H5), 984 (n-Pr6C60H6).Other examples of the method shown in the table.The reaction was carried out at room temperature (22-23oC). The temperature rise is impractical because there is no significant increase in the yield of the target products. At lower temperatures sijaitsevalle respectively fullerene C60and PrMgHal. The way to obtain 1-(n-propyl)-2-minihaloesfullerenes, wherein the toluene solution of fullerene C60interacts with excess ethereal solution of n-propylaniline (n-PrMgBr) or n-propylaniline (n-PrMgCl), taken in a molar ratio of C60: n-PrMgHal = 1 : (50 - 150), in the presence of zirconatetitanate (Cp2ZrCl2as the catalyst, taken in an amount of 1 to 3 mol.% in relation to n-PrMgHal, in an argon atmosphere under normal conditions within 8 - 12 hours
FIELD: metallurgy, aircraft industry, power engineering, semiconductor technique.
SUBSTANCE: plate tar cake is ground to produce fractional makeup having at least 97 mass % of <0.09 mm-fraction and at least 91 % of <0.045 mm-fraction. Grinded cake is mixed with 35-40 % of coal-tar asphalt and 0.015-1.5 mass % of organic additive at 120-130°C. As organic additive space-hindered phenols and/or phenylphosphites are used. Obtained mass is formed, cooled and crushed followed by pressing to produce semimanufactured article with density of1.01-1.06 g/cm3. Said articles are sintered at 800-1300°C and black-leaded at 3000°C. Finished black-leaded material has bulk density of 1760-1950 kg/cm3, compression strength of 90-105 MPa and blending strength of 60-75 MPa. Material of present invention is useful in production of electrodes, seal assembly and material of high purity.
EFFECT: black-leaded material with improved physical characteristics.
1 tbl, 10 ex
FIELD: aircraft industry, power production.
SUBSTANCE: carbon-carbonic material is impregnated with mixture, containing potassium hydrophosphate, manganese hydrophosphate, phosphoric acid and water in mass ratio of (0.5-0.7):(1.0-2.8):(1.8-2.2):(10-50), respectively. Then material is dried and heat treated with temperature rising rate of 15-20°C/h up to 650-700°C to produce 2.0-5.0 mass % of ultraphosphate as calculated to starting material weight. Dried material is cooled, impregnated with mixture of furfuryl alcohol and phenol-phormaldehyde resin in mass ratio of (8.0-9.0):(1.2-2.0), respectively, heat treated again with temperature rising rate of 8-20°C/h up to 280-350°C to produce solid residual content of 0.5-5.0 mass %. Method of present invention makes it possible to reduce oxidative losses when heating at 600°C in air up to 0.1-0.25 %/h and to obtain material with compressive resistance of 120-150 MPa and long-term serviceability at 520-550°C.
EFFECT: decreased oxidation losses; material with increased compressive resistance and serviceability.
1 tbl, 5 ex
SUBSTANCE: solid carbon materials are calcined at 1200-1300°C, crushed, riddled, dosed, and mixed with binder for 3-5 min at 140-180°C. Following amounts of ingredients are employed: 23-57% thermoanthracite, 25-55% iron coke, and coal-tar pitch in balancing amount. Molten electrode mass is treated to mold briquettes. Carbon electrodes made from mass according to invention show resistance 83.9-96.4 Ohm*mm2/m and conductivity 2.6-4.8 W/m*deg.
EFFECT: improved performance characteristics.
FIELD: carbon materials.
SUBSTANCE: reaction space is evacuated and filled with helium to pressure 0.1-0.4 atm, coaxial graphite electrodes are brought together to ignite electric arc between them, and graphite is evaporated at voltage 40-60 v and current intensity 250-400 A. Simultaneously, electrodes are continuously affected by video pulse packets characterized by duration 2·10-4-2·10-3 s, relative pulse duration in packet 10-100, and power 1-15 W. Resulting products are moved in helium flow and precipitated in carbon black collector in the form of fullerene-containing carbon black. To remove carbon black from inner surfaces of working chamber and carbon black collector, the surfaces are affected by alternate-polarity pulses with repetition frequency 50-500 Hz and power 1-10 W. To remove fragments of destroyed graphite rods and cathode deposit scoria from chamber space to bottom part of working chamber, pulse magnetic field with frequency 3-15 Hz and magnetic induction 0.05-0.1 Tl.
EFFECT: increased content of fullerenes in carbon black and reduced power consumption.
FIELD: electrode making industry branch, metallurgy.
SUBSTANCE: method comprises steps of baking hard carbon- containing material such as thermoanthracite, anthracite, coke, breaking them and treating in vapors of coal tar separated from liquid phase of heavy coal-tar products whose mass consists 25 -30 % of mass of hard carbon- containing materials; sieving treated carbon-containing materials, metering them and mixing with binder for 3 - 5 min at 140-180°C; shaping briquettes of melt electrode mass. Self-firing electrodes made of composition according to invention features next characteristics: density, 1.71 - 1.98 g/cm3; specific electric resistance, 73.3 - 81.4 Ohm mm2/m, compression strength, 34.1 - 35.2 MPa.
EFFECT: enhanced properties of electrodes.
3 cl, 1 tbl, 6 ex
FIELD: carbon materials.
SUBSTANCE: powderlike catalyst is continuously fed into tubular reactor and displaced along reactor axis. Following composition of catalyst can be used: 70-90% Ni and 10-30% MgO or 40-60% Co and 40-60% Al2O3, or Mo, Co, and Mg at molar ratio 1:5:94, respectively. Process is carried out continuously at countercurrent catalyst-hydrocarbon contact. In the first zone(s) catalyst is activated by gases leaving hydrocarbon pyrolysis at 450-600°C. Residence time of catalyst ranges from 5 to 180 min. Activated catalyst is passed into pyrolysis zone(s) at 550-1000°C. Into the same zone(s), hydrocarbons, e.g. methane, are countercurrently passed. Residence time of catalyst in pyrolysis zone(s) ranges from 0.5 to 180 min. Invention can be used in sorbent, catalyst, and composite manufacturing processes.
EFFECT: enabled continuous manufacture of layered nanotubes or bent hollows fibers, reduced number of stages and consumption of reagents.
4 cl, 2 dwg, 7 ex
SUBSTANCE: proposed method includes evacuation of hermetic chamber 1 and filling it with helium. Then voltage is supplied to cathode 4 and anode 5 located respectively in cathode lead-in 2 and anode lead-in 3. Cathode lead-in 2 moves in longitudinal direction and anode lead-in 3 is immovable. After burning of anode 5, its replacement is performed automatically from rod loader 11. Anode 5 and cathode 4 are enclosed in metal casing 6 with open ends; it is mounted coaxially relative to electrodes. Casing 6 is turnable and its longitudinal axis coincides with axis of upper flange 7 and lower flange 8. Upper flange 7 is provided with axle with piston 9 for forcing fullerene-containing black to storage chamber 10 mounted on lower flange 8. Black thus obtained is subjected to treatment in Soxlet apparatus with aromatic solvent-toluene. To this end, use is made of excessive amount of black relative to saturated solution of mixture of fullerenes in toluene. Extract containing up to 95% of C60 settles on hot bottom of apparatus. Solution above sediment is enriched with C70 up to 70%. Then fullerence C60 and C70 are separated independently and in parallel in chromatographic columns with use of activated charcoal as immovable phase. Toluene or chlorobenzene is used as movable phase. Target product is crystallized and is additionally cleaned by re-crystallization or sublimation in vacuum, thus obtaining C60 at purity of 99.9% and C70 at purity of 99.5%.
EFFECT: enhanced reliability and facilitated procedure of method.
4 cl, 1 dwg
FIELD: electrical production of ferro-alloys and steel; manufacture of self-roasting electrodes.
SUBSTANCE: proposed electrode mass contains thermo-anthracite, coal-tar pitch and modifying agent in form of polymers of benzene separation at the following ratio of components, mass-%: thermo-anthracite, 70-79; coal-tar pitch, 20-28; polymers of benzene separation (wastes of by-product coke industry), 1-2. Ratio of fractions of thermo-anthracite in electrode mass, mass/%: -16+6 mm, 11-21; -6+0.063 mm, 28-38; the remainder being lesser than +0.063 mm. Benzene separation polymers have the following ratio of components, mass-%: agents not soluble in toluene, 2.0-4.0; water, 0.05-0.10; ash, 0.10-0.15; the remainder being aromatic hydrocarbons. Mechanical strength of electrodes is equal to 19.7-22.3 Mpa and porosity of electrodes is equal to 19.8-20.6%.
EFFECT: enhanced efficiency.
3 cl, 2 tbl
FIELD: by-product-coking industry; electrode industry; production of compositions for impregnation of graphitized carbon products.
SUBSTANCE: the invention is pertaining to the compositions for impregnation of graphitized carbon products and may be used in the by-product-coking industry and electrode industry. The impregnating composition of graphitized carbon products includes a coal-tar pitch and a plasticizer, in capacity of which use polymeric compounds of the benzene group (wastes of the by-product-coking process), at the following ratio of the components (in mass %): the coal-tar pitch - 94-96; polymeric compounds of the benzol group - the rest. The polymeric compounds of the benzol group have following composition(in mass %): substances insoluble in a toluene - 1.0-3.0; water - 0.05-0.10; ash - 0.10-0.15; aromatic hydrocarbons - the rest. Density of the graphitized carbon products impregnated with this composition after burning makes 1.78÷1.89 g/cm3; after graphitization - 1.85÷1,90 g/cm3, porosity - 19.2÷19.9 %, a mechanical strength - 26.5÷27.5 MPa. The invention also allows to improve production conditions due to reduction of the content of the carcinogenic substances in the peck.
EFFECT: the invention ensures an increased density of the graphitized carbon products impregnated with this composition by several percents, improved production conditions due to reduction of the carcinogenic substances share in the peck.
2 cl, 2 tbl