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Gurbanova Rena Vagif Hajiyeva Reykhan Shamardan, Azerbaijan State Oil and Industry University Avenue: 20Azadlig, Baku AZ1010. Azerbaijan E-mail: rena06.72@yandex.ru
Research the catalytic activity of the complexes in olefin acrylonitrile Oxidation reactions
Abstract: There has been studied for the first time the process of transition metal and metals salts chlorides to the polymerizing mixture have been shown to effect markedly on the properties of the forming immobilized polymers.
Keywords: Acrylonitrile complex compounds, homogeneous catalytic, Transition, metals, immobilized polymers.
Introduction The understanding of the fundamental processes
The development of new highly efficient ho- determining the formation of active centers in cata-mogeneous catalytic systems on the basis of metal lysts in the course of their preparation as well as dur-complex compounds and their use in the synthesis ing their interaction with reaction medium is neces-processes of polymeric materials for different pur- sary for catalysis theory and creation of new highly poses are of significant interest for catalysis. efficient catalysts for commercial realization [1].
In this connection the research on development of general approaches to the synthesis of transition metal salts with acrylonitrile and study of their structure and physical and chemical properties complexes has been carried out.
The possibility of using the compounds obtained as monomers in polymerization reactions has been studied.
The synthesis of acrylonitrile (ACN) complexes with oxygen intromission and without oxygen intromission has been performed previously by the procedure described in [2; 3].
Results and discussion
ACN complexes solubility in different solvents is of great and principal importance and this, in its turn, determines their application as catalysts in metal-locomplex catalysis. In this connection the influence of solvents nature on ACN complexes solubility has been analyzed. Three types of solvents have been taken: polar (water, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), dimethylformamide (DMF)), middle polar (benzene, toluene) and nonpolar (n-hexane, stable compression process gasoline). It has been found that at the expense of high coordinating ability ACN complexes of iron, manganese, nickel, cobalt chlorides are very well soluble in strong- and middle-polar solvents and moderately in non-polar ones (table 1).
Table 1. - Solubility of acrylonitrile
It was interesting to consider the influence of alkalis and acids upon the properties of the ACN complexes synthesized, i. e. to learn which of the processes, redox or hydrolysis of the starting products, is a dominating one. Ions of iron (II), cobalt (II), manganese (II) unlike those of nickel (II), zinc (II) and cadmium (II) have reductive nature and little stability due to the tendency to form M" compounds. These ions display the reductive properties under the conditions pH>7 and at pH<7 they are very easily oxidized to M (OH)3, such oxidation is accompanied by the change of color.
As a result of alkalis action on iron complexes the solution color changes from pale-yellow to blue color that indicates the formation of iron (II) hydroxide and proceeding the process of starting product hydrolysis, in the case of redox process the pale-yellow color of solution should change to brown — the formation of iron (III) hydroxide.
As a result of hydrochloric acid action on ACN complexes of transition metals the process of the synthesized complexes proceeds as a result of which the regeneration of starting hydrate dichloride and the oxidation of nitrile group to imide one occur. The absorption bands VCONHi of region 17201690 cm-1 are observed in IR-spectra.
complexes of transition metals
Complexes MCl H n H2Q1 mg/l Benzene, mg/l, 20 °C DM SO, mg/l, 20 °C DMF, mg/l, 20 °C Stable compression process gasoline, (fr. 80-140 °C), mg/l, 20 °C
20 °C 50 °C 100 °C
NiCl2 H 20 80 100 45.0 150.0 155.5 36.5
CoCl2 H 11 70 110 40.0 155.7 150.5 5.2
ZnCl, H 9 60 105 38.5 140.5 155.3 3.7
MnCl2 H 12 90 115 35.6 145.7 150.0 30.6
FeCl2 H 10 80 108 43.4 145.6 155.4 31.5
CdCl2 H 8 50 90 37.6 144.5 153.5 2.75
CuCl2 H 11 95 118 40.0 143.4 155.0 6.1
The boiling of these complexes by reactions accompanied by the formation of mixed ligand 1 and 2 in TGF and ethanol (96%) solutions is complexes.
(CH2 = CH-CN)nMCl2 + mEt(OH) ——CH = CH-CN)2MCl2 ■ (EtOH)2 (1)
(CH2 = CH - CN)n MCl2 + m(TGF)2 ——(CH = CH - CN)2 MCl2 ■ (TGF)2 (2)
where M=Ni (II), Co (II), Mn (II), Cd (II), Cu (II), Zn (II) (n=4); M=Fe (II) (n=6).
IR-spectra proved the presence in the complexes the coordinated with metal atom molecules of TGF (VC-O: 810; 1040 cm-1) and ethanol (VOH: 3510 cm-1).
The researches on determination of pour points of the complexes synthesized have been carried out (complexes melt without decomposition), Depending on the nature of central atom pour points vary for Fe (II), Mn (II), Co (II), Ni (II) metals within the temperature range 95-140 °C and for Zn (II), Cu (II), Cd (II) metals within the range 85-130 °C.
The complex structure and ligand iconicity degree determining further its reactivity were judged by the results of thermo stability of the complexes synthesized. To these end thermo graphic studies of acrylonitrile complexes of manganese (II), iron (II) and cadmium (II) without intromission and with intromission of air oxygen within the temperature range 20-550 °C have been conducted.
As thermo graphic studies shows during the heating of iron acrylonitrile complex (ACN)6 FeCN at temperature 65 °C four endothermic points are observed corresponding to temperatures 130 °C, 250 °C, 330 °C, 480 °C. The first three points correspond to ligand (ACN) removal, as to the fourth en-dothermal point, in this case decomposition of iron dichloride is observed. And depending on proceeding condition (in the presence of air oxygen) the products of iron (II) complex (ACN)6FeCl thermo decay at low temperature are mono- and di-acryloni-triles and at high temperature (T>200 °C) the oxidation of acrylonitrile to acrylamide, acrylic acid and the other unidentified derivatives occur.
However, under the similar conditions the thermo decay of manganese (II) acrylonitrile complex (ACN)4MnCl: within the temperature range 20-550 °C differs in principle from thermo decay of iron (II) acrylonitrile complex. This is connected, above all, with the fact that even the traces of oxygen at reduced temperature lead to the polymerization of the removing from coordination sphere manganese (II) atom of acrylonitrile ligand.
At temperature above 200 °C decomposition of chlorine-containing manganese complex occurs.
As to cadmium (II) acrylonitrile complex (ACN)4CdCl2, in this case no specific changes are observed, only at temperature 250 °C cleavage and dimerization of acrylonitrile take place.
The immobilized complexes synthesized have been tested as catalysts for alcohols and ketones oxidation. For this purpose isopropyl alcohol and 2-heptyl cyclopentanone have been used as starting products. Isopropyl alcohol oxidation reaction was carried out in a glass reactor. 60 g of isopropyl alcohol and 0.07% of the catalyst synthesized were charged into reactor. Into the reaction mixture a pure oxygen was fed by means of compressor for 6 hours at feed rate 0.03 cm-1.
The oxidation reaction of isopropyl alcohol was studied within the temperature range from 40 to 80 °C. The results are set in table 2.
For 2-heptyl cyclopentanone oxidation 90 g of the starting synthesized catalyst was charged into the reactor. For oxidation reaction was performed similarly within the temperature range 40-90 °C. The results are set in Table 3.
Table 2.
Temperature, °C Yield of product, % Conversion,% Selectivity,%
40 70 73,7 95,0
50 75 ,5 oo 7 95,6
60 80 82,5 97,0
70 82 84,0 97,6
80 85 87,0 98,0
Table 3.
Temperature. °C Yield of product, % Conversion,% Selectivity,%
1 2 3 4
40 65 66 97,5
50 70 73,7 95,0
1 2 3 4
60 78 81,3 96,0
70 84 86,6 97,0
80 88 90,7 97,0
90 90 91,8 98,0
According to this work a number of specific conclusions may be drawn:
1. The whole complex of the data obtained on conditions for synthesis of transition metals acrylonitrile complexes, influence of solvents, alkalis, acids, the possibility for hydrolysis proceed, origin of the used anhydrous salts of transition metals on the complexing process allowed to realize the selection of optimal conditions for the synthesis
of pure acrylonitrile complexes for further study of their physicochemical properties and application them in metallocomplex catalysis.
2. The immobilized polymers displayed themselves as catalysts for oxidation reaction of isopropyl alcohol and 2-heptyl cyclopentanone providing the proceeding of conversion reactions to the corresponding ketones and esters with high activity and selectivity at low temperatures.
References:
1. Movsumzade E. M., Talipov R. F., Rekuta Sh. F., Agaguseynova M. M., "Organonitrile complexes." Ufa. -GINTL 'Reaktiv',1998.
2. Agaguseynova M. M., Shuman H., Kuliyeva R. V., "Synthesis and study of organonitrile complexes- perspective additives to oils». Moscow, Nefetepererabotka and neftekhimiya, - № 1, P. 48-50, 2004.
3. Agaguseynova M. M., Kuliyeva R. V., Izvestiya VTUZ - № 2 P. 48-50, 2002.
