RADIATION POLYMERIZATION OF n.HEPTENE IN THE PRESENCE OF TiCI~
Yu. A. K o l b a n o v s k i i , L. S. P o l a k a n d E. B. Shlikhter, N e f t e k h i m i y a 3, No. 2, 222-226, 1963. TIlE radiation polymerization of n-hept- 1-ene in the presence of TiC14 has been studied, together with the influence of the dose, the dose rate, the temperature of the irradiation, the amount of catalyst, and the dilution on the yield of polymer. The optimum conditions for polymerization with TiC14 are dilute solutions and high temperatures. When only the energy absorbed by the monomer is taken into account, the radiation-chemical yields amount to ~ 50 mole/100 eV. It has been established that the yield of polymer depends on the 0"8-th power of the dose rate. THE REASON FOR THE CONSTANCY OF THE RATE OF REACTION IN THE OXIDATION OF n.DECANE
V. M. Gol'dberg a n d L. K. O b u k h o v a , N e f t e k h i m i y a 3, No. 2, 233-237, 1963. IN TIIE autoxidation of n-decane, the rate of regeneration of the radicals increases proportionally to the amount of unchanged hydrocarbon. An equation has been given which describes the kinetics of the decomposition of n-decane. A magnitude kz/.~/~ which characterizes the reactivity of a hydrocarbon has been measured; its nmnerical magnitude for n-decane is 2.0 × 10-a l 1/~ mole -1/* sec -I/$. Di-tbutyl peroxide was used as the initiator of the process. THE INTERMEDIATE STAGES OF THE LIQUID-PHASE OXIDATION OF SECONDARY ALCOHOLS TO KETONES
Yu. B. K r y u k o v , R. M. S m i r n o v a , V. A. Seleznev, V. V. K a m z o l k i n a n d A . N. B a s h k i r o v , N e f t e k h i m i y a 3, No. 2, 238-245, 1963. USING tetradecanols as example, it has been established that the liquid-phase oxidation of higher secondary alcohols with molecular oxygen enriched with the heavy isotope 180 is accompanied by an isotope-exchange reaction of the oxygen between the reaction products ketone and water. The reaction leading to the exchange of oxygen goes at a rate exceeding the rate of oxidation process itself. The actual process of oxidation of the secondary alcohol to the ketone is not connected with the replacement of the hydroxyl group by oxygen from the oxidizing agent. In the liquid-phase oxidation of secondary alcohols the intermediate product--a hydroperoxide (or its radical)--decomposes to form kctones without rupture of the O--O bond in the peroxide bridge. An experimentally based scheme of the mechanism of the oxidation of secondary alcohols to ketones including within its scope conditions of oxidation both in the liquid and in the gas phase has been proposed. ISOLATION OF ACROLEIN FROM DILUTE AQUEOUS SOLUTIONS
V. N. Vostrikova, R. E. Gurovich, M. E. Aerov, G. L. Motina a n d R. G. Z a l y a l e t d i n o v a , N e f t e k h i m i y a 3, No. 2, 254-258, 1963. THE conditions for isolating acrolein from the aqueous solutions have been determined and a technological interpretation of the process of producing a technical product for organic synthesis has been given.
Methods have been developed for the intensive drying of acrolein a n d the comparative results of such drying have been shown b y rectification in vacuum or b y extractive distillation with xylene as extractant. B y this means, the advantage of using some method or other which enables d.ry aerolein to be used for processes of organomctallic synthesis has been shown. PRODUCTION OF HEXANE-I,2,6-TRIOL FROM ACROLEIN
V. V. F e d o r o v a , 2 5 9 - 2 6 6 , 1963.
G. P . P a v l o v a n d I . D. S i n o v i c h , N e f t e k h i m i y a
3, N o . 2,
THE conditions for the formation of acrolein dimer and for hydrolysing the dimer to 2-hydroxyadipaldehyde have been studied. Preliminary d a t a for the development of an industrial process for producing hexanetriol from acrolein have been obtained. CATALYTIC REDUCTION OF 2-HYDROXYADltPALDEHYDE TRIOL
V. I . K a r z h e v , B. ¥ a . N o . 2, 2 6 7 - 2 7 0 , 1963.
a n d G. D. ¥ e v s e y e v ,
THE o p t i m u m conditions for the hydrogenation of 2-hydroxyadipaldehyde to hexanetriol have been determined. I n a d d i t i o n to the desired p r e d u c t - - h e x a n e t r i o l - - h y d r o g e n a t i o n forms hexanedJol a n d condensation products as by-products. Hexanetriol of high p u r i t y can be isolated from the hydregenation products b y rectification. CHANGES IN THE STRUCTURE OF SUPPORTS FOR PHOSPHORIC ACID CATALYSTS IN THE HYDRATION OF ETHYLENE
K . V. T o p c h i e v a , S. M. R a k h o v s k a y a , I. K . K u c h k a y e v a , I. S. S h a m i n a A . A . Y u r k e v i c h , N e f t e k h i m i y a 3, No. 2, 2 7 1 - 2 7 5 , 1963.
A COMPARATIVE study of the structures of synthetic supports and natural foundry sands, and changes in their structure under the conditions of ethylene h y d r a t i o n has been made b y adsorption-structural, porometric, and X-radiographic methods. The main directions of the change in structure of all supports during the industrial process are analogous and do not depend on the nature of their original structure. The crystallization of the samples, accompanied b y a m a r k e d decrease in the magnitude of the specific surface and the total sorption volume which is observed during the process does not affect the acid capacity and activity of catalysts made with synthetic supports a n d leads to an increase in the a c t i v i t y of catalysts made from regenerated samples of foundry sand. F r o m the results obtained, it m a y be concluded t h a t the best support structure, giving the highest a c t i v i t y of the catalyst in the h y d r a t i o n of ethylene is as follows: the support has a p r e d o m i n a n t l y monodisperse structure with a m a x i m u m lying in the range of pore radii of 400-500/~ and above. The analogy which we have noted in the nature of the changes in structure of synThe Publisher will be pleased to quote for the supply of a full English translation of a n y papers a b s t r a c t e d in these pages.