III International Conference

PP-II-108(K⋅10 6 l/mole⋅mg⋅equiv.s); KU-2x2-10,2; KU-2x6-8,24; KU-2x8-6,84; KU-2x8p-9,64;KU-2x12-4,02; KU-23-11,42, H 2 SO 4 -13,46.Taking accessibility of active sites of homogeneous catalysts (H 2 SO 4 ) 100 % as acriterion, accessibility of active sites of cationites has been estimated. In particular,accessibility of active sites of chlorosulfocationite KU-2x8 is ≈42 %. With increase ofporosity of modified resins (KU 2x8 p and KU-23) accessibility of acid sites increases up to86 %. On grinding granules of modified cationites (to 0,125 mm), their activity practicallycoincides with activity of homogeneous catalysts (H 2 SO 4 ). When using chlorosulfocationiteKU-2x8 containing 9,5 mass% of chlorine in reactions of induced oxidation of the abovementioned olefins, the main products of reaction within 30-50 o C range are the correspondingepoxides (68-76 %) (Table 2). At above 60 o C the rate of secondary reactions oftransformation of oxirane compounds into diols and its monoacetates increases.Table 1. Influence of work duration of modified cationites on chlorine content in oxidationreaction of acetic acid (CH 3 COOH:H 2 O 2 =4:1; temperature 40 o C)Chlorinecontent, mass%.Catalyst work duration, hourКU-2х2 КU-2х6 КU-2х8 КU-2х8p КU-2-12 КU-230 300 500 1500 1300 1600 12002,2 400 600 2500 1800 2100 16007,5 600 800 300 2500 2500 21009,5 700 900 3500 3100 2900 2800Table 2. Influence of various factors on parameters of process of induced epoxidation oftritsiklo [5,2,1,0 2,6 ] dekadiene-3,8 by hydrogen peroxide (cat. Chlorosulfocationite KU-2x8.,9,5 mass%Cl)Initial concentration, mole⋅l -11Yield of monoanddiepoxide,%T,K τ, min. Conversion H 2 O 2 , %H 2 O 2 CH 3 COOH diene1 1 1 293 420 55.8 47.31 1 1 303 360 70.3 62.81 1 1 313 300 80.0 65.02 1 1 313 300 73.3 65.12 1 1 323 240 82.1 68.02 2 1 323 180 90.4 76.01.5 3 1 313 313 95.0 63.2References1. Polyanskiy N.G. Catalysis by ionites. M.:19732. A.S.1685932 (the USSR), 1991,B.I. №39363