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A Handbook of Most Reliable Quantitative Solubility by Atherton Seidell

By Atherton Seidell

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From the other hand the time necessary for diffusion transfer of lowmolecular radical r* (tr) may be expressed from the formula for diffusion coefficient [161]: Do= O2 (6tr)-1. In given case O is the distance on which r* radical should transfer from comonomer M1 to reach the bond M2H and initiate free valency M2*, or from monomer M2 to reach the bond Ɇ1ɇ and initiate free valency M1
. It is obvious that initiating of free valency will proceed in the case when: O12 (6Dɨ1)-1 > (kc[Ɇ1H])-1 or O22 (6Dɨ2)-1 > (k1c [Ɇ2H])-1 Thus, initiating ability of low-molecular radical in reaction with any of comonomers will depend on the ratio between transport properties of copolymer and parameters of chemical reaction including effective constants kc, k1c of rates of reactions between low-molecular radical and Ɇ1H, M2H-bonds and also concentration of monomer units.

Initial sections of kinetic curves of oxygen absorption by samples of PP1 and PP2 at Tox = 130qC, PO2 = 150 millimeters of mercury. Parameter "b" is connected with ratio of constants of rates of separate stages of oxidation process by the following expression [161]: '1ɨ20,5 = (DVk22k4 [RH]3)0,5 L / (8k6) 0,5, 0,5 where '1ɨ2  change of amount of absorbed oxygen at initial stage of oxidation process when oxidation rate is determined by the rate of accumulation of hydroperoxide and concentration of monomer units remains constant; L  segment that is cut off by linear anamorphosis on axis of time; k2, k6  constants of rate of continuation and quadratic termination of kinetic chains of oxidation; k4  constant of hydroperoxide decomposition rate; D  yield of hydroperoxide per 1 mole of absorbed oxygen; V  probability of degenerated branching of kinetic chains of oxidation.

This phenomenon occurs as a result of change of molecular structure of interlamelar interlayers. 4a, b (the data were obtained by IR-spectroscopy). 4b). Structural reconstructions may be caused by the influence of high temperature and oxidation process. Comparison of data of X-ray SA of oxidized samples of PP1 and PP2 and of samples annealed in vacuum at the same temperature showed that changes of crystallites structures were connected with both annealing and oxidation process. 1). Annealing of PP1 and PP2 in vacuum leads to the increase of crystallinity degree, sizes of crystallites and of large period.

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