Initiator efficiency determination

PIB yields and molecular weights (Mvs) obtained using Et2AlCl in conjunction with f-BuCl and t-BuBr initiators and MeCl and MeBr solvents are given in Table 4. Initiator efficiencies determined at -60 °C are reported in Table 8. Polymerization was absent using f-BuI initiator or Mel solvent. 

Efficiency, initial The efficiency determined prior to the first loading cycle in a filter test. 

Thus, the size and the reactivity of the initiator-derived radicals and the medium viscosity (or microviscosity) are important factors in determining the initiator efficiency. Thus, the extent of the cage reaction is likely to increase with... 

The importance of the cage reaction increases according to the viscosity of the reaction medium. This contributes to a decrease in initiator efficiency with conversion. 15 1 155 Stickler and Dumont156 determined the initiator efficiency during bulk MMA polymerization at high conversions ca 80%) to be in the range 0.1-0.2 depending on the polymerization temperature. The main initiator-derived byproduct was phenyl benzoate. 

Buback et a A9 1 11,532 applied FTIR to follow the course of the initiation of S polymerization by AIBN and to determine initiator efficiency. Contributions to the IR signal due lo cyanoisopropyl end groups, AIBN, and the kelenimine can be separated using curve resolution techniques. 

Polymer formed using radiolabeled initiators may be isolated and analyzed to determine the concentration of initiator-derived residues and calculate the initiator efficiency. Radiolabeled initiators have also been used extensively to establish the relati ve reactivity of monomers towards radicals. 107,5 -5 2... 

Examples of radicals which are reported to meet these criteria are diphenylpicrylhydrazyl [DPPH, (22)], Koelsch radical (26), nitroxides [e.g. TEMPO (23), Fremy s Salt (24)], triphenylmethyl (25), galvinoxyl (27), and verdazyl radicals [e.g. triphenylverdazyl (28)]. These reagents have seen practical application in a number of contexts. They have been widely utilized in the determination of initiator efficiency (Section 3.3.1.1.3) and in mechanistic investigations (Section 3.5.2). 

In ATRP, the initiator (RX) determines the number of growing chains. Ideally, the degree of polymerization is given by eq. 7 and the molecular weight by cq. 8. Note the appearance of the initiator efficiency (/ ) in the numerator of these expressions. In practice, the molecular weight is ofien higher than anticipated because the initiator efficiency is decreased by side reactions. In some cases, these take the form of heterolytic decomposition or elimination reactions. Further redox chemistry of the initially formed radicals is also known. The initiator efficiencies are dependent on the particular catalyst employed. 

The effect of f-BuX, Et2 A1X and MeX on PIB yield and polymerization rate was studied (Sections V, VI, VII). Relative initiator reactivities were determined based on yields, initiator efficiencies at —60 °C, polymerization rates and floor temperatures. Initiator reactivity orders can be summarized as follows ... 

This very large amount of information can be readily rationalized on the basis of a mechanism developed to explain the results of cationic model initiation and termination experiments10,34. It is postulated that the initiator efficiencies in isobutylene polymerization using r-BuX/Et2AlX/MeX systems are mainly determined by the overall rate of initiation, R. Initiation according to numerous... 

Using the f-BuX/Me3Al/MeX system, a preferred reagent addition sequence has been found to be /-C4Hg/MeX/Me3 Al/t-BuX. This sequence has been used in these investigations. Based on polymerization rates at —40 °C, overall polymer yields, floor temperature and initiator efficiencies at —40 °C, overall initiator reactivity is found to decrease as f-BuCl > f-BuBr > t-BuI = 0 and initiator reactivity is dependent on solvent as MeCl > MeBr > Mel = 0. Similarity of reactivity sequences in isobutylene polymerization and in cationic model initiation and termination studies13) suggest that initiator reactivities are determined by the rate of initiation, Rj. 

Rate of Formation of Primary Precursors. A steady state radical balance was used to calculate the concentration of the copolymer oligomer radicals in the aqueous phase. This balance equated the radical generation rate with the sum of the rates of radical termination and of radical entry into the particles and precursors. The calculation of the entry rate coefficients was based on the hypothesis that radical entry is governed by mass transfer through a surface film in parallel with bulk diffusion/electrostatic attraction/repulsion of an oligomer with a latex particle but in series with a limiting rate determining step (Richards, J. R. et al. J. AppI. Polv. Sci.. in press). Initiator efficiency was... 

The Instantaneous values for the initiator efficiencies and the rate constants associated with the suspension polymerization of styrene using benzoyl peroxide have been determined from explicit equations based on the instantaneous polymer properties. The explicit equations for the rate parameters have been derived based on accepted reaction schemes and the standard kinetic assumptions (SSH and LCA). The instantaneous polymer properties have been obtained from the cummulative experimental values by proposing empirical models for the instantaneous properties and then fitting them to the cummulative experimental values. This has circumvented some of the problems associated with differenciating experimental data. The results obtained show that ... 

INITIATING EFFICIENCY (OR STRENGTH) OF INITIATING DEVICES DETERMINATIONS. A list with refs is given in Vol 1, p XVIII... 

Detailed studies on the decomposition of organic peroxides are of fundamental interest and of high importance in polymerization reactions. The time-scales of intermediate radical formation and of their subsequent decomposition determine process parameters such as the initiator efficiency in radical polymerizations. An improved understanding of the mechanism and dynamics of photo-induced fragmentation is achieved by systematic investigations in which quantum-chemical calculations are carried out in conjunction with highly time-resolved experiments. 

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