Reaction initiation efficiency

The significant thing about these and numerous other side reactions that could be described for specific systems is the fact that they lower the efficiency of the initiator in promoting polymerization. To quantify this concept we define the initiator efficiency f to be the following fraction ... 

It is the aim of this chapter to describe the nature, selectivity, and efficiency of initiation. Section 3.2 summarizes the various reactions associated with initiation and defines the terminology used in describing the process. Section 3.3 details the types of initiators, indicating the radicals generated, the byproducts formed (initiator efficiency), and any side reactions (e.g. transfer to initiator). Emphasis is placed on those initiators that see widespread usage. Section 3.4 examines the properties and reactions of the radicals generated, paying particular attention to the specificity of their interaction with monomers and other components of a polymerization system. Section 3.5 describes some of the techniques used in the study of initiation. 

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... 

Suspension polymerizations are often regarded as "mini-bulk" polymerizations since ideally all reaction occurs w ithin individual monomer droplets. Initiators with high monomer and low water solubility are generally used in this application. The general chemistry, initiator efficiencies, and importance of side reactions are similar to that seen in homogeneous media. 

The concentration of monomers in the aqueous phase is usually very low. This means that there is a greater chance that the initiator-derived radicals (I ) will undergo side reactions. Processes such as radical-radical reaction involving the initiator-derived and oligomeric species, primary radical termination, and transfer to initiator can be much more significant than in bulk, solution, or suspension polymerization and initiator efficiencies in emulsion polymerization are often very low. Initiation kinetics in emulsion polymerization are defined in terms of the entry coefficient (p) - a pseudo-first order rate coefficient for particle entry. 

Initiator efficiency increases with reaction temperature (Table 3.4). It is also worth noting that apparent zero-conversion initiator efficiencies depend on the method of measurement. Better scavengers trap more radicals. The data in Table 3,4 suggest that monomers (MMA, S) are not as effective at scavenging radicals as the inhibitors used to measure initiator efficiencies. The finding suggests that in polymerization the initiator-derived radicals have a finite probability of... 

Ideally all reactions should result from unimolecular homolysis of the relatively weak 0-0 bond. However, unimolecular rearrangement and various forms of induced and non-radical decomposition complicate the kinetics of radical generation and reduce the initiator efficiency.46 Peroxide decomposition induced by radicals and redox chemistry is covered in Sections 3.3.2.1.4 and 3.3.2.1.5 respectively. 

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. 

The low conversion initiator efficiency of di-r-butyl pcroxyoxalatc (0.93-0.97)1-1 is substantially higher than for other peroxyeslers [/-butyl peroxypivalale, 0.63 /-butyl peroxyacetate, 0.53 (60 °C, isopropylbenzene)195]. The dependence of cage recombination on the nature of the reaction medium has been the subject of a number of studies. 12I,1<>0 20CI The yield of DTBP (the main cage product) depends not only on viscosity but also on the precise nature of the solvent. The effect of solvent is to reduce the yield in the order aliphatic>aromatie>protic. It has been proposed199 that this is a consequence of the solvent dependence of p-scission of the f-butoxy radical which increases in the same series (Section 3.4.2.1.1). 

Photolysis or thermolysis of persulfate ion (41) (also called peroxydisulfate) results in hoinolysis of the 0-0 bond and formation of two sulfate radical anions. The thermal reaction in aqueous media has been widely studied."51 232 The rate of decomposition is a complex function of pH, ionic strength, and concentration. Initiator efficiencies for persulfate in emulsion polymerization are low (0.1-0.3) and depend upon reaction conditions (Le. temperature, initiator concentration)."33... 

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 molecular weight in reverse ATRP will depend on the concentration of the initiator (In) and the initiator efficiency (/) and ideally is given by eq. 11. Side reactions between the catalyst and the initiator and the radicals formed from the initiator may lead to efficiencies being lower than those observed in conventional radical polymerization. 

The initiator efficiency has to be considered jointly with the monomers involved The nucleophilicity of the initiator should be matched to the electron affinity of the monomer, as initiation should be fast and quantitative 7). If it is too small, initiation may be slow (and/or incomplete), which implies broadening of the molecular weight distribution and possibly loss of molecular weight control. If the nucleophilicity of the initiator is too high, side reactions may occur, as in the case of methyl methacrylate, where the ester carbonyl is attacked15). 

This mathematical treatment shows that in the early stages of polymerisation the rate of reaction should be proportional to the square root of the initiator concentration, assuming/is independent of monomer concentration. This assumption is acceptable for high initiator efficiencies, but with very low efficiencies, / may become proportional to [M], making the rate proportional to... 

In the above reactions, I signifies an initiator molecule, Rq the chain-initiating species, M a monomer molecule, R, a radical of chain length n, Pn a polymer molecule of chain length n, and f the initiator efficiency. The usual approximations for long chains and radical quasi-steady state (rate of initiation equals rate of termination) (2-6) are applied. Also applied is the assumption that the initiation step is much faster than initiator decomposition. ,1) With these assumptions, the monomer mass balance for a batch reactor is given by the following differential equation. 

The mechanism(s) by which these photocatalyzed oxidations are initiated remain uncertain. Early proposals have included involvement of either the photo-produced holes (h+) arising directly from semiconductor photo-excitation, or the (presumed) derivative hydroxyl radical (OH) which was argued to arise from the hole oxidation of adsorbed hydroxyls (h+ + OH-—> OH ). Recent subambient studies [4] with physisorbed chloromethane and oxygen suggest the dioxygen anion (02 ) as a key active species, and the photocatalytic high efficiency chain destruction of TCE is argued to be initiated by chlorine radicals (Cl) [5]. The chlorine-enhanced photocatalytic destruction of air contaminants has been proposed [1, 2, 6] to depend upon reactions initiated by chlorine radicals. 

Polymerization of HEMA incorporated in the PET films is dependent both on the initiator concentration and reaction temperature. In order to overcome the low initiation efficiency inside the PET, due to the low mobility of the free radicals formed inside the PET structure, as well as that of the monomer itself, high initiator concentrations were used. The results are listed in Table II. However, satisfactory conversions of HEMA in pHEMA were obtained only when the polymerization was carried out at 80-85°C for 20-40 hr, even if the initiator concentration was high (Figure 3). 

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 ... 

The net result is a decrease in initiator efficiency and an attendant increase in polymer molecular weight. In fact, all of our work on radical polymerization of phenol-containing vinyl monomers suggests that inhibition and transfer problems are at most minor, if AIBN is used as initiator and oxygen is carefully excluded from the reaction mixtures (9). 

A third important group of reactions that may be discussed with the first two groups is not necessarily photosensitized. The dimerizations and additions of cyclic a,/S-unsaturated ketones can be initiated by direct n-n excitation of the ketone, followed by addition reactions. However, the reactions are efficiently photosensitized by triplet sensitizers, and it is reasonable to propose that the unsensitized cycloaddition reactions also proceed via triplet states. 8>63>94> Examples are given in Eqs. 28—... 

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