Lifetime of living polymers

An intriguing question may be posed is the lifetime of living polymers prolonged by keeping them supplied with their monomer The answer depends on the mechanism of propagation. In many systems propagation takes place directly in one step ... 

For such systems the lifetime of living polymers is determined by kd only, independently of [M], although the maximum DPn achieved in such a system does depend on [M], However, when propagation proceeds through intermediates, e.g.,... 

Provided that the uncomplexed species is suceptible to destruction, while the complex is protected, the lifetime of living polymer increases at higher monomer concentrations. Cationic polymerization of propylene induced by AlBr3. HBr studied by Fontana and Kidder22) exemplifies perhaps such a system. 

Lifetime of live polymer chain is of the order 0.1—1.0 seconds [9]. 

In the case of PMMA dissolved in acetone, the change of LSI could be correlated both with the separation of fragments and, to some extent, with the lifetime of the intermediates which contribute to the main-chain scission [71]. The LSI decreased in two modes, probably due to the two pathways for the main-chain scission. The fast mode with a lifetime of about 20 ps was influenced neither in its extent nor in its rate by the addition of 02 or mercaptane. Therefore the first mode was ascribed to the diffusional separation of fragments which are generated by the main-chain scission through the direct decomposition of electronically excited or ionic intermediates. The slow mode with a lifetime of 6 ms was suppressed, to an extent, depending on the ( -concentration it was attributed to long-lived polymer radicals. The added 02 reacts with lateral polymer radicals to prevent their decomposition. 

Anionic polymerizations, when carried out in aprotic solvents, are characterized by the long lifetime of the carbanionic (or oxanionic) sites l2). When neither spontaneous transfer nor termination reactions are involved, the polymers obtained exhibit sharp molecular weight distributions, and their number average degree of polymerization is determined by the [Monomer]/[Initiator] molar ratio, provided initiation is fast as compared to propagation. However, the major advantage of these methods, as far as synthesis is concerned, is the socalled living character of the polymers 12) After completion of the polymerization the active sites retain their reactivity and can be used for functionalizations at the chain end. 

Positrons emitted for a radioactive source (such as 22Na) into a polymeric matrix become thermalized and may annihilate with electrons or form positronium (Ps) (a bound state of an electron and positron). The detailed mechanism and models for the formation of positronium in molecular media can be found in Chapters 4 and 5 of this book. The para-positronium (p-Ps), where the positron and electron have opposite spin, decays quickly via self-annihilation. The long-lived ortho positronium (o-Ps), where the positron and electron have parallel spin, undergo so called pick-off annihilation during collisions with molecules. The o-Ps formed in the matrix is localized in the free volume holes within the polymer. Evidence for the localization of o-Ps in the free volume holes has been found from temperature, pressure, and crystallinity-dependent properties [12-14]. In a vacuum o-Ps has a lifetime of 142.1 ns. In the polymer matrix this lifetime is reduced to between 2 - 4 ns by the so-called pick-off annihilation with electrons from the surrounding molecule. The observed lifetime of the o-Ps (zj) depends on the reciprocal of the integral of the positron (p+(rj) and electron (p.(r)) densities at the region where the annihilation takes place ... 

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