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Feynman showed that in quantum mechanics, a particle actually follows all possible paths and that it is only in the classical limit that most of them interfere destructively, leaving only that single path where the action is minimum! Here we always use Hamiltonians, so this is all that we are going to say about Feynman's formulation of quantum mechanics The curious reader might wish to have a look at the recommended reading at the end of the chapter..



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Various stable radicals such as nitroxide, triazolinyl, trityl, and dithiocarbamate have been used as the mediating or persistent radical (deactivator) for SFRP. Nitroxides are generally more ef cient than the others. Cyclic nitroxide radicals such as 2,2,6,6-tetramethyl-1-piperidinoxyl (TEMPO) have been extensively studied. SFRP with nitroxides is called nitroxidemediated polymerization (NMP). Polymerization is carried out by two methods that parallel those used in ATRP [Bertin et al., 1998; Georges, 1993; Hawker, 1997; Hawker et al., 2001]. One method involves the thermal decomposition of an alkoxyamine such as 2,2,6,6-tetramethyl-1-(1-phenylethoxy)piperidine into a reactive radical and a stable radical (Eq. 3-236). The other method involves a mixture of a conventional radical initiator such as

FIAT LUX!

3-236





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In quantum electrodynamics it is the radiation field that is quantized9 rather than the Coulomb field of the charged particles. The radiation field is special because it has a "life" of its own. In more technical terms: It has its own degrees of freedom, whereas the Coulomb field has none. The Coulomb field is determined completely by the degrees of freedom of the charged particles. To illustrate this point, we derive an important result in electrodynamics called the Helmholtz theorem. We start by noticing that according to Section F.I.5 of Appendix F, given a square-integrable vector field F(r), we can write

AIBN or benzoyl peroxide and the nitroxide radical. Nitroxide radicals are suf ciently stable (due to steric hindrance) that they can be stored at ambient temperatures without change and some are available for purchase from chemical vendors. The reactive radical initiates polymerization while the stable radical mediates the reaction by reacting with propagating radicals to lower their concentration. The overall process (Eqs. 3-237 3-239) is analogous to ATRP. The nitroxide radical, although unreactive with

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3-237

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F(r) = -

3-238

~ r'l'

3-239

(2.33)

itself, reacts rapidly with the propagating radical to decrease the concentration of propagating radicals suf ciently that conventional bimolecular termination is negligible The propagating radical concentration is much lower than that of the dormant species; speci cally, K is small, and this results in living radical polymerization with control of molecular weight and molecular weight distribution The general characteristics of ATRP described in Sec 3-15b apply to NMP, that is, reaction variables control polymerization rate, molecular weight, and PDI in the same way [Ananchenko and Fischer, 2001; Greszta and Matyjaszewski, 1996; LacroixDesmazes et al, 2000, 2001; Lutz et al, 2001; Yoshikawa et al, 2002] NMP with TEMPO generally requires higher temperatures (125 145 C) and longer reaction times (1 3 days) compared to ATRP, and only styrene and 4-vinylpyridine polymerizations proceed with good control of molecular weight and polydispersity Narrow molecular weight distributions with PDI below 1.

As V2 acts only on r, we can take it outside the integral sign. Then using (E.2!) with a = b = V and c being the integral, we get

1 12 are dif cult to achieve with other monomers The sluggishness of TEMPO systems is ascribed to K values being too low K values are lower than in ATRP Various techniques have been used to increase Rp Adding a conventional initiator with a long half-life (slowly decomposing) to continuously generate reactive radicals throughout the reaction works well Another technique is the addition of an acylating agents to reduce the concentration of nitroxide radicals via their acylation [Baumann and Schmidt-Naake, 2001] Self-initiation in styrene polymerization also enhances the reaction rate However, it is not easy to increase reaction rates and maintain narrow PDI Some improvements occurred by changing to nitroxides with a hydrogen on at least one of the a-carbons of the piperidine ring, in contrast to TEMPO, which has no hydrogens on a-carbons.

F(r) =

However, the major breakthrough came by using sterically hindered alicyclic nitroxides with a hydrogen on one of the a-carbons t-Butyl 2-methyl-1-phenylpropyl nitroxide (LVIII) and t-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide (LIX) are examples of.

~ {V 1\

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