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There has been considerable debate on the correct terminology to use for these systems because the propagating radicals do not have a signi cant lifetime in the absence of monomer as do the anionic living systems Terms such as controlled, living, and pseudoliving have been used instead of living to distinguish these radical systems from the anionic living systems This proliferation of terms adds confusion, not clarity [Darling et al, 2000; Penczek, 2000] It seems simpler and reasonable to de ne living polymerizations as those systems where irreversible terminations and transfers are suf ciently suppressed so that block copolymers can be synthesized by sequential addition of monomers..



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(3.139) Thus the SchrOdinger-like equation (3.124) can also be ,written as (3.140) This equation was derived before in ways completely different from the present approach by a number of authors, including Oppenheimer [472], Good [241], and Bialynicki-Birula [53-55]. As noted by Bialynicki-Birula [54], this equation has the same form (the iT matrices are different, of course) as Weyl's equation for neutrinos [638]. Moreover, from it we see that the component of spin that is a good quantum number (i.e., that commutes with the Hamiltonian) is the component along





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Living radical polymerizations include atom-transfer radical polymerization (ATRP) and stable free-radical polymerization (SFRP), which proceed with reversible termination, and reversible addition fragmentation transfer (RAFT), which proceeds with reversible chain transfer. Until the extensive exploration of these living polymerizations starting in the mid-1990s, radical polymerization was thought to be a mature process with relatively little left to discover. There is an ongoing effort to exploit the synthetic possibilities of living radical polymerization. Much of the driving force for the effort derives from the belief that wellde ned materials from living radical polymerization will offer substantial advantages to build nanostructures for microelectronics, biotechnology, and other areas. 3-15b 3-15b-1 Atom Transfer Radical Polymerization (ATRP) Polymerization Mechanism

the direction of the momentum of the photon: the helicity. This is another reminder that momentum rather than configuration space is the right place for introducing the wavefunction of a relativistic particle. So we will go to momentum space. In momentum space, (3.140) reads simply

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ATRP, SFRP, and RAFT differ in the method of radical generation. Radical generation in atom-transfer radical polymerization involves an organic halide undergoing a reversible redox process catalyzed by a transition metal compound such as cuprous halide [Kamigaito et al., 2001; Lutz and Matyjaszewski, 2002; Matyjaszewski, 1998a,b, 2002; Matyjaszewski and Xia, 2001; Nanda and Matyjaszewski, 2003; Patten and Matyjaszewski, 1998, 1999; Wang and Matyjaszewski, 1995a; Yoshikawa et al., 2003]. ATRP proceeds as described in Eqs. 3-219 through 3-221:

Select a Column or Row 1 Position the mouse pointer over the header of the column or row that you want to select.

R Br + CuBr(L)

& ih--'l/J = ciT . p'l/J, &t-

+ CuBr2(L)

(3.141)

3-219

'!!!.(p, t) =

CuBr2(L)

J(27l')3h e-

3-220

'l/J(r, t).

+ CuBr(L)

(3.142)

3-221

Click the column or row. Excel selects the entire column or row. To select multiple columns or rows, you can click and drag across the column or row headings. You can select multiple noncontiguous columns or rows by pressing and holding while clicking column or row headings.

(3.143)

where L is a ligand that complexes with the cuprous salt and helps to solubilize it in the organic reaction system. ka are kd are rate constants for activation and deactivation of the halide initiator, with K ka =kd . Activation of the initiator involves the CuBr metal center undergoing an electron transfer with simultaneous halogen atom abstraction and expansion of its coordination sphere. R is the reactive radical that initiates polymerization. CuBr2 (L) is the persistent (metallo)radical that reduces the steady-state concentration of propagating radicals and minimizes normal termination of living polymers. The initiator and persistent (metallo)radical are also called the activator and deactivator, respectively. The free-radical nature of ATRP is well established through a number of studies [Matyjaszewski et al., 2001]. The effects of inhibitors and retarders, solvents, and chaintransfer agents are the same in ATRP as in conventional radical polymerization. The regioselectivity, stereoselectivity, and copolymerization behaviors are also the same. The concentration of propagating radicals in ATRP is obtained as

R K I Cu Cu2 3-222

iP2 -ipl -P'

from the equilibrium expression for Eq. 3-219. Combination with the expression for propagation (Eq. 3-22) yields the polymerization rate as

(3.144)

Rp kp K M I Cu Cu2 3-223

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