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The reason for this is that the extent of crystallinity developed in a polymer is both kinetically and thermodynamically controlled, while the melting temperature is only thermodynamically controlled Polymers with rigid chains are dif cult or slow to crystallize, but the portion that does crystallize will have a high melting temperature (The extent of crystallinity can be signi cantly increased in such polymers by mechanical stretching to align and crystallize the polymer chains) Thus compare the differences between polyethylene and poly(hexamethylene adipamide) Polyethylene tends to crystallize easier and faster than the polyamide because of its simple and highly regular structure and is usually obtained with greater degrees of crystallinity On the other hand, the Tm of the polyamide is much higher (by $130 C) than that of polyethylene because of the much greater secondary forces 1-6 APPLICATIONS OF POLYMERS 1-6a Mechanical Properties.



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Many polymer properties such as solvent, chemical, and electrical resistance and gas permeability are important in determining the use of a speci c polymer in a speci c application. However, the prime consideration in determining the general utility of a polymer is its

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aluminum isopropoxide) and NMP through the alcohol and nitroxide functions, respectively, and the sequence is not critical. 2. An alkoxyamine with an appropriate functional group can be used to terminate a nonNMP polymerization to yield a polymer with an alkoxyamine end group, which subsequently initiates NMP of the second monomer, such as termination of a cationic polymerization by LX. 3. An existing polymer with an appropriate end group can be reacted with an alkoxyamine; for instance, alkoxide polymerization of ethylene oxide yields a hydroxylterminated polymer that undergoes substitution (in the presence of sodium hydride) with a halogen-containing alkoxyamine. Star polymers are produced by using a core molecule that contains three or more alkoxyamine functions [Hawker, 1995; Miura and Yoshida, 2002]. Graft and comb (brush) polymers are obtained by using a polymer containing alkoxyamine groups. For example, a chlorinecontaining polymer (from vinyl chloride or p-chlorostyrene units) could be reacted with the sodium salt of LX to place alkoxyamine groups on the polymer for subsequent initiation of NMP. Or an alkoxyamine with a vinyl group can be polymerized or copolymerized to yield the alkoxyamine-containing polymer.

(2.34)

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NMP has some advantages and disadvantages compared to ATRP. A wide range of initiators (organic halides) are readily available for ATRP. Relatively few initiators for NMP, either nitroxides or alkoxyamines, are commercially available. The initiators need to be synthesized. K is generally larger for ATRP compared to NMP and is more easily adjusted by changing the initiator, transition metal, and ligands. Larger K values mean faster polymerization and milder reaction conditions. On the other hand, ATRP requires a relatively large amount of metal (0.1 1% of the reaction mixture) that needs to be removed from the nal polymer product. In both NMP and ATRP, control of the reaction through establishment of a steady-state concentration of radicals is achieved by the balance between activation and deactivation. Conventional radical polymerization involves a balance between the rates of initiation and termination. 3-15d Radical Addition Fragmentation Transfer (RAFT)

ATRP and NMP control chain growth by reversible termination. RAFT living polymerizations control chain growth through reversible chain transfer [Barner-Kowollik et al., 2001, 2003; Chiefari and Rizzardo, 2002; Cunningham, 2002; D Agosto et al., 2003; Goto et al., 2001; Kwak et al., 2002; Moad et al., 2002; Monteiro and de Brouwer, 2001; Stenzel et al.,

F(r') 1\ V-I_1_'1 = -F(r') 1\ V'-I_1_'1 r-r r-r _ V' 1\ F(r') _ V' 1\ [ F(r') ] Ir - r'l Ir - r'l '

2003]. A chain-transfer agent such as cumyldithiobenzoate reversibly transfers a labile end group (a dithioester end group) to a propagating chain (Eq. 3-241).

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3-242 3-241

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