Polymerization of NCAs carrying a substituent at the 3-position

The presence of a substituent in the 3-position of the NCA precludes equilibrium (6) and hence prevents the occurrence of reaction (18). It follows that, on the basis of the mechanisms described above, such NCA s should not polymerize unless a protic base (for example a primary or secondary amine) or other source of protons (for example, 3-methyl hydantoin) is present. If it could be established that polymerization does proceed with an aprotic base in aprotic media then some other mechanism of polymerization must be operative. This matter has been of central importance in discussions of various mechanisms of polymerization which have been advanced (Section 3). Experimentelly, it is not easy to obtain definitive evidence because of the high sensitivity of NCA s to protonic impurities (such as water and alcohols) in the presence of bases. It has been shown [18, 19, 38a] that proline NCA (X) and sarcosine NCA (I Ri = R2 = H, R3 = CH3) do not polymerize in the presence of tertiary bases under strictly aprotic conditions. With alkoxides, realization of such conditions is difficult, but it would appear that, at least with proline NCA, such strong bases can bring about ionization of the methine hydrogen and hence initiate polymerization as shown in (26). Evidence for this mechanism is provided by the observation that while sodium methoxide enriched 

If B is methoxide ion enriched with C, the latter should be incorporated in the polymer according to (27) or (28). Further, carbamate anions such as Ph CH2COJ should initiate polymerization when R3 H and lead to incorporation of C. None of these results is found in practice. See also refs. 38 and 80. 

Since the forward reaction in (29) is exothermic, the equilibrium is displaced to the left by increase in temperature this factor accounts in part for the anomalous temperature coefficient of reaction rate mentioned above. The apparent catalysis by propagating base is also explicable as acid catalysis since the carbamic acid is stoichiometrically derived from the base by reaction (29). That true base catalysis is not operative has been shown by the observation that addition of tertiary bases does not affect the reaction rate [17]. Further, the polymerization is catalysed by other weak acids such as hydrocinnamic [17] and a-picolinic acids [10, 17], which, if present in sufficient concentration under conditions of low CO2 pressure, reduce the order in initiating base to unity. Thus, under such conditions, with hydrocinnamic acid (HX) as catalyst the simple kinetic form (30) is achieved. 

The mechanism of the complex propagation reaction is now thought to be that illustrated in eqns. (31)—(34). 

If the equilibrium in (31) is established and lies well over to the left we have [XXI] = K[M] [I], hence it follows from (38) that 

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