By McIlwraith C. G., Cox R. T.
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AG O in the polymerization of substituted oxiranes R - C H - C H 2 at 25 ° < (Ref. 94 (25 oc) Cationic Ring-Opening Polymerization 19 the size of substituent and polymerizability. IAG°I increases with increasing p K B, thus, with decreasing basicity which may be affected by substituents. The lone electron pairs on the oxygen are too far from each other in the macromolecule for a strong repulsion but can interact with s'ubstituents. Another possibility is that monomersolvent and polymer-solvent interactions are stronger for the more basic monomers.
M o l - 1 . K - 1 (monomer), AS (fusion) = 49 J • mo1-1 • K -1 (polymer) 81). Recently a model system involving TXN, TTXN, and low molecular weight polyformaldehyde of the formula CH3OCH20(CH20)4CH2OCH a was studied using C 6 H 6 solvent by ~H- and 13C-NMR spectroscopy to determine the thermodynamic parameters of polymerization. 14. The equilibrium concentration of TXN depends on the state of polymer (crystalline or in solution). [TXN]e is also solvent dependent and correspondingly [TXN] .... 003 mol • 1-1 in CH2C12, C6HsNO 2, and Ct0H22, respectively 81).
Another possibility is that monomersolvent and polymer-solvent interactions are stronger for the more basic monomers. However, to discuss this point in detail we would need not merely the pK B of monomer but the p K B of monomer and of the corresponding polymer unit. It is possible that a relatively strong monomer-solvent interaction of the more basic monomer renders polymerization energetically less favorable, on account of the larger energy demand to break the solvent-monomer interaction. How much of this energy is released because of the emerging polymer-solvent interaction is not known for cationic ring opening polymerizations studied to date.
Apparent Evidence of Polarization in a Beam of -Ray by McIlwraith C. G., Cox R. T.