By Mazzone F.D., Cuenya H.H.
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Additional info for A Characterization of Best fi-Approximants with Applications to Multidimensional Isotonic Approximation
Thus, substitution, mostly affecting the enthalpy of polymerization, usually decreases polymerizability. 6. The effect of substitution is also demonstrated in the conformational strain, caused by the interaction of groups located either in the immediate neighbourhood or across the ring (transannular strain). The conformational strain in the macromolecule formed may, however, be higher than the conformational strain in the monomer molecules. A typical case where the substituents are kept apart in the monomer but may interact in the macromolecule may be shown schematically as follows: + -----~ (2-38) In small rings the angular strain is sufficiently high to compensate the conformational strain in the macromolecule.
Therefore, as Qt and 13 are less than unity, the equilibrium concentration of monomers, M1 and M2 is reduced in copolymerization ([M] e < [M]e (homo)): [M1]e = at[M1]~ (homo) [M2]~ = 13[M2]¢ (homo) (2-53) M o n o m e r equilibrium concentrations in copolymerization will be discussed in more detail in the next section, which is devoted to the polymerization of 1,3,5-trioxepane. According to Scheme (2-50) copolymerization consists o f four different reactions characterized by specific enthalpy and entropy changes.
Phys. 25, 1228 (1956) 38. Tobolsky, A. : J. Polym. Sci. C12, 71 (1966) 39. : "Thermodynamics of Polymerization", New York, Marcel Dekker, 1976 40. Dainton, F. , Ivin, K. J. : Quart. Rev. 12, 61 (1958) 41. Cairns, T. , Joyce, R. M. 1948) 42. Kazanskij, K. S. : in: Soviet Encyclopedia of Polymers, Vol. I, p. 413, Moscow 1974 43. , Hatano, M. : J. Chem. Soc. , Ind. Chem. Sect. 61,904 (1958) 44. Farthing, A. C. : J. Chem. Soc. 1955, 3648 45. , Riande, E. : Macromolecules 14, 1132 (1981) 46. : J. Polym.
A Characterization of Best fi-Approximants with Applications to Multidimensional Isotonic Approximation by Mazzone F.D., Cuenya H.H.