By Germain P., Nguyen Q.S., Suquet P.
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1). 1 General scheme of ring-opening polymerization accompanied by chain transfer to macromolecule with chain rupture. K bb(y ) = [. . −m x − . ][M (y )]eq [. . −m x − y − . 17) where M(y) represents the macrocycle containing y repeating units of …-m-…. 18) Thus, the equilibrium concentration of a given macrocycle should decrease monotonically with increasing ring size. Detailed studies of the equilibrium distribution of cyclic siloxane oligomers provided a very good agreement between the theoretical and experimental values for y > 25; that is, for this range of cyclopolysiloxane sizes the plot of ln[M(y)]eq versus ln y was a straight line with a slope of −5/2 .
The conclusion reached was that, for the enzymatic process, the thermodynamic and kinetic polymerizabilities with regards to monomer ring size were in reverse sequence. 2 Kinetics of Living Polymerization Living polymerization constitutes a particularly useful model system for conducting rigorous and systematic kinetic studies to determine the absolute rate constants of involved elementary reactions. As the kinetics of ROP has been reviewed on several occasions in the past [3a, 4, 7, 12, 23, 24, 105–107], we will at this point present only a brief summary of the most important phenomena, complemented with some recent ﬁndings.
BL] > [CL]), then BL addition proceeds faster than that of CL. 5 Dependence of γ-butyroyl (bl) units content in the γ-butyrolactone (BL)/ε-caprolactone (CL) copolymer (Fbl = 100[bl]/([bl] + [cl])), on the BL monomer content in the feed ( fBL = 100[BL]0/([BL]0 + [CL]0). cl = ε-caproyl unit content . g. e. average x in –[CH2CH(CH3)Sx]n–) was increased from 1 to 7 when the 8[S8]0/[PS]0 ratio was increasing from 0 to 10 [65, 66]. The situation of a monomer incapable of producing high polymers above Tc or below Tf is similar to a that of monomer which cannot homopolymerize at a given temperature but is reaching its polymer–monomer equilibrium.
Continuum Thermodynamics by Germain P., Nguyen Q.S., Suquet P.