Fig 1.
Molecular structures of cited lactones.
Table 1.
Amounts of monomer used for reactions and molar composition of final products.
Fig 2.
Characteristic temperatures: a onset temperature, b peak temperature, c offset temperature, and b’ projection of b; values were used to calculate S.
Fig 3.
Thermodynamic equilibrium concentration [M]eq vs. starting monomer concentration [M]0 at different temperatures (experimental data, from Eq 4); b) [M]eq vs. reaction temperature for different ECL/GVL ratios in the starting monomer mixture; c) calculated [ECL]eq vs. reaction temperature for different ECL/GVL ratios in the starting monomer mixture; d) calculated [GVL]eq vs. reaction temperature for different ECL/GVL ratios in the starting monomer mixture; monomer ratios are indicated in figure legend.
Table 2.
[M]eq (Eq (1)), calculated [ECL]eq and [GVL]eq (Eqs (4) and (5)), experimental (GPC) and calculated (Eq (2)) Mn; values of Mn are referred to the polyester block, polydispersity index PDI calculated as the ratio Mw/Mn from GPC data; reported GPC data are the mean of a triplicate synthesis.
Fig 4.
Linear fitting of ln([M]eq) vs. 1/T, material: a) 100/0, b) 90/10, c) 80/20 and d) 70/30; fitting equations are indicated for each material.
Table 3.
Molar enthalpy ΔHp and entropy ΔSp of polymerization, R2 of linear fitting of experimental data, Tc from Eq (3), calculated ΔHp and ΔSp from GPC and 1H-NMR data.
Table 4.
Kinetic constant k, reaction order n and R2 from residual monomer analysis in low-conversion reactions.
Fig 5.
a) Onset and b) peak temperatures in non-isothermal polymerizations at different heating rates, as a function of the ECL/GVL ratio in the reaction feed.
Fig 6.
n from geometric method and multi-linear regression, Ea and ln(A) for analyzed ROPs.