Monomer consumption, linear first-order

For binary NdCl3-based catalyst systems such as NdCl3 nL/AlR.3 a few publications are available in which linear first-order plots regarding monomer conversion are given. In this context the study by Hsieh et al. deserves special attention as the first-order plots with respect to monomer consumption were reported to be ideally linear at different polymerization temperatures (30, 50 and 70 °C) [134],... 

Living polymerizations exhibit a linear first-order plot of monomer consumption (provided that initiation is fast) which indicates that the number of propagating chain ends is constant. Such a plot is obtained by considering the relationship between time (x-axis) and logarithmic monomer consumption. If the chain ends propagate at a constant rate in the absence of detectable amounts of chain termination, then a linear relationship results. Deviations from ideal linear behavior are observed as a result of termination events that decrease the slope, or slow initiation processes that increase the slope. However, this method is not sensitive to chain transfer. 

In the temperature range from 0 to 30 °C, on the other hand, the perchloric acid-initiated polymerization of styrene follows a stationary-state kinetics, giving a linear first-order plot for monomer consumption Based on the absence of UV absorptions... 

The kinetics of the e-CL bulk polymerization by lipase CA showed linear relationships between the monomer conversion and Mn of the polymer however, the total number of polymer chains was not constant during the polymerization.173 The monomer consumption apparently followed a first-order rate law. 

Isobutylene polymerisation initiated by 1,2-epoxy-2,4,4-trimethylpentane (TMPO-l)/TiCl4 was studied using IR fibre optics. The initiating mechanism involves the formation of tertiary carbocations, by both SNi and SN2 paths. From the linearity of the first-order plots of monomer consumption, and the near uniformity of the polyisobutylene, it was concluded that living polymerisation conditions prevailed (i.e., no termination step) (32). The ATR head can monitor very low concentrations (0.1 mmol/1) (49). 

Figure 3 shows the first-order kinetic plots for the polymerization of monomer ethyl ethylene phosphate (EEP) at different temperatures, where [A ]o/ [M], and [A ]eq are concentrations of EEP at time 0, time t, and equilibrium. The linearity of these plots demonstrated that the EEP consumption is in first order with reaction time and can be described by... 

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