A novel interpretation of measured and simulated PLP data
May 20-25, 2018
Figure 1 - Simulated ν dependency of the observed kp in vinyl acetate PLP at 323 K. Case 1 (♦): chain length independent head-to-tail prop., Case 2 (■): chain length dependent head-to-tail prop., Case 3 (●): chain length dependent head-to-tail, head-to-head, tail-to-tail, and tail-to-head prop., and Case 4 (▲): Case 3 with backbiting by head and tail radicals, and mid-chain prop.
Pulsed laser polymerization (PLP) is an interesting technique to study individual reactions.1-4 In PLP, photoinitiator radical fragments are generated at laser pulses with a frequency ν (or dark time Δt = ν-1). Depending on the PLP conditions and the monomer type, the molar mass distribution (MMD) can possess specific characteristics, allowing the determination of intrinsic rate coefficients. Most known is that under well-chosen conditions a multimodal MMD with inflection points Lj (j = 1, 2, …) is obtained, allowing the determination of the propagation rate coefficient kp ([M]0: initial monomer concentration):
In this contribution, kinetic Monte Carlo (kMC) modeling is applied to allow a further understanding and exploitation of PLP. For PLP of acrylates, regression analysis to low frequency inflection point data at various solvent volume fractions is proposed as an additional new method to estimate the backbiting rate coefficient kbb.5 Moreover, it is demonstrated that photodissociation, chain initiation and termination reactivities can be extracted from the complete PLP MMD.6 For the first time, the ratio of MMD peak heights has been used for the fast and reliable estimation of the photodissociation quantum yield,Φ.7
For PLP of vinyl acetate a unique combination of ab initio calculated rate coefficients and kMC simulations is considered to explain the experimental8 ν dependency of the observed kp (cf. Case 4 in Figure 1; Eq. (1) with kpobs). Via a stepwise extension of the kMC model (cf. 4 cases in Figure 1), the ν dependency is attributed to backbiting of tail radicals formed via head-to-head propagation.9 In contrast to acrylates, backbiting of head radicals is shown to be kinetically insignificant in VAc PLP, further highlighting the chemical difference between both vinyl monomer types.
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Yoshi W. Marien, Paul H.M. Van Steenberge, Gilles B. Desmet, Marie-Françoise Reyniers, Guy B. Marin, Christopher Barner-Kowollik, and Dagmar R. D’hooge, "A novel interpretation of measured and simulated PLP data" in "Polymer Reaction Engineering X (PRE 10)", John Tsavalas, University of New Hampshire, USA Fouad Teymour, Illinois Institute of Technology, USA Jeffrey Stubbs, HP Inc., USA Jose R. Leiza, University of the Basque Country, Spain Eds, ECI Symposium Series, (2018). https://dc.engconfintl.org/prex/50