Pulsed laser studies of cationic reactive surfactant radical propagation kinetics

Pulsed laser polymerization coupled with size exclusion chromatography (PLP-SEC) was implemented to study the micellar radical homopropagation kinetics of cationic surfmer, polycaprolactone choline iodide ester methacrylate (PCLnChMA with n = 2 average polyester units), at concentrations of 5, 10, a...

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Bibliographic Details
Published in:Polymer (Guilford) 2017-11, Vol.130, p.39-49
Main Authors: Rooney, Thomas R., Chovancová, Anna, Lacík, Igor, Hutchinson, Robin A.
Format: Article
Language:English
Subjects:
Acrylamide
Aqueous solutions
Cationic polymerization
Choline
Copolymerization
Iodides
Kinetics
Macromonomer
Polycaprolactone
Polymerization
Polymers
Propagation
Propagation (polymerization)
Pulse propagation
Radical polymerization kinetics
Reaction kinetics
Size exclusion chromatography
Surfmer
Temperature
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Summary:Pulsed laser polymerization coupled with size exclusion chromatography (PLP-SEC) was implemented to study the micellar radical homopropagation kinetics of cationic surfmer, polycaprolactone choline iodide ester methacrylate (PCLnChMA with n = 2 average polyester units), at concentrations of 5, 10, and 20 wt% in aqueous solutions at 25, 50, 70, and 85 °C. PCL2ChMA can propagate in both aqueous and compartmentalized phases, with the relative importance of the two reaction loci changing with temperature. As the corresponding saturated macromonomer concentration, [M], inside the growing polymeric micelles cannot be easily determined, only the product of propagation rate coefficient (kp) and [M] are measured by PLP-SEC; at 25 °C, a minimum kp of 863 ± 95 L mol−1 s−1 is estimated assuming bulk [M]. (Macro)monomer composition drifts for batch acrylamide (AM)/PCLnChMA micellar copolymerizations in D2O at 50 °C are well represented by the apparent reactivity ratios rAM = 0.31 ± 0.03 and rPCL3ChMA = 8.79 ± 0.38. [Display omitted] •PCLnChMA is a cationic methacrylate macromonomer containing degradable polyester units.•The radical propagation kinetics are studied by pulsed-laser polymerization.•The study is complicated by the surface activity of the macromonomer.•Reaction occurs in both compartmentalized and aqueous phases.•First estimates of the propagation rate coefficient are reported.
ISSN:0032-3861
1873-2291
DOI:10.1016/j.polymer.2017.09.064