Terpolymerization kinetics of methyl methacrylate or styrene/dodecyl methacrylate/octadecyl methacrylate systems

Abstract

This study describes low-conversion terpolymerization kinetic investigations of methyl methacrylate/dodecyl methacrylate/octadecyl methacrylate (MMA/DDMA/ODMA) and styrene/dodecyl methacrylate/octadecyl methacrylate (ST/DDMA/ODMA) systems. Terpolymerizations were performed isothermally (70-105• C), in 1 mol dm −3 xylene solutions, using 0.01 mol dm −3 of bifunctional peroxide initiator 1,1-di(tertbutylperoxy)-3,3,5-trimethylcyclohexane or monofunctional tert-butylperoxy-2-ethylhexanoate. Synthesized terpolymers were characterized with respect to composition and molar mass distribution. Initial polymerization reaction rates as well as terpolymer average molar masses decreased with increasing MMA or ST content in the monomer mixture, for both initiators and all investigated temperatures. Overall reaction rates were found to be significantly larger for the MMA/DDMA/ODMA system. In the MMA/DDMA/ODMA system, experimental terpolymer compositions were found to be similar to the initial monomer feed compositions -all the experimental monomer feed mixtures were close to the azeotropic composition. The Alfrey-Goldfinger terpolymerization equation was successfully used for the description of MMA/DDMA/ODMA terpolymerization kinetics, where the existence of the true azeotropic ternary point was established. The same equation did not perform as well for the ST/DDMA/ODMA terpolymerization system.

Free radical copolymerization of N,N‐dimethylaminoethyl methacrylate with styrene and methyl methacrylate: monomer reactivity ratios and glass transition temperatures

“…The observed linear conversion versus time relationship is evidence that the experiments were performed under stationary conditions. Thus, the results may be used to calculate the initial polymerization rates, R p , for both systems investigated using the equation30 where m is the total monomer mass, X is the total monomer mass conversion, V is the volume of the dilatometer and t is the reaction time. M R is the average monomer molar mass: where M i and F R , i are the molar masses and average molar fractions, respectively, of particular monomers in the copolymer, previously established from NMR measurements.…”

Thermal properties and side chain crystallinity of styrene and n‐alkyl methacrylate terpolymers

“…The terpolymer composition was determined by the 1 H‐NMR spectroscopy method , using a Bruker Avance 300 MHz instrument. Molar mass distributions were measured by the size exclusion chromatography method, using a Polymer Laboratories GPC 20 chromatography system.…”

Kinetic Investigations on Microwave-Assisted Statistical Terpolymerizations of 2-Oxazoline Monomers

“…Up to this moment, only few kinetic investigations were reported on free radical statistical terpolymerizations, whereby no good control over the monomer distribution in single polymer chains could be achieved due to the use of the uncontrolled polymerization method. [35][36][37][38][39] In addition, one example of kinetic investigations on controlled nitroxide-mediated free radical terpolymerizations was reported to result in well-defined polymers, but the monomer distribution throughout the chains was not determined. [40] As such, detailed kinetic investigations on the monomer incorporation and, thus, the monomer distribution have not been determined for living or controlled statistical terpolymerizations.…”