Emulsion-precipitation polymerization of diisopropyl fumarate

Abstract

The emulsion polymerization of diisopropyl fumarate initiated with a redox initiator and an anionic emulsifier was investigated. The study includes conversion and particle number determinations as a function of time, temperature and the concentrations of initiator, emulsifier and monomer. The reaction is characterized by a limiting conversion following a linear increase of the conversion with time from the beginning on. The reaction rate is very much higher than those obtained in bulk or in solution polymerization. Taking into account the results and the response of the system to an addition of styrene and toluene, a mechanism of radical occlusion together with a diffusion‐controlled propagation in the polymer matrix is proposed. The very high apparent activation energies for the propagation and limiting conversion suggest a complex behavior.

Living radical polymerization of diisopropyl fumarate to obtain block copolymers containing rigid poly(substituted methylene) and flexible polyacrylate segments

“…It was reported that the propagation and termination rate constants of DRF ( k p = 0.058–0.68 L/mol s and k t = 26–560 L/mol s) were much smaller than the values for conventional vinyl monomers (typically, k p = 10 2 –10 4 L/mol s and k t = 10 6 –10 8 L/mol s) . (j) The produced PDRFs exhibited unique properties from the viewpoints of both fundamental researches and industrial applications; for example, polymerization kinetics, reaction mechanism, reaction processes, copolymerization, functional polymer syntheses, thermal degradation, tacticity, solution property, solid‐state dynamic, mechanical property, thin film and surface properties, gas permeation, liquid crystals, electronic property, electro‐optical property, optical property, and optical materials application . Recently, various approaches for controlled polymer synthesis and materials design using living radical polymerization techniques have been reported, but no report on the living radical polymerization of DRF is seen in the literature .…”

Homo- and copolymers based on dialkyl fumarates: A review on radical polymerization, properties, current and future applications

“…Other polymerization methodologies have been researched, with the aim of achieving reaction rates comparable to those of other vinyl or acrylic monomers. Thus, the emulsion polymerization of diisopropyl fumarate (DIPF) using a redox initiator was studied [16]. It was found that the reaction rate was very much higher than those obtained in bulk or solution polymerization; although at short times (20 min) a limit conversion was reached.…”

Production and Polymerization of Biobased Acrylates and Analogs

“…[ 503 ] The rate of polymerization of D i PrFm could be increased by an emulsion polymerization process in water. [ 504 ] Poly(DEFm) could also be obtained in water by complexing the monomer with cyclodextrin. [ 505,506 ] Microwave initiation also proved to be faster than thermal initiation for poly(D i PrFm) formation.…”