Kinetics of the free radical copolymerization of diethyl maleate with methyl methacrylate

Abstract

The kinetics of the free radical copolymerization of diethyl maleate (M1 ) with methyl methacrylate (M2) was studied in bulk at 60°C with azoisobutyronitrile (AIBN) as initiator. The reactivity ratios of the system were determined by means of H NMR spectroscopy. The obtained values show that diethyl maleate is not only unable to homopolymerize (rI2 = 0) but also displays a very low tendency to incorporate in the polymer chain (rZ1 = 370) under the present conditions. Molecular weight measurements showed that a normal, although very slow growth reaction involving diethyl maleate takes place. Therefore, chain transfer could be neglected in the kinetic analysis. The dependence of the initiation rate constant on the monomer feed was analysed by means of the inhibition method. An equation for describing the observed dependence of polymerization rate on feed composition was derived taking into account the influence of solution viscosity on the termination rate constant (diffusion theory). a) Part of Ph. D. Thesis.

One‐step functionalization of an ethylene/propylene random copolymer with two different reactive groups

“…19 For the same reason, MAH, after reacting with the primary radicals derived from the initiator, could induce homopropagation (thereby generating not-grafted oligomers from MAH), thereby reducing the amount of monomer available for the reaction with the macroradicals of the polyolefins, reducing FD, and increasing the probability of crosslinking. This is probably not valid for DEM; indeed, the reactivity ratios determined for the copolymerizations of the DEM/ methylmethacrylate 20 and DEM/styrene 21 systems showed that DEM participated only to a very small extent in the propagation step.…”

Synthesis of block copolymers by radical polymerization and telomerization

“…A series of at least 14 papers [200][201][202][203][204][205][206][207][208] have been published dealing with the synthesis of telechelic polymers or block copolymers from the radical polymerization of various vinyl monomers with substituted l,l,2,2-tetraphenyl ethanes. These aromatic compounds, known for over a century [209], are efficient in radical polymerization [201,210].…”

“…These aromatic compounds, known for over a century [209], are efficient in radical polymerization [201,210]. They behave as both initiators and terminating agents [200] that can be involved in living radical polymerization as illustrated in the following reaction: Rl = H or CH3, R 2 = C6H 5, or RI= CH 3 and R2= CO2R R= H, CH 3, nC4H 9, tf4H 9, CH2C6H 5 .…”

“…These oligomers have shown novel applications, such as being efficient agents for thermal curing of unsaturated polyester resins [200]. Interestingly, methacrylate oligomers synthesized via this method are original macroinitiators for further polymerizations that can be performed at mild temperatures leading to diblock copolymers [203,204].…”

“…Braun [200] reported that oligobenzopinacoles obtained by UV irradiation of bisbenzophenones and bishydroles are efficient initiators for the polymerization of styrene at 70-100°C, allowing the formation of the following diblock …”