Radical polymerization behavior of dimethyl vinylphosphonate: Homopolymerization and copolymerization with trimethoxyvinylsilane

Abstract

Dialkyl vinylphosphonates such as dimethyl vinylphosphonate (DMVP) and diethyl vinylphosphonate were quantitatively polymerized with dicumyl peroxide (DCPO) at 1308C in bulk. The polymerization of DMVP with DCPO was kinetically studied in bulk by fourier transform near-infrared spectroscopy (FTNIR) and electron spin resonance (ESR) spectroscopy. The initial polymerization rate (R p ) was given by R p 5 k [DCPO] 0.5 [DMVP] 1.0 at 1108C, being the same as that of the conventional radical polymerization involving bimolecular termination. The overall activation energy of the polymerization was estimated to be 26.2 kcal/mol. The polymerization system involved ESR-observable propagating polymer radicals under the practical polymerization conditions. ESR-determined rate constants of propagation (k p ) and termination (k t ) were k p 5 19 L/mol s and k t 5 5.8 3 10 3 L/mol s at 1108C, respectively. The molecular weight of the resultant poly(DMVP)s was low (M n 5 3.4 2 3.5 3 103 ), because of the high chain transfer constant (C m 5 3.9 3 10 22 at 1108C) to the monomer. DMVP (M 1 ) showed a considerably high reactivity in the radical copolymerization with trimethoxyvinylsilane (TMVS) (M 2 ) at 1108C in bulk, giving an inorganic component-containing functional copolymer with potential flame-retardant properties; r 1 5 1.6 and r 2 5 0.

Rare Earth Metal‐Mediated Group Transfer Polymerization of Vinylphosphonates

“…Later attempts confirmed independently the poor polymerizability of vinylphosphonates by radical means, which failed to yield high‐molecular‐weight polymers, produced many side products and exhibited incomplete conversion of the monomer 8. In 2008, Hirano and co‐workers achieved quantitative conversion of dimethyl vinylphosphonate (DMVP) in bulk with dicumyl peroxide at 130 °C, however, only low‐molecular‐weight polymers ( M n < 3.5 kg mol −1 ) were afforded 9…”

Preparation of Organic/Inorganic Hybrid Materials Using Agregates of Poly{2-methyl-N-[2-(phenylthio)phenyl] Acrylamide-co-2-(Trimethylsyloxy)Ethyl Methacrylate} as Precursor and Vibrational Investigation of the Polymerization

“…Copolymers with reactive or functional monomers are gaining importance steadily. Many polymers with reactive functional groups are now being synthesized, tested and used not only for their macromolecular properties, but also for the properties of functional groups (4)(5)(6)(7)(8). These functional groups provide an approach to a subsequent modification of the polymer for specific end applications (9).…”

Novel flame retardant flexible polyurethane foam: plasma induced graft-polymerization of phosphonates

“…However, only few examples of this approach exist in the literature. Liepins et al 23,24 and Sato et al 25 reported that dimethylvinylphosphonate (DMVP) and diethylvinylphosphonate (DEVP) exhibit re retardant properties of interest. Following this work, recent papers were published using this multilayer concept or a one pot coating concept.…”