Copolymerization of diethyl 2‐(methacryloyloxy) ethyl phosphate with alkyl acrylates: Reactivity ratios and glass transition temperatures

Abstract

Soluble copolymers of diethyl 2‐(methacryloyloxy) ethyl phosphate (DMP) with methyl methacrylate (MMA), methyl acrylate (MA), ethyl acrylate (EA) and butyl acrylate (BA) were synthesized by radical copolymerization in benzene solution using azobis(isobutyronitrile) (AIBN) as initiator. The monomer reactivity ratios of these systems at 60°C were determined by the conventional schemes using the methods of Fineman–Ross, Joshi‐Joshi, and Kelen–Tüdos. DMP underwent a completely random and azeotropic copolymerization with MMA whereas in its reaction with the other acrylates DMP entered preferentially into the polymer chain. The reactivities of DMP‐terminated polymer radicals towards the acrylate monomers were found to be in the order: MMA > EA > MA > BA. An increase in solvent polarity decreased the relative reactivity of DMP for the DMP‐MMA pair. An examination of the molecular weights of the copolymers revealed the occurrence of chain transfer caused by DMP. The copolymer glass transition temperatures were determined and the variations of Tg with copolymer compositions were discussed according to the theory of Johnston, taking into account the effect of the sequence distributions of the comonomers on Tg. The Tgs of the alternating copolymers of DMP with the four alkyl acrylates were calculated.

Thermal properties of flame retardant cotton fabric grafted by dimethyl methacryloyloxyethyl phosphate

“…In the present work, thermal properties of flame retardant cotton fabric (FR cotton) grafted by dimethyl methacryloyloxyethyl phosphate (DMMEP) via atom transfer radical polymerization (ATRP) method were investigated. DMMEP was self-made according to the reported reference [2].…”

Pyrolysis Combustion Flow Calorimetry Studies on Some Reactively Modified Polymers

“…Syntheses of phosphorus-and phosphorus and nitrogen-containing unsaturated compounds were carried out following literature precedents [5][6][7]. The P-containing monomers prepared for this study included: two acrylic phosphonates: diethyl(acryloyloxymethyl)phosphonate (DEAMP) (R = H, structure 1, Figure 1) and diethyl(1-acryloyloxyethyl)phosphonate (DE1AEP) (R = CH3-, structure 1, Figure 1); acrylic phosphate: diethyl-2-(acryloyloxy)ethyl phosphate (DEAEP) (R = H, structure 2, Figure 1), and a methacrylic phosphate: diethyl-2-(metharyloyloxy)ethyl phosphate (DEMEP) (R = CH3-, structure 2, Figure 1).…”

Graft copolymerization modification of silk fabric with an organophosphorus flame retardant

“…Flame-retardant DMMEP was synthesized in our lab referred to the method reported by Nair et al [15] (Scheme 1). Other chemicals are reagent grade.…”