Synthesis and Polymerization of Ethyl Alpha Chloromethylacrylate and Related Derivatives

Document Type


Publication Date



Polymers and High Performance Materials


Ethyl α-hydroxymethylacrylate (EHMA) was synthesized from ethyl acrylate and paraformaldehyde, and converted to ethyl α-chloromethylacrylate (ECMA) by reaction with thionyl chloride. ECMA was bulk polymerized at 65°C with α,α′-azobis(isobutyronitrile) (AIBN) to give a homopolymer with a viscosity of 0.084 dL/g. Spontaneous polymerization at ambient temperature surprisingly gave material with an intrinsic viscosity of 0.45 dL/g. Combined size exclusion chromatography-laser light scattering in THF for the former gave Mn = 21,900, Mw = 26,500, and Mz = 34,340 with a dn/dc = 0.079 mL/g. The homopolymer of ECMA was substituted with octadecyl mercaptan in THF using solid NaOH and Aliquat 336 as base and catalyst, respectively. Copolymers of ECMA with styrene were synthesized by free radical polymerization with relatively high conversion. Copolymer compositions were determined using proton NMR and were found to be similar to feed ratios as expected for high conversion products. Both copolymers were reacted with 2-ethyl-2-oxazoline (1:50 mole ratio) in an attempt to graft the oxazoline onto the polymer chain with only limited success. Two potential monomers were synthesized by reacting ECMA with 2-ethyl-2-oxazoline neat and octadecyl mercaptan in CHCl3 using triethylamine as a catalyst. Neither material polymerized under normal radical conditions. Characterization of monomers and polymers involved FTIR and 13C NMR spectroscopy, differential scanning calorimetry, viscosity, and size exclusion chromatography-laser light scattering.

Publication Title

Journal of Polymer Science Part A: Polymer Chemistry





First Page


Last Page