Facile Synthesis and Polymerization of Ether Substituted Methacrylates

Abstract

New difunctional methacrylate monomers containing f3 heteroatoms have been synthesized from o:-hydroxymethylacrylate esters or o:-chloromethylacryloyl chloride. These monomers are more reactive than their alkane counterparts (e.g., ethacrylates), giving polymers with molecular weights comparable to poly(itaconate)s. The simple synthetic approach described allows a wide range of difunctionalized acrylate monomers to be produced. Variations in both ester and ether substituents were explored for ease of synthesis and polymerization.

Modeling the free radical polymerization of acrylates

“…Furthermore, acrylates, having capto‐substituents, produce more stable propagating radicals as compared with allyl radicals and therefore, the propagation reaction is more exothermic in the case of acrylates 7, 23. Insertion of a heteroatom on the methylene group has a positive effect on the polymerizability of the monomer 13–17. Wong and Radom 8 have reported that large substituents would not affect the maximum overlap between the unpaired electron of the propagating radical and the unoccupied π orbitals of the double bond.…”

“…In contrast, the addition reaction is known to be disfavored entropically; therefore, the elimination of chlorine atom is entropy driven. Methyl α‐methoxymethylacrylate (MC 1 MA) and methyl α‐acetoxymethylacrylate (MAcMA) have been reported to show even better conversions to high‐molecular‐weight than MMA 17–19. In contrast, the ether group of MC 1 MA and the ester group of MAcMA have been reported to lower the propagation rate constant to some extent due to the through space interactions of the approaching radical and the monomer substituents 17, 19.…”

“…Methyl α‐methoxymethylacrylate (MC 1 MA) and methyl α‐acetoxymethylacrylate (MAcMA) have been reported to show even better conversions to high‐molecular‐weight than MMA 17–19. In contrast, the ether group of MC 1 MA and the ester group of MAcMA have been reported to lower the propagation rate constant to some extent due to the through space interactions of the approaching radical and the monomer substituents 17, 19. Also, for MC 1 MA and MAcMA, the degradative chain transfer reaction rate is lower than the propagation reaction rate, and the net result is the production of higher‐molecular‐weight polymers than MMA 17, 19.…”

“…Polymerization of acrylates is one of the most efficient processes for the rapid production of polymeric materials in high performance inks, coatings, stereo‐lithography, dental restorative fillers and the preparation of contact lenses 7. Because of the wide variety of their industrial usage, acrylate derivatives have been synthesized and studied extensively 5–19.…”

Synthesis of polymer gel with chiral helical cavity by molecular imprinting using bifunctional vinyl monomers

“…To improve the chiral recognition ability of these gels, we designed novel a-(benzyloxymethyl)acrylic acids (X-BMAA; X ¼ p-OMe, o-OMe, m-OMe, p-Me, p-Cl, p-Br) as the monomer, which has two different types of substituents on an olefin [11,12], and carried out the radical copolymerization with EDMA in the presence of (þ )-poly(D2PyMA). Because the bifunctional X-BMAAs can interact with the template polymer through a p -p interaction, in addition to the hydrogen bonding between the carboxylic and pyridyl groups, these monomers may effectively reflect the template structure and create a chiral helical cavity more precisely than MAA during the molecular imprinting process.…”