Approaching new biomaterials: copolymerization characteristics of vinyl esters with norbornenes, allyl esters and allyl ethers

Abstract

Vinyl ester‐based monomers for radical photopolymerization have recently been shown to be promising alternatives to (meth)acrylates through lower irritancy and cytotoxicity. Vinyl ester monomers are becoming increasingly important on account of new, more cost‐efficient synthetic production methods, not to forget their increased reactivity and improved material properties in combination with thiol–ene polymerization. Due to their biocompatibility and degradability, these monomers are more frequently used in tissue engineering. Nevertheless, the material properties can be improved by possible copolymerizations with other monomers. Therefore, the copolymerization behavior of vinyl ester with norbornene, allyl ether and allyl ester has been studied fundamentally in a photoreactor via free radical photopolymerization. Here, the consumption of double bonds of the monomers has been identified using NMR spectroscopy. Copolymerization parameters have been determined using the Kelen–Tüdös method. Results show equal consumption of vinyl ester and co‐monomer double bonds leading to alternating copolymerizations. The double bond conversion was confirmed via in situ real‐time near‐infrared photorheology. Mono‐ and difunctional vinyl esters with co‐monomers have also provided further insight into the polymer network of these copolymers. © 2021 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

Synchronously improved toughness and dielectric properties of cyanate ester resins via modification with biobased poly(N‐phenylmaleimide‐co‐limonene)

“…Meanwhile, PML microspheres with smooth surface and significantly narrow particle size distribution (PSD) were successfully formed (PSD decreased from 1.65 to 1.01–1.03, which was calculated using Equation (S3) in the Supporting information). Generally, the copolymerization of allyl monomers usually resulted in low molecular weight polymer products due to degradative chain transfer reaction of allyl monomer 34 . Hence, the slightly decreased number‐average molecular weight ( M n ) was mainly attributed to increasing molar ratio of LIM in monomer feed.…”

“…Generally, the copolymerization of allyl monomers usually resulted in low molecular weight polymer products due to degradative chain transfer reaction of allyl monomer. 34 Hence, the slightly decreased numberaverage molecular weight (M n ) was mainly attributed to increasing molar ratio of LIM in monomer feed.…”