Soluble high polymers from allyl methacrylate

Abstract

Allyl methacrylate has been polymerized by free‐radical methods and found to yield a soluble polymer in carbon tetrachloride, dioxane, and diallyl ether solutions. The overall rate equation in diallyl ether is Rp = k[ln]0.7[M]1.6. It is suggested that propagation and cyclization reactions proceed only via addition to the methacrylyl groups of the monomer. Some degradative chain transfer occurs with the allyl groups, and it is considered that the solvents may ensure the production of soluble polymers by reactions in which allyl–radical side chains are terminated without crosslinking.

Solventless Synthesis and Patterning of UV‐Responsive Poly(allyl methacrylate) Film

“…We then explored the effect of different iCVD conditions on the polymerization of AMA. According to literature, the polymerization temperature plays a decisive role in the retention of the allyl group . In contrast to liquid‐based synthesis where monomers and initiator are mixed during polymerization, the cleavage of initiator and polymerization of monomers are separated in the iCVD process.…”

“…The allyl peaks at 986 and 935 cm −1 persisted, indicating large retention of pendent allyl groups . Conversion of a small portion of allyl groups was also observed as a small peak at 1773 cm −1 corresponding to the CO stretching vibration in γ‐butyrolactone moiety that appeared in iCVD PAMA, which was resulted from the intramolecular cyclization of allyl groups (Figure c) …”

“…[12,13] However, radical polymerization of AMA under normal conditions may lead to crosslinking or cyclization of the side chain, depleting allyl groups at an early stage of polymerization ( Figure 1c). [10,[14][15][16][17][18][19] So far, to retain the allyl group of AMA for further reactions, harsh conditions such as low temperature and/ or additional additives are usually required during polymerization. [7,11,20] Vapor deposition offers a more advantageous approach in synthesizing crosslinked films than traditional liquidbased methods, since polymerization and crosslinking take place during film formation as opposed to liquid-based film fabrication.…”

Green methacrylated lignin model compounds as reactive monomers with low VOC emission for thermosetting resins

“…The enthalpy of the reaction (ΔH) illustrated in Table 2, is also observed to be higher in the VEOCN sample containing styrene than in the samples containing MG and ME which indicates a lower degree of curing or crosslinking in VEOCN sample containing styrene than in the samples containing MG and ME [24]. When comparing the reactivity of ME and MG from Figure 6 and Table 2, it can be seen that ME is found to be less reactive than MG, as the allyl substituent present at the para position of the methacrylate group in ME forms a stable free radical ion due to the resonance stabilization and this stable free radical ion of the allyl substituent present in ME competes with the normal propagation reaction step during the curing reaction between ME and the VEOCN resin system and inevitably disrupts and decelerates the chain growth by DCT reaction [25]. The resulting allyl free radical does not readily add to the VE monomer but once all the methacrylic C = C groups of the ME molecule undergo copolymerization with vinylic C = C groups of the VEOCN, the allylic C = C groups would further take part in the copolymerization [26].…”

Structure-property correlation study of bio-based multifunctional vinyl ester resin in presence of methacrylated lignin model compounds

“…On com paring the reactivity of ME and MG from Fig. 9, it can be seen that methacrylated eugenol is found to be less reactive than MG, since the allyl substituent present at para position to methacrylate group in ME form a sta ble free radical due to resonance stabilization and this stable free radical of allyl substituent present in ME competes with the normal propagation reaction step during the curing reaction between ME and VTMPAE resin system which inevitably disrupts and decelerate chain growth by degradative chain transfer (DCT) reaction [24]. The resulting allyl free radical does not readily add to the vinyl ester monomer but once all the methacrylic C=C groups of the ME are consumed in copolymerization, the allylic C=C groups start copo lymerizing [25].…”