Synthesis, characterization, and cyclopolymerization of a functional non-symmetric divinyl monomer

Abstract

A non-symmetric divinyl monomer with a terminal carboxylic acid functionality was readily synthesized from the reaction of ethyl α-hydroxymethylacrylate (EHMA) with maleic anhydride. The new monomer (EHMA-MA) was homopolymerized in both bulk and ethyl acetate using AIBN as an initiator to give cyclopolymers. The synthesis of the monomer and cyclopolymers were followed by 13 C NMR, 1 H NMR, and FTIR. 1 H NMR was also utilized to obtain the degree of cyclization of the polymers, which were found to be 95% or higher in all cases. The molecular weights of the cyclopolymers were around 40-60,000 g/mol as estimated by SEC. The cyclopolymers were thermally stable up to 150 o C. Although the cyclopolymers obtained were not water-soluble; they were soluble in aqueous 1M NaOH solution. In addition to the carboxylic acid functionality present, the cyclopolymers also had an ethyl ester and a lactone moiety. These functional groups were reacted with hexylamine to obtain a polymer with imide and amide moieties.

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

“…In a recent example, Mathias cyclopolymerized in both bulk and ethyl acetate a nonsymmetric divinyl monomer, obtained from the reaction of ethyl a-hydroxymethylacrylate with maleic anhy- dride, to afford, similarly to P10, exclusively five-membered ring structures in the repeating unit. 57 In back-to-back reports, 58,59 Frećhet and co-workers expanded on their initial studies 45 by implementing carbon and cage-rich, cyclopolymerizable monomers 13 and 14, for use as photoresists in 193 nm lithography. With the aid of cyclization studies on model compounds and refined NMR spectroscopic techniques, they were able to rationalize that, whereas allyl systems cyclopolymerize to from exclusively five-membered repeating structures (P13), the methallyl systems (14) cyclopolymerize to give both the fiveand the six-membered structures (Figure 5).…”

“…The methallyl group in the α-substituent facilitates more significantly the cyclopolymerization than the allyl group, although they were not able to substantiate which one of the two forms (either five or six membered rings in Figure ) was predominant in cyclopolymers P11 and P12 . In a recent example, Mathias cyclopolymerized in both bulk and ethyl acetate a nonsymmetric divinyl monomer, obtained from the reaction of ethyl a-hydroxymethylacrylate with maleic anhydride, to afford, similarly to P10 , exclusively five-membered ring structures in the repeating unit …”

Cyclopolymerization of α,ω‐heterodifunctional monomers containing styrene and maleimide moieties

“…At the very beginning, the majority of researches were confined in the cyclopolymerization of monomers typically proceeded via formation of thermodynamically stable five‐ or six‐membered rings before or during the period of polymerization process . Then, cyclopolymerizations proceeded via various mechanisms were discovered.…”

“…[3][4][5] At the very beginning, the majority of researches were confined in the cyclopolymerization of monomers typically proceeded via formation of thermodynamically stable five-or six-membered rings before or during the period of polymerization process. [6][7][8][9][10][11] Then, cyclopolymerizations proceeded via various mechanisms were discovered. The enhancements of cyclization by bulky substituents were reported by Holmes and coworkers 12,13 and Prata and coworkers.…”

Synthesis and characterization of rigid functional anionic polyelectrolytes: Block copolymers and star homopolymers

“…Cyclolinear polymers derived from alkyl α‐(hydroxymethyl)acrylate (RHMA) ether dimers exhibit a high degree of local cyclization and, therefore, display increased polymer backbone rigidity, high glass transition temperatures ( T g s), and reduced shrinkage during polymerization when compared with noncyclic linear analogs 3. As shown by previous studies involving conventional free‐radical polymerization,4 the cyclopolymerization of RHMA ether dimers can be achieved through intermolecular propagation and intramolecular cyclization,5 resulting in polymers with six‐membered tetrahydropyran repeating units. The major obstacle to overcome in these polymerizations is incomplete cyclization, which leads to unreacted double bonds that can act as cross‐linking sites.…”