Two- and Three-Component Post-Polymerization Modifications Based on Meldrum’s Acid

Abstract

Meldrum’s acid-based condensations were employed as a new method to develop two- and three-component postpolymerization modifications of polymers with conversion up to more than 99% at room temperature. Acrylic polymers containing Meldrum’s acid could be functionalized with a diverse scope of aldehydes yielding Knoevenagel condensates and functionalized with both aldehydes and nitromethane, leading to a library of polymers containing γ-nitrocarbonyl groups. Additionally, a novel thermal and aggregation-induced emission dual active polymer was constructed via two-component postpolymerization modification of a copolymer featuring thermal-responsive and Meldrum’s acid units.

Facile Multicomponent Polymerization and Postpolymerization Modification via an Effective Meldrum's Acid‐Based Three‐Component Reaction

“…Only one example was the postpolymerization modification by the effective three‐component reaction of Meldrum's acid, nitromethane and furfural. [ 39 ] Multicomponent polymerization via Meldrum's acid‐based multicomponent reactions has not yet been reported. Thus, developing Meldrum's acid‐based multicomponent polymerization is highly desirable to produce novel Meldrum's acid‐containing polymers with potential applications.…”

“…As shown in Figure S12 and S13, Supporting Information, 2‐(2‐methyl‐4,6‐dioxo‐1,3‐dioxan‐2‐yl)ethyl acrylate (MEA) was designed as a Meldrum's acid‐containing monomer, which was prepared according to the literature. [ 39 ] MEA copolymerized with methyl acrylate (MA) by reversible addition‐fragmentation chain transfer (RAFT) polymerization ( Figure A), resulting in PMEA‐ co ‐PMA with number‐average molecular weight ( M n ) of 30.0 kDa and Ð of 1.08 (Figure 3D). Conversions of both the two monomers were very high and the copolymer structure was confirmed by 1 H NMR and 13 C NMR measurements.…”

Self-foaming polymers: Opportunities for the next generation of personal protective equipment

“…Indeed, ketenes can be formed through thermal treatment of Meldrum's acid (MA), with the concomitant release of acetone and CO2 (Figure 3.5) [199]. They can dimerize or quantitatively react by condensation or addition reactions with a wide range of nucleophiles, making them highly appealing reagents in organic chemistry [200][201][202][203][204][205] and polymer science. [206][207][208][209] Various studies reported the combination of MA to high Tg polymers, i.e.…”

Malononitrile‐involved Michael addition polymerization: An efficient and facile route for cyano‐rich polyesters with programmable thermal and mechanical properties

“…Other diacrylate compounds were synthesized via the esterification reaction between diol and acryloyl chloride following a modified procedure in the literature. 48…”