Baylis–Hillman Reaction as a Versatile Platform for the Synthesis of Diverse Functionalized Polymers by Chain and Step Polymerization

Abstract

The Baylis–Hillman reaction, which is a carbon–carbon bond forming reaction between an aldehyde and an activated alkene, was utilized to prepare densely functionalized monomers suitable for chain and step polymerization. By reacting formaldehyde with various alkyl acrylates, a series of alkyl α-hydroxymethyl acrylate monomers were synthesized. These monomers efficiently underwent RAFT polymerization to provide α-hydroxymethyl-substituted polyacrylates with well controlled molecular weight and low polydispersity. The resulting homopolymers were also efficient macro-chain transfer agents for further RAFT polymerization. The Baylis–Hillman reaction was also utilized to synthesize alkene functionalized diols which underwent step-growth polymerization to provide polyesters and poly(ester urethane)s. Furthermore, it was demonstrated that the alkene group can be quantitatively functionalized by thiol–ene click chemistry to provide a series of polymers with diverse physical properties.

Aza‐Michael addition reaction: Post‐polymerization modification and preparation of PEI/PEG‐based polyester hydrogels from enzymatically synthesized reactive polymers

“…It is envisaged that the presented post‐functionalization and gelation schemes can be extended to other families of reactive polyesters carrying an aza‐Michael acceptor along the polymer backbone. These include free‐radically prepared allylic sulfide ester polymer family established by Evans and Rizzardo and Baylis‐Hillman derived poly(ester urethane)s developed by Peng and Joy …”

“…These include free-radically prepared allylic sulfide ester polymer family established by Evans and Rizzardo 42 and Baylis-Hillman derived poly(ester urethane)s developed by Peng and Joy 43. ACKNOWLEDGMENTSDanish Agency for Science, Technology and Innovation for funding is gratefully acknowledged for financial support.…”

Preparation of Tetrasubstituted Olefins Using Mono or Double Aerobic Direct C–H Functionalization Strategies: Importance of Steric Effects

“… 16 Experimental data were in accordance with those reported in the previous literature. 17 1 H NMR (CDCl 3 , 400 MHz): δ 6.25 (q, J = 1.3 Hz, 1H), 5.82 (q, J = 1.4 Hz, 1H), 4.33 (m, 2H), 4.20 (t, J = 6.6 Hz, 2H), 1.67 (qu, J = 7.4 Hz, 2H), 1.40 (sex, J = 7.4 Hz, 2H), 0.95 (t, J = 7.4 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz): δ 166.5, 139.6, 125.7, 64.9, 62.8, 30.7, 19.2, 13.8.…”

Synthesis, Functionalization, and Controlled Degradation of High Molecular Weight Polyester from Itaconic Acid via ADMET Polymerization

“…Postpolymerization modification of polyesters with similar vinyl groups synthesized via the Baylis−Hillman reaction has been reported. 50,51 However, the molecular weights of the polymers are low, the synthetic procedure is complicated, and the monomers are limited and nonrenewable. Moreover, compared with the vinyl groups generated by the Baylis−Hillman reaction, the itaconate vinyl groups have distinct properties.…”