Sequential and one-pot post-polymerization modification reactions of thiolactone-containing polymer brushes

Abstract

Polymer brushes carrying pendent thiolactone functional groups were explored for the design of multifunctional homopolymer brush architectures using sequential and one-pot postpolymerization strategies.

Photocrosslinking of Polyacrylamides Using [2 + 2] Photodimerisation of Monothiomaleimides

“…The synthesis of TLA monomer was achieved by the addition of acryloyl chloride to D,L-homocysteine thiolactone hydrochloride according to a literature procedure. 28 The monomer was characterized by 1 H and 13 C NMR (Figure S1, Supporting Information) with the most important finding for the TLA monomer characterization being the presence of the olefin group at 5.65 and 6.18 ppm, thus indicating the successful synthesis of the monomer. Additionally, the N−H peak of the amide group was observed at 8.46 ppm, which confirmed the formation of the acrylamide monomer.…”

Thiolactone chemistry, a versatile platform for macromolecular engineering

“…96 Interestingly in a paper of Reese et al, the double post-polymerization modification of poly(acrylamide-homocysteine thiolactone) brushes was performed with 4-bromobenzylamine and 1H,1H-perfluoro-N-decyl acrylate using either sequential or one-pot strategies, enabling a comparison of both pathways. 77 Interestingly, the functionalization rate of the second step was higher in the case of the one-pot strategy (59% aminolysis conversion, 74% thiol-Michael conversion) than in the case of the sequential process (54% aminolysis conversion, 11% thiol-Michael conversion). The authors assumed that the one-pot process enabled both reactants to readily diffuse into the brush resulting in a more efficient double conjugation.…”

“…homocysteine-γ-thiolactone (Figure 5.2) initiated by AIBN in DMF at 70°C, 76 or by micro-wave assisted surface-initiated radical polymerization. 77 PAM-TL were successfully applied in industrial waste-water for capturing Ag(I), due to the highly selective and highly effective adsorption ability of thiolactones toward Ag(I). 76 Alternatively, PAM-TL brush surfaces were modified with amines and functional acrylates or maleimides in DMSO in the presence of TEA at room temperature, in order to prepare various multifunctional polymer surfaces.…”

“…76 Alternatively, PAM-TL brush surfaces were modified with amines and functional acrylates or maleimides in DMSO in the presence of TEA at room temperature, in order to prepare various multifunctional polymer surfaces. 77 A thiolactone-functionalized maleimide (Figure 5.3) was synthesized by Rudolph et al and polymerized by free radical polymerization using either AIBN as initiator in THF at 70°C or Lucirin TPO in dichloromathane/or in the bulk under UV irradiation. 78 In addition, free radical copolymerization of thiolactone-containing norbornene monomer (Figure 5.4) and methyl acrylate were carried out using AIBN as initiator at 80°C in butyl acetate for 3 hours.…”

Main-chain/side-chain type phosphine oxide-containing reactive polymers derived from the same monomer: controllable RAFT polymerisation and ring-opening polycondensation

“…[1][2][3][4][5] Monomer design and post-polymerisation modification techniques are regarded as the two main routes to prepare reactive polymers, and recent advances in this field have undoubtedly provided great possibility for synthesizing reactive polymers with different purposes. [6][7][8][9][10][11][12] Among them, post-polymerisation modification, known as the polymer analogous reaction, is one of the most versatile and successful synthetic tools. However, conversions of the original groups to expected functionalities are interfered by the steric hindrance and probability effect, resulting in unmodified groups remaining along the main chains or side chains.…”