Sequence-regulated vinyl copolymers with acid and base monomer units via atom transfer radical addition and alternating radical copolymerization

Takamasa Soejima,Masami Kamigaito,Kotaro Satoh

doi:10.1039/c6py00965d

Abstract

Sequence-regulated vinyl copolymers with acid and base monomer units were prepared via atom transfer radical addition and alternating radical copolymerization.

Highlights

Natural functional macromolecules, such as proteins, consist of controlled sequences of “monomers” that possess hydrophobic, hydrophilic, polar, nonpolar, ionic, nonionic, aliphatic, aromatic, acid, base, or other moieties with various properties and functions
A series of maleimide-ended sequence-regulated acid- or basefunctionalized oligomonomers were prepared by atom transfer radical addition (ATRA) between t-butyl acrylate (tBA), DMAEA, or styrene and their unimer halides followed by SN2 reaction between the resulting dimer halides and furan-masked maleimide anion with a retro Diels–Alder reaction to deprotect the furan group
As previously reported,[17,18] we selectively employed RuCp*Cl(PPh3)[2] for styrene terminal halides (Cl–S, Br–S) and acrylate terminal chloride (Cl–B), and CuBr/PMDETA was employed for acrylate terminal bromide (Br–Ap). These ATRAs proceeded as those reported for methyl acrylate (MA) with no functional moieties[17,18] even though the products gradually decomposed during purification via lactonization of Br–SAp or quaternization between the halide and pendent amine moiety in Cl–SB and Cl–BS

Summary

Introduction

Natural functional macromolecules, such as proteins, consist of controlled sequences of “monomers” that possess hydrophobic, hydrophilic, polar, nonpolar, ionic, nonionic, aliphatic, aromatic, acid, base, or other moieties with various properties and functions. Main- and side-chain sequence-regulated vinyl copolymers with acid and base monomer units were prepared using atom transfer radical addition (ATRA) and alternating radical copolymerization. A series of maleimide-ended sequence-regulated “oligomonomers” were prepared by ATRA of t-butyl acrylate (tBA: Ap) (i.e., a protected acrylic acid (A)) or an amine-functionalized acrylate, (2-(dimethylamino)ethyl acrylate (DMAEA: B)), and styrene (S) followed by an SN2 reaction of furan-protected maleimide (M) anion and its deprotection.

Results

Conclusion