Alternating Copolymerization by Nitroxide‐Mediated Polymerization and Subsequent Orthogonal Functionalization

Abstract

A novel method for the preparation of functionalized alternating copolymers is presented. Nitroxide-mediated polymerization of hexafluoroisopropyl acrylate with 7-octenyl vinyl ether provides the corresponding alternating polymer, which can be chemically modified using two orthogonal polymer-analogous reactions. A thiol-ene click reaction followed by amidation provides dual-functionalized alternating copolymers. The potential of this method is illustrated by the preparation of a small library (15 examples) of functionalized alternating copolymers.

Coding and decoding libraries of sequence-defined functional copolymers synthesized via photoligation

“…Generating an ensemble of perfectly sequence-defined identical macromolecules containing exactly the same chemical information at the molecular scale—in contrast to existing avenues to disperse and irregularly coded species when compared with natural analogues—via a simple process constitutes a key technological gate for data storage, biological and material applications, yet requires reaction concepts that provide perfect yields and orthogonality under equimolar reaction conditions. Although solid-state peptide synthesis was introduced by Merrifield6—the first example of a true synthetic sequence-defined peptide—macromolecular chemists have initially focused on and developed a diverse number of solution-based polymerization strategies for imparting a certain level of control over statistical polymerization processes and exploited these for controlling the order of the building blocks (sequence-controlled polymers)7891011121314151617181920. In addition, the advent of modular synthetic strategies21222324 has contributed significantly towards achieving a high level of control over macromolecular formation processes.…”

Organometallic‐Mediated Alternating Radical Copolymerization of tert‐Butyl‐2‐Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof

“…For other monomer pairs, highly ordered monomer sequence control is still challenging . Regarding fluorinated polymers, recently, Studer and coworkers and the Scherf's team attempted the synthesis of predominantly alternating copolymers composed of hexafluoroisopropyl acrylate with 7‐octenyl vinyl ether and N ‐dialkylated benzothiadiazolodithienopyrrole with a dibrominated terephthalophenone derivative, respectively. Recently, Jordan's group reported (phosphinoarenesulfonate)Pd fluoride complex catalyst reactivation following β‐F elimination in ethylene/vinyl fluoride copolymerization …”

Orthogonal Click Postfunctionalization of Alternating Copolymers Prepared by Nitroxide‐Mediated Polymerization

“…Along these lines, we have recently introduced alternating nitroxide‐mediated polymerization (NMP) of 1,1,1,3,3,3‐hexafluoroisopropyl acrylate (HFIPA) 1 and (7‐octenyl)vinyl ether (OVE). The resulting poly(HFIPA‐ alt ‐OVE) was orthogonally postfunctionalized via radical thiol–ene click reaction and subsequent amidation . It is well known that the properties of polymers can be altered significantly by chemical postfunctionalization and numerous recent reports deal with the modification of polymers by thiol click chemistry, Cu‐catalyzed alkyne–azide click reaction (CuAAC), amidation reactions, and many others, including combinations thereof.…”