Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N‐substituted Maleimides

Abstract

In the present Feature Article, a kinetic strategy for controlling the microstructure of synthetic polymer chains prepared via a radical chain‐growth polymerization process is presented. This approach was recently developed in our laboratory and relies on the controlled kinetic addition of ultrareactive N‐substituted maleimides during the atom transfer radical polymerization of styrene. This method is experimentally straightforward and can be applied to a broad library of functional N‐substituted maleimides. Thus, this platform allows synthesis of unprecedented polymer materials such as 1D macromolecular arrays. The basic kinetic requirements, the experimental conditions, and the synthetic scope of this approach are discussed in details herein. magnified image

Functional Polymers with Controlled Microstructure Based on Styrene and N ‐Substituted Maleimides

“…indicated a pronounced alternating tendency for the tert-butyl 4-vinyl benzoate and N-benzylmaleimide pair, but the value obtained (r t-BuVBA/BzMI = 0.14) was slightly higher than the one previously obtained for styrene and N-substituted maleimides [18] suggesting a lower incorporation precision. N-substituted maleimides were added to polymerization medium at the beginning of the polymerization or 2 h after the homopolymerization of tert-butyl 4-vinyl benzoate, corresponding to approximately half conversion of this monomer.…”

“…Our research group has been especially interested in using styrene and maleimides as comonomer pairs and taking advantages of their specific copolymerization behavior to prepare well-defined copolymers with controlled microstructure (Figure 7.1) [18]. In this chapter, we first review the copolymerization of these monomer pairs under conventional and controlled radical polymerization conditions before introducing the strategy developed in our laboratory allowing the precise positioning of various N-substituted maleimides on a polystyrene backbone.…”

Sequence-controlled polymers via reversible-deactivation radical polymerization

“…This means that the minor monomer selectively propagates over the primarily existing monomer even though there is a big difference in the injected amounts of the comonomers. Lutz and co-workers [36][37][38][39][40][41][42][43][44] noticed the crossover propagation feature of the alternating copolymerization for achieving local functionalization of a polymer chain using RDRP (Figure 6a). In this approach, styrene or the derivative is polymerized with RDRP (ATRP or NMP), and a slight excess of an MI derivative is added to the growing chains during the RDRP for pinpoint insertion.…”

Photocrosslinkable Star Polymers via RAFT-Copolymerizations with N-Ethylacrylate-3,4-dimethylmaleimide

“…Disubstituted double bonds are known to propagate very slowly [32]. Maleimide is nevertheless known to undergo copolymerizaton with styrene [33] and with acrylates [34] to some extent. Additional substitution of the double bond with two methyl groups on either side is further reducing the probability of being partner in a radical polymerization.…”