Controlled/living RAFT polymerization of N‐phenyl maleimide and synthesis of its block copolymers

Abstract

ABSTRACT:The controlled/living radical polymerization of N-phenyl maleimide (NPMI) was achieved using 2,2 0 -azobisisobutyronitrile as the initiator and 2-cyanopropyl-2-yl dithiobenzoate as the reversible addition-fragmentation chain transfer agent at 75 C in dichloroethane/ethylene carbonate (60/40, w/w) mixed solvent. The block copolymers of polystyrene-b-polyNPMI and poly(n-butyl methacrylate)-b-polyNPMI were successfully prepared by chain extension from dithiobenzoate-terminated polystyrene and poly (n-butyl methacrylate) to NPMI, respectively. The obtained NPMI-based (co)polymers were characterized by gel permeation chromatography and 1 H-NMR spectroscopy.

High Glass Transition Temperature Fluoropolymers for Hydrophobic Surface Coatings via RAFT Copolymerization

“…The aliphatic region of the 1H NMR spectrum of all copolymers consisted of the anticipated resonances of backbone protons due to PFS (between 1.5 and 2.8 ppm) and NMI/PFPMI (between 3.0 and 4.2 ppm) units in the polymer chain. [6,21,26] The tendency for alternating copolymerization of PFS and NMI can potentially be explained in terms of π-π interactions between the aromatic ring of NMI and the fluorinated aromatic ring of PFS. The highly electronegative nature of fluorine means that significant electron density is shifted away from the ring, resulting in a quadrupole moment (see Scheme 2).…”

“…[24] In all of these techniques, a particular polymer chain length is able to be targeted through the molar ratio of monomer(s) to specific control agent; RAFT is typically considered the most versatile of the RDRP techniques due to its ability to mediate the polymerization process for a wide range of monomers of differing reactivity. Alternating copolymers of styrene and NMI have been prepared via ATRP, [25] poly(NMI) and poly(styrene-block-NMI) have been prepared by dithiobenzoate-medaited RAFT polymerization, [26] and recently Yang et al reported the RAFT synthesis of a styrene-NMI copolymer in the context of polymerization-induced self assembly. [27] To our knowledge, PFS and NMI have not been copolymerized previously via the RAFT process.…”

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

“…Zhao et al reported the copolymerization of styrene with N-phenyl maleimide in the presence of an ATRP initiator bearing a polyarylether dendron in anisole [61] or with N-hexyl maleimide [62], N-phenyl maleimide [63], N-cyclohexyl maleimide [63], and N-butyl maleimide [63] in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. Block copolymers of N-phenyl maleimide and styrene were prepared under RAFT conditions using 2,2 -azobisisobutyronitrile as the initiator and 2-cyanopropyl-2-yl dithiobenzoate as chain-transfer agent [64]. Homopolymerization of N-phenyl maleimide was first evaluated, which indicated the ability to reach relatively high monomer conversion up to 65% with good control over the molecular weight distribution while following first-order kinetics.…”

Fundamental investigations into the free‐radical copolymerization of N‐phenylmaleimide and norbornene

“…Although the radical homopolymerization of N‐substituted maleimides, as well as its copolymerization with electron‐rich olefins such as styrene, n‐butyl vinyl ether, 3‐methylenecyclopentene, and isobutene monomers have been investigated, no such systematic and fundamental investigations into the free‐radical copolymerization behavior of norbornene and N‐substituted maleimides has ever been reported to the best of the author's knowledge. Additionally, given that certain controlled radical copolymerizations of N‐substituted maleimides and electron‐rich olefins have been reported to proceed in a predominantly alternating manner, but not in a strictly alternating fashion, a fundamental study into the polymerization kinetics and relative reactivity ratios for this particular pair of monomers is needed to fully understand the structure of their resultant copolymers.…”