Combination of RAFT and Pd(II)-Initiated Isocyanide Polymerizations: A Versatile Method for Facile Synthesis of Helical Poly(phenyl isocyanide) Block and Star Copolymers

Abstract

We report a new method for facile synthesis of block and star copolymers composed of helical poly(phenyl isocyanide) and polyacrylate segments via combination of Pd(II)initiated isocyanide polymerization and reversible addition− fragmentation chain transfer (RAFT) controlled radical polymerization. First, an alkyne−Pd(II) complex containing benzyl trithiocarbonate substituent was designed and synthesized. The Pd(II) moiety of the complex can catalyzed the living polymerization of phenyl isocyanides, while the benzyl trithiocarbonate unit can be used as a chain transfer agent for RAFT polymerization. Upon combination of the two living polymerizations, a series of block copolymers containing poly(phenyl isocyanide) and polyacrylate, poly(aryl vinyl) blocks with expected molecular weights (M n s) and narrow molecular weight distributions (M w /M n s) can be facilely prepared under controlled manner. Some of these block copolymers exhibited interesting self-assembly and stimuli-responsive properties. Taking advantage of this synthetic approach, core cross-linked star block copolymer carrying polyacrylate-block-polyisocyanide arms can be readily prepared through the copolymerization with a cross-linker, ethylene glycol dimethacrylate. Moreover, miktoarm star copolymers carrying helical polyisocyanides and polyacrylates arms can also be prepared under controlled manner.

Facile Synthesis of Helical Rod–Coil Block Polymers by the Combination of ATRP and Pd(II)‐Initiated Isocyanides Polymerizations

“…However, the ATRP did not take place even at higher temperature (100 °C in toluene) or longer reaction time. Probably, the ATRP process was interfered by the CN double bonds in the polyisocyanide segment . To confirm the negative effect of the CN double bonds on ATRP, the classical ATRP homopolymerization of 1a was carried out with additional poly‐ 2a 50 .…”

An acrylate AIE-active dye with a two-photon fluorescent switch for fluorescent nanoparticles by RAFT polymerization: synthesis, molecular structure and application in cell imaging

“…Therefore, RAFT polymerization is considered to be an important and effective way to prepare multifunctional copolymers, which is widely used in materials science, biology, electronics, etc. [26][27][28][29][30][31][32] For example, amphiphilic block copolymer p(HEMA-b-Azo-IEM) was successfully prepared by RAFT polymerization, in water solution, which selfassembled into micelles, and its size and shape changed with the different light irradiation (visible/UV light). 33 Phenylboronic acid derivatives have been widely used in the synthesis of glucose-sensitive materials in the eld of biomedicine due to their specic interaction with biological molecules such as glucose and glycoproteins.…”

Vapor treatment, liquid crystal formation, magnetic orientation, and crystallization (VLMC) to form helical polyisocyanides with oriented crystal‐like structure

“…Previous studies reported synthesis of poly(phenyl isocyanide) derivatives with optical activity and a helical structure. [ 5–10 ] This required controlling the winding direction of the helix, as the orientation of the chiral side chain in the polymer dictates main‐chain helicity and macroscopic morphology of the polymer. Preparation of chiral polyisocyanides using a chiral oligomer as an initiator was previously employed to obtain chiral polymers, with the use of liquid crystal solvent isocyanide polymerization allowing the formation of one‐handed, optically active, helical polyisocyanides capable of analysis by atomic force microscopy and molecular calculations.…”