Synthesis of Well‐defined Amphiphilic Block Copolymers by Organotellurium‐Mediated Living Radical Polymerization (TERP)

Abstract

Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method.

Stereospecific catalytic precision polymerization of 2-vinylpyridine via rare earth metal-mediated group transfer polymerization with 2-methoxyethylamino-bis(phenolate)-yttrium complexes

“…24,25 The group of Natta introduced the anionic polymerization of 2VP with metallorganic compounds in the early 60s. [32][33][34][35][36] In addition Frustrated Lewis pair, 37,38 anionic [39][40][41][42][43][44] and radical [45][46][47][48] polymerizations have been applied to synthesize functional but atactic P2VP based materials. Subsequent mechanistic studies of Soum and Fontanille with organomagnesium compounds revealed that the stereocontrol derives from a Markov-chain end control through a favoured gauche coordination of two monomers to the metal cation.…”

“…[28][29][30][31] Apart from the mentioned examples only few groups investigated the stereospecific polymerization of 2VP. [32][33][34][35][36] In addition Frustrated Lewis pair, 37,38 anionic [39][40][41][42][43][44] and radical [45][46][47][48] polymerizations have been applied to synthesize functional but atactic P2VP based materials. Rare earth metal-mediated group transfer polymerization (REM-GTP) in contrast is a relatively recent polymerization method for 2VP.…”

Polymersomes: Breaking the Glass Ceiling?

“…Since most of these polymerizations are conducted above 60 °C, the high‐temperature morphology can be kinetically trapped upon cooling to room temperature. PISA has also been reported with other polymerization techniques, such as atom‐transfer radical polymerization, organotellurium‐mediated radical polymerization, and ring‐opening metathesis polymerization . Interestingly, many of the hydrophobic blocks grown via the PISA process have been glassy in nature.…”

A synthetic route to ultra-high molecular weight polystyrene (>106) with narrow molecular weight distribution by emulsifier-free, emulsion organotellurium-mediated living radical polymerization (emulsion TERP)

“…[25][26][27] The possible reversible activation processes of TERP are degenerative chain transfer (DT) and thermal dissociation (TD) mechanisms, in which the TD can be negligible below 100°C (Scheme 1). [25][26][27] The possible reversible activation processes of TERP are degenerative chain transfer (DT) and thermal dissociation (TD) mechanisms, in which the TD can be negligible below 100°C (Scheme 1).…”