Synthesis of poly(aryl ether sulfone)‐graft‐polystyrene and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] through atom transfer radical polymerization

Abstract

A new graft copolymers poly(aryl ether sulfone)‐graft‐polystyrene (PSF‐g‐PS) and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] (PSF‐g‐(PS‐b‐PMMA)) were successfully prepared via atom transfer radical polymerisation (ATRP) catalyzed by FeCl2/isophthalic acid in N,N‐dimethyl formamide. The products were characterized by GPC, DSC, IR, TGA and NMR. The characterization data indicated that the graft copolymerization was accomplished via conventional ATRP mechanism. The effect of chloride content of the macroinitiator on the graft copolymerization was investigated. Only one glass transition temperature (Tg) was detected by DSC for the graft copolymer PSF‐g‐PS and two glass transition temperatures were observed in the DSC curve of PSF‐g‐(PS‐b‐PMMA). The presence of PSF in PSF‐b‐PS or PSF‐g‐(PS‐b‐PMMA) was found to improve thermal stabilities. © 2002 Society of Chemical Industry

Recent advances in the preparation of functionalized polysulfones

“…Moreover, the halomethylated polysulfones used as macroinitiators in ATRP can be easily prepared by a Friedel−Craft alkylation reaction. Various types of polymers including polyacrylamide, poly( N ‐isopropylacrylamide), polystyrene, poly(sodium 4‐styrene sulfonate), poly(2‐gluconamidoethyl methacrylate), poly(2‐hydroxyethyl methacrylate), poly(glycidyl methacrylate) and poly(ethylene glycol) methacrylate were successfully attached on the polysulfone backbone via a grafting‐from ATRP approach. The hydrophilic/hydrophobic balance in the graft copolymers can be adjusted by tailoring the chain lengths of side chains, which can be controlled by the reaction time in the ATRP.…”

Synthesis and characterization of well defined polysulfone-g-poly(styrenesulfonic acid) graft copolymers for proton exchange membrane

“…SSNa was graft polymerized to PSF-DTB via RAFT polymerization to prepare PSF-g-PSSNa. RAFT polymerization is one of 'controlled' radical polymerization techniques, and offers advantages when it comes to the variety of radically polymerizable monomers, 28 and in the choice of polymerization solvent. Molecular weight can be successfully controlled by simply manipulating the monomer conversion and RAFT agent concentration.…”

“…In the first step, chloromethylation of PSF was carried out. 28 To a 250 mL two neck flask equipped with condenser, magnetic bar, and dropping funnel, were charged 10 g of polysulfone and 140 mL of tetrachloroethane. After the solution was heated to 110 o C, 23.8 mL (286 mmol) of chloromethyl methyl ether was added and 0.185 mL (1.58 mmol) of tin tetrachloride was added slowly over a period of 15 min.…”

Synthesis of well‐defined polystyrene‐graft‐poly(methyl methacrylate)

“…In the ‘grafting‐through’ technique via ATRP, a macromonomer is copolymerized with a low‐molecular‐weight comonomer, producing graft copolymers with good control of (1) the length of the side‐chain made by living polymerization, (2) the chain length of the backbone controlled by the living ATRP process and (3) the average side‐chain density and the spacing distribution of the side‐chains determined by the apparent reactivity ratio of the macromonomer in the copolymerization and the ratio of the macromonomer in the feed. In the ‘grafting‐from’ technique via ATRP,18–53 a polymer having ATRP‐active halide atoms as side‐groups is used as a macroinitiator for the ATRP of a second monomer. Generally, the macroinitiators can be obtained directly by copolymerizing a monomer containing an ATRP‐initiating group by using a polymerization mechanism different from ATRP20–30, 36, 37 or by copolymerization of a monomer carrying a precursor group that can be transformed to an ATRP‐initiating group 31–34, 38–53.…”

“…The macroinitiators with benzyl chloride or bromide initiating groups are the most widely used for the synthesis of graft copolymers in the ‘grafting‐from’ technique via ATRP 20–23, 36–46, 52, 53. However, benzyl halide is a poor initiator for methacrylate monomers, with slow initiation when compared with propagation, and then low initiation efficiency 54.…”