Synthesis of polyethylene oxide end‐capped with perfluoroalkyl groups/polystyrene prototype brushes

Abstract

Polystyrene (PS)/poly(ethylene oxide) (PEO) prototype brushes were prepared by alternating free-radical copolymerization of methacryloyl-terminated PS and ␣-vinylbenzyl--hydroxy or ␣-vinylbenzyl--perfluoroalkyl (R f ) PEO macromonomers with the addition of Lewis acid (SnCl 4 ). It was found from their dilute-solution properties that PS/PEO end-capped with R f (PBR f ), and PS/PEO having OH groups at terminal ends (PBOH) prototype brushes formed a single molecule in benzene and aggregates in chloroform, respectively. However, the brush PBOH formed a single molecule in N,Ndimethylformamide. Such aggregation behaviors seemed to be caused by the interaction between hydroxy groups of PEO chain ends. The brush PBOH was also converted into PBR ftype brush by chemical modification, using corresponding acid chloride. The substitution of R f groups was ϳ70% due to slipping of terminal hydroxy groups into PEO internal domains.

Precision Synthesis of ω-Branch, End-Functionalized Comb Polystyrenes Using Living Anionic Polymerization and Thiol–Ene “Click” Chemistry

“…Most of the branch end-functionalized combs reported in the literature have been prepared by ring-opening polymerization or conventional radical polymerization. − There are a few examples applying controlled radical polymerization to synthesize such combs. − However, no one has taken advantage of precise control and high efficiency provided by living anionic polymerization to prepare vinyl-based combs with functionalized branch ends. Macromonomers with functionalizable groups at one end and polymerizable groups at the other end are suitable building blocks to prepare branch end-functionalized comb polymers by living anionic polymerization.…”

Synthesis and Self-Assembly Behavior of Four-Arm Poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) Star Block Copolymer in Salt Solutions

“…The star block copolymers offer interesting properties concerning both micellization and microphase separation behavior compared to corresponding linear block copolymers. − The greater proportion of end functional groups induces higher solubility in various solvents compared to linear structure of identical molecular weights. Multiarm PEOs possess three-dimensional branched structures and higher densities of terminal functional groups. − …”

Atom transfer radical polymerization as a powerful tool in the synthesis of molecular brushes

“…anionic polymerization) of a monomer (e.g. styrene (St), methyl methacrylate (MMA), ethylene glycol or vinyl pyridines) and then end‐functionalized with a suitable polymerizable group, such as St, methacrylate or norbornene . MBs that vary widely in chemical nature and properties can be synthesized.…”