Atom Transfer Radical Polymerization of Potassium 3-Sulfopropyl Methacrylate:  Direct Synthesis of Amphiphilic Block Copolymers with Methyl Methacrylate

Abstract

The synthesis of potassium 3-sulfopropyl methacrylate (SPMA) homopolymers and amphiphilic block copolymers with methyl methacrylate (MMA) by ATRP in water/DMF mixed solvent at 20 °C using a Cu/bipyridine catalyst and halogen exchange is described. SPMA homopolymerization in pure water was poorly controlled even when 200% of Cu(II)Cl 2 with respect to Cu(I)Cl was added, leading to a relatively high polydispersity (1.38). In water:DMF 50:50 (v/v), addition of at least 60% of Cu(II)Cl2 with respect to Cu(I)Cl allowed to obtain a good control of the polymerization. Linear kinetic plots up to very high conversion were observed and the final polydispersities were relatively low (1.15-1.25). Good self-blocking efficiencies were demonstrated by chain extension experiments even when the first block conversion before the addition of the second feed was very high (>90%). Amphiphilic block copolymers with MMA (number-average degree of polymerization X n,SPMA ) 50, Xn,MMA ) 25) were directly prepared in water:DMF 40:60 (v/v) without using protecting group chemistry or post-polymerization derivatization. The first-order kinetic plot for MMA polymerization was linear up to 96% conversion. Two block copolymers with the same composition, p(SPMA 50-b-MMA25)1pot and p(SPMA50-b-MMA25)2pot, were prepared with "onepot" and "two-pot" procedures. p(SPMA50-b-MMA25)2pot prepared using a purified pSPMA macroinitiator for MMA polymerization gave well-defined core-shell spherical micelles with an average hydrodynamic radius of about 14 nm determined by dynamic light scattering (DLS) measurements. p(SPMA50-b-MMA25)1pot prepared using the sequential monomer addition gave large micellar clusters (more than 100 nm) in addition to simple but smaller micelles. A tentative explanation to the presence of the larger aggregates was given.

Morphology Control of Highly Sulfonated Block Copolymers by a Simple Thermal Process

“…[10] However, it was not easy to prepare non-polar/polar block copolymers by this route because of the insolubility of hydrophobic monomers in aqueous media. [11][12][13] We recently reported syntheses of well-defined 100% SPS-based copolymers (PDI<1.11) from neopentyl styrene sulfonate (NSS) and n-butyl acrylate (nBA)-based copolymers by CuBr catalyzed living radical polymerization system followed by thermolysis. [14] In this study, we synthesized a series of the block copolymer of nBA and NSS to examine the morphology changes before and after sulfonation by thermolysis, simple heating process at 150 8C.…”

Multiresponsive Reversible Gels Based on Charge‐Driven Assembly

“…[23][24][25][26] The molecular structure is given in Scheme 1 a. Poly(allylamine hydrochloride) 160 (PAH 160 ) was used as oppositely charged homopolymer (Scheme 1 b).…”

Soft hydrogels for dual use: Template for metal nanoparticle synthesis and a reactor in the reduction of nitrophenols

“…In other words, the polymer chains are tightly knitted with the increased amount used crosslinker, and the molecular mass between the crosslinks were decreased. Although there are very few investigations for p(SPM) in the literature such as the synthesis by atom transfer radical polymerization in a copolymeric form with HEMA and as brushes for the silver nanoparticle preparations inside p(sulfopropyl methacrylate) that render antibacterial and cytotoxic effect on the different surfaces [37][38][39][40].…”