Acrylic Graft Copolymers Via Macromonomers

Synthesis of Amphiphilic Graft Copolymers of n-Butyl Acrylate and Acrylic Acid by Atom Transfer Radical Copolymerization of Macromonomers

“…An alternative strategy for the synthesis of graft copolymers is the so-called grafting through or macromonomer approach, which is achieved by copolymerization of a macromonomer and a low molecular weight comonomer via ATRP. We have previously investigated the copolymerization of methacryloyl-terminated PMMA macromonomers and MMA at 60 °C in toluene via conventional free radical polymerization using AIBN as an initiator , and found that with increasing macromonomer concentration the relative reactivity of the macromonomer decreased due to the enhanced viscosity. In the copolymerization of PMMA macromonomers with nBA the incompatibility of backbone and side chains is an additional complication. , Roos et al investigated the copolymerization of n- butyl acrylate and ω-methacryloyl-PMMA macromonomers via ATRP and found a much higher macromonomer reactivity (1/ r 1 = 2.2) compared to that found in conventional radical polymerization (1/ r 1 = 1.37) at the same concentration.…”

“…We have previously investigated the copolymerization of methacryloyl-terminated PMMA macromonomers and MMA at 60 °C in toluene via conventional free radical polymerization using AIBN as an initiator , and found that with increasing macromonomer concentration the relative reactivity of the macromonomer decreased due to the enhanced viscosity. In the copolymerization of PMMA macromonomers with nBA the incompatibility of backbone and side chains is an additional complication. , Roos et al investigated the copolymerization of n- butyl acrylate and ω-methacryloyl-PMMA macromonomers via ATRP and found a much higher macromonomer reactivity (1/ r 1 = 2.2) compared to that found in conventional radical polymerization (1/ r 1 = 1.37) at the same concentration. They ascribed it to the increased time between two monomer additions in ATRP, facilitating the diffusion of the macromonomer to the active chain end.…”

Synthesis of Oligo(oxyethylene) Methacrylate-ended Poly(n-hexyl isocyanate) Rodlike Macromonomers and Their Radical Copolymerization Behavior with Methyl Methacrylate

“…Among them, the incompatibility is a particularly important factor to be considered when designing graft copolymers showing microphase separation between the grafted chains and the trunk main chain. 4,5,14,15 The nature of solvent, 16,17 the total concentration of monomers, 18 the molar ratio of monomers 19 and the molecular weight of macromonomers 15 have also been pointed out as factors affecting the copolymerizability.…”

“…[1][2][3] Advances in syntheses using a macromonomer technique have afforded a variety of star-, brush-or comb-shaped polymers via homopolymerization, and graft copolymers by copolymerization with low molecular weight comonomers. 4,5 A fundamental issue to be considered in a use of macromonomers is their reactivities in co-and homo-polymerization, because this is a key factor in controlling the design of the branched polymers. 6 The copolymerizabilities of macromonomers are influenced by various factors, [7][8][9][10][11][12][13] including thermodynamic repulsions between the macromonomer and the propagating chain, kinetically excluded volume effects, decreases in the mobility of the reactive species, and properties of the solvent.…”