Controlled radical copolymerization of styrene with acrylic acid and tert-butyl acrylate under conditions of reversible addition-fragmentation chain transfer: Control of the chain microstructure

Abstract

The copolymerization of styrene and acrylic acid and the copolymerization of styrene and tert butyl acrylate that are mediated by benzyl dithiobenzoate and dibenzyl trithiocarbonate as reversible addi tion fragmentation chain transfer agents are studied for the first time. It is shown that the copolymerization of these monomer pairs mediated by reversible addition fragmentation chain transfer agents occurs via the pseudoliving radical mechanism and is characterized by a linear increase in the number average molecular weight with an increase in the total conversion of the monomers and by the formation of narrowly dispersed copolymers. Variation in the conditions of the radical copolymerization of styrene and acrylic acid (in the type of reversible addition fragmentation chain transfer agent and the addition of a polar solvent) and of the radical copolymerization of styrene and tert butyl acrylate (in the composition of the monomer mixture) makes it possible to control the chain microstructures of the copolymers.

Synthesis of amphiphilic copolymers based on acrylic acid, fluoroalkyl acrylates and n-butyl acrylate in organic, aqueous–organic, and aqueous media via RAFT polymerization

“…Recently, we have shown that, in the RAFT copolymerization of polar-non-polar monomer pair, relative monomer reactivities could be adjusted not only by varying the polarity of the solvent, but also by governing the hydrophilicity/hydrophobicity of the polymeric RAFT agent. 59 The similar effect of the macroinitiator and the macromonomer on the relative monomer reactivities was also described for the case of the stable free radical polymerization 60 and for the conventional radical polymerization. 61 Hence, one can conclude that the similar effect of variations in the relative monomer reactivities is observed for the systems under study in the presence of Pol-A and Cop-H5.…”

Control over the relative reactivities of monomers in RAFT copolymerization of styrene and acrylic acid

“…For example, if we compare the copolymer prepared via copolymerization in bulk and in DMF in the presence of BDB, we find that the former is more enriched with AA units. 38 This may come from the solvent-induced dissociation of the dimers of carboxylic acids and the formation of H-complexes of DMF and AA, which leads to a decrease in AA reactivity. Another factor related to the effect of preferential solvation is when the polar monomer (AA) is replaced by the polar solvent from the macromolecular coil.…”

“…Solvent effect (copolymerization in bulk) also has an influence on the relative monomer activities. 38 …”

“…RAFT polymerization was mostly used for the controlled synthesis of either polyacrylic acid or its block-copolymers predominately with poly( n -butyl acrylate). 34–37 In our previous research, 38 we have applied the RAFT technique to the copolymerization of styrene either with acrylic acid or with tert -butyl acrylate for the first time. RAFT copolymerization was carried out both in bulk and in the presence of DMF with a monomer feed containing 85 mol% of styrene and a molar ratio of acrylic acid to DMF equal to 1 : 3.…”

Copolymerization on Selective Substrates: Experimental Test and Computer Simulations

“…The carboxylic acids in the A block self-associate strongly through the hydrogen-bond interaction. In addition, the copolymerization of this pair is well-studied in detail, , including modern living polymerization schemes, both RAFT , and NMP. , …”