Preparation of Polyisobutene-graft-Poly(methyl methacrylate) and Polyisobutene-graft-Polystyrene with Different Compositions and Side Chain Architectures through Atom Transfer Radical Polymerization (ATRP)

Abstract

Polyisobutene‐graft‐poly(methyl methacrylate) and polyisobutene‐graft‐polystyrene with controlled compositions and side chain architectures were prepared through atom transfer radical polymerization (ATRP). Poly[isobutene‐co‐(p‐methylstyrene)‐co‐(p‐bromomethylstyrene)] (PIB) was used as a macroinitiator in the presence of CuCl or CuBr as a catalyst and dNbpy as a ligand. The compositions were controlled by the conversion of the monomer with polymerization time. The molecular weight distributions of the side chains were controlled through ATRP in the presence/absence of a halogen exchange reaction. DSC and DMA measurements showed that graft copolymers have two glass transition temperatures suggesting microphase separated behavior, which was also confirmed by SAXS measurements. The phase and dynamic mechanical behaviors were strongly affected by the compositions and/or the side chain architectures. The properties of the graft copolymers were controlled in a wide range leading to toughened glassy polymers or elastomers.

Successful Chain Extension of Polyacrylate and Polystyrene Macroinitiators with Methacrylates in an ARGET and ICAR ATRP

“…Halogen exchange has been successfully applied to a number of systems where the addition of the second monomer would form a more active chain end than that present on the added (macro)initiator. 15,[17][18][19][20][21][22][23][24][25] Recently, methods to conduct ATRP with very low catalyst concentrations have been developed. These methods, known as activators regenerated by electron transfer (ARGET) and initiators for continuous activator regeneration (ICAR) have allowed polymerization to occur with as low as only a few parts per million of copper.…”

Polymerization of Styrene Sulfonate Ethyl Ester and Styrene Sulfonate Dodecyl Ester by ATRP: Synthesis and Characterization of Polymer Brushes

“…A similar copolymer, poly[isobutylene-alt-(p-bromomethylstyrene)], has been used by Matyjaszewski for the synthesis of branched polymers. [34] Only very recently, a styrene-type macroinitiator that can be used for polymer brush synthesis by photo-initiated ATRP has been reported (III). [35] Following Janata's procedure for the synthesis of II, [33] the resulting macroinitiators with 10-100% reactive site density are used for the polymerization of styrene sulfonate dodecyl ester (SSD) and styrene sulfonate ethyl ester (SSE), as will be discussed in the next sections.…”

Amphiphilic poly(acrylic acid-b-styrene-b-isobutylene-b-styrene-b-acrylic acid) pentablock copolymers from a combination of quasiliving carbocationic and atom transfer radical polymerization

“…This general process has been termed site transformation. Many polymerization techniques including condensation (step growth) [13], anionic [14], ring-opening [15], and especially cationic [16][17][18][19][20][21][22][23][24] processes have been combined with ATRP to yield novel polymer structures that were previously unattainable.…”

“…Commercially available poly(isobutylene-co-p-methylstyrene-co-p-bromomethylstyrene) (EXXPRO w ) was used as a macroinitiator for the ATRP of styrene [20,21] and methyl methacrylate (MMA) [21]. The mechanical properties of the final copolymers varied from an elastomer to a toughened glassy polymer when the weight fraction of the side chains was either low or high, respectively.…”