Synthesis of a New Macroperoxy Initiator with Methyl Methacrylate and T-Butyl Peroxy Ester by Atom Transfer Radical Polymerization and Copolymerization with Conventional Vinyl Monomers

Abstract

In this study, we present the synthesis of poly-MMA macroperoxy initiators obtained by the ATRP of MMA with bromo methyl benzyl t-butyl peroxy ester (t-BuBP) as an initiator, and CuX (X:Br or Cl)/2,2 -bipyridine (bpy) as a catalyst system at 0, 20, 30 and 40 • C. The peroxygen groups do not decompose during the ATRP reaction, because low reaction temperatures used for the ATRP reaction are not enough to decompose them. The peroxygen groups of poly-PMMA macroperoxy initiators can lead them to react with a monomer by using appropriate reaction conditions to obtain the block or graft copolymers. For this purpose, poly-MMA macroperoxy initiators were used to synthesize poly(MMA-b-S) block copolymers with S and used for graft copolymerization of polybutadiene (PBd) and natural rubber (RSS-3) to obtain crosslinked poly(MMA-g-PBd) and poly(MMA-g-RSS-3) graft copolymers. Swelling ratio values of the crosslinked graft copolymers in CHCl 3 were calculated. The characterizations of the polymers were achieved by FT-IR, 1 H-NMR, GPC, DSC, SEM, and the fractional precipitation (γ ) techniques. The reaction schemes were also performed using the HYPERCHEM 7.5 program. The mechanical properties of the products were investigated.

One‐step synthesis of block‐graft copolymers via simultaneous reversible‐addition fragmentation chain transfer and ring‐opening polymerization using a novel macroinitiator

“…This can be attributed to the high miscibility of the polymerizable methacrylate groups of poly‐ n BMA with poly‐EPCH and poly‐CL moieties of the copolymers. The same situation (the observation of only one glass transition) can also be seen our previous articles . T g value reported in the literature for homo poly‐EPCH, for homo poly‐CL, and homo poly‐ n BMA as 15, −72, and 20 °C, respectively.…”

Synthesis and characterization of poly(vinyl chloride-graft-2-vinylpyridine) graft copolymers using a novel macroinitiator by reversible addition-fragmentation chain transfer polymerization

“…Fractional precipitations of the polymers were carried out according to the procedure reported in the literature (43,61). Vacuum-dried graft copolymer sample (approximately 0.5 g) was dissolved in 5 ml of THF.…”

“…Polymers of a well-defined structure and molecular weight can be synthesized by controlled radical-polymerization methods, such as nitroxide-mediated polymerization (37,38), atom-transfer radical polymerization (25,(39)(40)(41)(42)(43)(44), and reversible addition-fragmentation chain transfer (RAFT) polymerization (33,(45)(46)(47)(48)(49)(50)(51)(52)(53)(54)(55)(56)(57)(58)(59)(60). RAFT polymerization is one of the most recently developed controlled radical-polymerization methods and is an important technique for the synthesis of copolymers.…”

L‐menthol‐based initiators for atom transfer radical polymerization of styrene

“…The structure and performance of the initiator are the key factors for ATRP reaction . In general, organohalides, organotelluriums, organostibines, organobismuthines, and so on were used. The different functional groups present in the initiator can be very useful for tunable chain end formation of well‐defined polymer chains.…”

“…reported the synthesis of dual ATRP and conventional initiator bromomethyl benzoyl t‐butyl peroxy ester and used for the synthesis of PMMA‐b‐PSt via ATRP of methyl methacrylate (MMA) to prepare PMMA macroperoxy initiator followed by styrene polymerization via heating. They also reported a novel macromonomer ATRP initiator synthesized from methacryloyl polyethylene glycol and 2‐bromo propanoyl bromide and used the same for the synthesis of low crosslinked homopolymer as well as graft copolymer with N ‐isopropylacrylamide (NIPAM) via ATRP. Thus, the synthesis of effective ATRP initiators with different functionalities has been very useful in the field of controlled polymer synthesis.…”