Living Radical Polymerization of Alkyl Methacrylates with Ruthenium Complex and Synthesis of Their Block Copolymers

Abstract

Living radical polymerizations of ethyl and n-butyl methacrylates (EMA and BMA, respectively) have been achieved with ternary initiating systems that consist of carbon tetrachloride, tris(triphenylphosphine)ruthenium dichloride [RuCl2(PPh3)3], and aluminum compounds such as MeAl(ODBP)2 (ODBP, 2,6-di-tert-butylphenoxy) and Al(OiPr)3 in toluene at 60−80 °C. The produced polymers had narrow molecular weight distributions (MWDs) (M̄ w/M̄ n = 1.2−1.5) and controlled molecular weights that are nearly proportional to monomer conversion. Sequential living polymerizations of these methacrylates from methyl methacrylate (MMA) afforded AB-type block copolymers with narrow MWDs (M̄ w/M̄ n ∼ 1.2). Further addition of MMA into the living AB block copolymers gave ABA-type triblock copolymers poly(MMA-b-BMA-b-MMA).

Functionalization of polymers prepared by ATRP using radical addition reactions

“…Atom transfer radical polymerization (ATRP) is one of the most convenient methods to synthesize well-defined low molecular weight polymers [1][2][3][4][5][6] . The molecular weight of the polymer is determined by the monomer conversion and the amount of initiator used, DP = D[M]/[I] 0 ; polydispersities are low, M -w /M -n a 1.3.…”

Kinetic Studies on Bulk Atom Transfer Radical Polymerization of Styrene

“…The residual was dissolved in CHCl 3 and washed with 50 mL of water three times. The aqueous parts were combined and shaken with 50 mL of fresh CHCl 3 …”

“…In polymer chemistry, the development of Living Radical Polymerization (LRP) via ATRP technique constitutes one of the key developments in the field of synthetic polymer chemistry, allowing for the synthesis of a variety of polymers with molecular weight distributions and well defined architectures, with precise control over the compositions and structures [1][2][3]. In general, a combination of an alkyl halide [R-X, X= Cl or Br)] and a transition metal catalyst in lower oxidation state (Cu(I)X/2,2ʹ-bipyridine) is used to initiate the ATRP system [4][5][6].…”

“…For example, styrene is polymerized by atom transfer radical additions using 1-phenylethyl chloride [8] or arenesulfonyl chloride [9] as an initiator and CuCl/4,4ʹ-diheptyl-2,2ʹ-bipyridine or 4,4ʹ-di(5-nonyl)-2,2ʹ-bipyridine (dNbipy) complex as the catalyst to yield a well-defined polymer with a narrow molecular weight distribution (M w /M n = 1.05). The kinetics of syndiospecific slurry polymerization of styrene in heptane has been investigated with pentamethylcyclopentadienyl titanium trimethoxide [Cp*Ti(OMe) 3 ] catalyst with methylalmuninoxane [10]. Confinement effect of graphene nanoplatelets on the kinetics of styrene atom transfer radical polymerization was studied by a grafting from reaction [11].…”

Well-Defined Graft Copolymers of Methacrylate, Acrylate, and Styrene via Ruthenium-Catalyzed Living Radical Polymerization

“…Although the ruthenium-catalyzed polymerization has been used for the synthesis of various end-functionalized, 43,44 block, 45 and star polymers, [46][47][48][49] no applications of the systems to the graft polymer synthesis have been reported.…”