Sequence Distribution and Stereoregularity of Methyl Methacrylate and Butyl Acrylate Statistical Copolymers Synthesized by Atom Transfer Radical Polymerization

Abstract

1 H and 13 C NMR spectra of copolymers of methyl methacrylate (M) and butyl acrylate (B) were analyzed in terms of sequence distribution and stereoregularity of monomer units. The copolymers were prepared by atom transfer radical polymerization (ATRP) in bulk and 25% (v/v) benzonitrile solution. The different experimental conditions resulted in different levels of polymerization control. Under our experimental conditions, the experimental data agreed well with data calculated from the Mayo-Lewis terminal model and Bernoullian statistics with monomer reactivity ratios of rM ) 1.44 ( 0.11 and rB ) 0.56 ( 0.06 and an isotacticity parameter of σM ) 0.23 and coisotacticity parameter of σ ) 0.30. Therefore, the copolymer compositions and microstructures are independent of the controllability of the ATRP process.

Synthesis of PMMA-b-PU-b-PMMA tri-block copolymers through ARGET ATRP in the presence of air

“…The tacticity of PMMA can be identified using the integration values of peaks at 0.75, 0.91, and 1.07-1.28 ppm which correspond to syndiotactic (rr), atactic (mr), and isotactic (mm) PMMA, respectively [4]. The ratio among rr, mr, and mm in our study for CM4BrP6 is 53:34:13 which is similar to the reported tacticity ratio of PMMA prepared by ATRP [15]. The molar content of PMMA in the tri-block copolymers (4) can easily be found out by comparing molecular weights (obtained by GPC) of MBP-PU-MBP and copolymers which are given in Table 3 ).…”

Glass Transition Temperatures of Poly[(methyl methacrylate)-co-(butyl acrylate)]s Synthesized by Atom-Transfer Radical Polymerization

“…In previous work, [4] 1:3). It was confirmed that the number-average molecular weight of the copolymers increased linearly with conversion, agreed well with the theoretical one, and their polydispersity values were relatively narrow, as seen in Figure 2.…”

“…In previous work, [4,5] the synthesis and characterization of methyl methacrylate/butyl acrylate (MMA-BA) statistic copolymers synthesized via ATRP, as well as the copolymerization kinetics were studied. It was confirmed that this system followed the Mayo-Lewis terminal model with monomer reactivity ratios of r MMA = 1.44 and r BA = 0.56, and Bernoullian statistics with an isotacticity parameter of r MMA = 0.23 and coisotacticity parameter of r MMABA = 0.30.…”

A Comparative Study of Methyl Methacrylate/Butyl Acrylate Copolymerization Kinetics by Atom-Transfer and Conventional Radical Polymerization

“…[7][8][9][10][11][12][13][14][15][16][17] Several research groups have carried out living/controlled free-radical copolymerization of methyl methacrylate with butyl acrylate. In some cases only a feed composition of equimolar amounts of monomers has been copolymerized.…”

“…In a previous work [16] we have reported the reactivity ratios, sequence distribution, and stereoregularity of methyl methacrylate/butyl acrylate copolymer obtained by means of ATRP, from which several relevant conclusions were obtained. Firstly, the composition and microstructure are independent of the initiator/catalyst/solvent system used, that is, independent of the control level achieved in the ATRP process.…”