Photomediated atom transfer radical polymerization of MMA under long-wavelength light irradiation

• DOI: 10.1007/s13726-018-0661-2
• Publication Date: 2018-09-20T17:47:41Z
• Authors: Le-Lin Zeng; Wan-Yun Xie; Cai-Xia Yang; Enxiang Liang; Guo-Xiang Wang
• Keywords: 02 engineering and technology; 0210 nano-technology; 01 natural sciences; 0104 chemical sciences

In this study, a novel photocatalyst, pentarylenebis(dicarboximide) dye: (1,6,13,18-tetra(4-(2,3,3-trimethylbut-2-yl)phenoxy)-N,N’-(2,6-diisopropylphenyl)-pentarylene-3,4,15,16-tetracarboxidiimide) (TTPDPT), was first used in metal-free photoinduced atom transfer radical polymerization (ATRP) of methyl methacrylates (MMA). The initiator was methyl α-bromoisobutyrate (MBI) and the light source was mild near-infrared (NIR) light irradiation (λmax ≈ 870 nm). The TTPDPT-mediated ATRP relies on in situ photoreduction of a MBI through an electron transfer process to generate the desired alkyl radical, which could induce polymerization of the monomer. The photoinduced metal-free ATRP of MMA shows typical characteristics of controlled free radical polymerization, showing the linear evolution of number-average molecular weight (Mn,GPC) with monomer conversion, where polymers with predetermined degree of polymerization have well-controlled molecular weights and narrow molecular weight distribution (Mw/Mn). The photoinduced metal-free ATRP of MMA can be carried out with just ppm level of TTPDPT. The polymerization initiation and propagation can be operated by the aid of pulsed light sequences while NIR light source was used to promote carbon–carbon bond formation and to produce poly(methyl methacrylate) (PMMA) with Mw/Mn as low as 1.5. The synthesized PMMA was characterized by 1H nuclear magnetic resonance (1H NMR). The resultant PMMA contained a bromide end group that can be employed to reinitiate styrene polymerization to produce block copolymers through chain extension experiments.