Iranian Polymer Journal

, Volume 27, Issue 11, pp 881–887 | Cite as

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

  • Le-Lin Zeng
  • Wan-Yun Xie
  • Cai-Xia Yang
  • Enxiang Liang
  • Guo-Xiang Wang
Original Research


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.


Perylene derivatives Living radical polymerization Photomediated Atom transfer radical polymerization Long-wavelength light 



We thank the National Natural Science Foundation of China (51674117, 51503063), Scientific Research Fund of Hunan Provincial Education Department (Grant Nos. 16K036, 15B101).

Supplementary material

13726_2018_661_MOESM1_ESM.docx (362 kb)
Supplementary material 1 (DOCX 361 KB)


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Copyright information

© Iran Polymer and Petrochemical Institute 2018

Authors and Affiliations

  1. 1.College of Chemistry and Chemical EngineeringHunan Institute of Science and TechnologyYueyangPeople’s Republic of China

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