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<p>Though homogeneous CuBr<sub>2</sub>/Ligand complex has facilitated Reversible Deactivation Radical Polymerization, its practical use in advanced applications is often restricted due to metal contamination and difficulty in catalyst separation. To address these issues, a heterogeneous catalyst, Cu(0)-wire, Supplemental Activator Reducing Agent (SARA) or other photo redox catalyst, were introduced. However, the system still relies on the inclusion of external Cu(II) salts, thereby retaining the characteristics of a homogeneous system. As a method for overcoming the challenges of metal contamination and catalyst separation, we demonstrate Photoinduced SARA Open vessel Atom Transfer Radical Polymerization, using Cu(0)-wire under UV light to polymerize well-defined polymethyl methacrylate (PMMA). This heterogenous catalytic system demonstrates both molecular weight and distribution, without the addition of external Cu(II) salts. With the attained minimum induction period, the effect of different light sources (UV, LED, IR), N,N, N′,N″,N′′-pentamethyldiethylenetriamine (PMDETA) concentration and the length of Cu(0) wire on the kinetics and control were investigated thoroughly. Here, the irradiation of Cu(0)/PMDETA complex using domestic 8&#xa0;W UV lamp (365&#xa0;nm, 4.2&#xa0;cm<sup>− 2</sup>) was sufficient for an efficient activation and deactivation cycle. The facile transfer of electrons to generate both Cu(II) and Cu(I) on UV irradiation was characterized through cyclic voltammetry. The synergy between Cu(0)/PMDETA and UV irradiation facilitate the synthesis of different degree of polymerization (DP<sub><i>n</i></sub>) ranging from 50 to 400. An efficient reinitiation and temporal control of the polymer chain were exemplified through intermittent irradiation. The high-end group fidelity of PMMA was further demonstrated through subsequent chain extension and block copolymerization.</p>

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Salt free open vessel photoinduced supplemental activator reducing agent atom transfer radical polymerization

  • 期刊论文

  • 发表日期：

    2026年3月16日

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  • Matthew Kirubakaran,
  • Kannapiran Rajendrakumar

摘要

Though homogeneous CuBr2/Ligand complex has facilitated Reversible Deactivation Radical Polymerization, its practical use in advanced applications is often restricted due to metal contamination and difficulty in catalyst separation. To address these issues, a heterogeneous catalyst, Cu(0)-wire, Supplemental Activator Reducing Agent (SARA) or other photo redox catalyst, were introduced. However, the system still relies on the inclusion of external Cu(II) salts, thereby retaining the characteristics of a homogeneous system. As a method for overcoming the challenges of metal contamination and catalyst separation, we demonstrate Photoinduced SARA Open vessel Atom Transfer Radical Polymerization, using Cu(0)-wire under UV light to polymerize well-defined polymethyl methacrylate (PMMA). This heterogenous catalytic system demonstrates both molecular weight and distribution, without the addition of external Cu(II) salts. With the attained minimum induction period, the effect of different light sources (UV, LED, IR), N,N, N′,N″,N′′-pentamethyldiethylenetriamine (PMDETA) concentration and the length of Cu(0) wire on the kinetics and control were investigated thoroughly. Here, the irradiation of Cu(0)/PMDETA complex using domestic 8 W UV lamp (365 nm, 4.2 cm− 2) was sufficient for an efficient activation and deactivation cycle. The facile transfer of electrons to generate both Cu(II) and Cu(I) on UV irradiation was characterized through cyclic voltammetry. The synergy between Cu(0)/PMDETA and UV irradiation facilitate the synthesis of different degree of polymerization (DPn) ranging from 50 to 400. An efficient reinitiation and temporal control of the polymer chain were exemplified through intermittent irradiation. The high-end group fidelity of PMMA was further demonstrated through subsequent chain extension and block copolymerization.