Diffusion‐Regulated Phase‐Transfer Catalysis for Atom Transfer Radical Polymerization of Methyl Methacrylate in an Aqueous/Organic Biphasic System. Issue 6 (3rd February 2015)

• Record Type: Journal Article
• Authors: Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin
• Is Part Of: Macromolecular rapid communications. Volume 36:Issue 6(2015:Mar.)
• Page Start: 538
• Page End: 546
• Publication Date: 2015-02-03
• Subjects: atom transfer radical polymerization (ATRP) -- catalyst recycling -- diffusion‐regulated phase‐transfer catalysis (DRPTC) -- initiators for continuous activators regeneration for atom transfer radical polymerization (ICAR ATRP); Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.201400639
• Languages: English
• ISSNs: 1022-1336

Abstract

Abstract : A concept based on diffusion‐regulated phase‐transfer catalysis (DRPTC) in an aqueous‐organic biphasic system with copper‐mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC‐based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α‐bromophenylacetate (EBrPA) as an initiator, and tris(2‐pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well‐defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling. Abstract : A rather simple, highly efficient, and thoroughly sustainable approach termed diffusion‐regulated phase‐transfer catalysis (DRPTC) for atom transfer radical polymerization (ATRP) catalyst separation and recycling is successfully established.