Facilely Recyclable Cu(II) Macrocomplex with Thermoregulated
Poly(ionic liquid) Macroligand: Serving as a Highly Efficient Atom
Transfer Radical Polymerization Catalyst
posted on 2016-10-17, 00:00authored byBingjie Zhang, Lan Yao, Xiaodong Liu, Lifen Zhang, Zhenping Cheng, Xiulin Zhu
Copolymer
poly(ionic liquids) (PILs) are fascinating new polymerized polyelectrolytes
that can provide the properties of ionic liquids with others combined
into one. In this work, a thermoregulated random copolymer PIL (PILL)
with the side chains of both ionic liquids and atom transfer radical
polymerization (ATRP) ligands was designed and synthesized to form
a macrocomplex with CuBr2 and serve as an ATRP catalyst
to establish a thermoregulated phase separated catalysis (TPSC) system
and further applied in a typical ICAR (initiators for continuous activator
regeneration) ATRP process for the catalyst separation and recycling in situ for the first time. This novel TPSC system could
simultaneously recycle transition metal catalyst and ligand easily
just by changing temperature from polymerization temperature to room
temperature. Additionally, even if the highly efficient recyclable
PILL with Cu catalyst was separated facilely and reused 10 times in situ, it nearly did not sacrifice the controllability
over polymerization. Furthermore, after polymerization and a TPSC
process, the metal catalyst residual in the polymer solution phase
remained just about 1.5 ppm, indicating highly efficient transition
metal catalyst recycling efficiency.