A Facile Strategy for Catalyst Separation and Recycling Suitable for ATRP of Hydrophilic Monomers Using a Macroligand.
How to simply and efficiently separate and recycle catalyst has still been a constraint for the wide application of atom transfer radical polymerization (ATRP), especially for the polymerization systems with hydrophilic monomers because the polar functional groups may coordinate with transition metal salts, resulting in abundant catalyst residual in the resultant water-soluble polymers. In order to overcome this problem, a latent-biphasic system is developed, which can be successfully used for ATRP catalyst separation and recycling in situ for various kinds of hydrophilic monomers for the first time, such as poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), N,N-dimethyl acrylamide (DMA), and N-isopropylacrylamide (NIPAM). Herein, random copolymer of octadecyl acrylate (OA), MA-Ln (2-(bis(pyridin-2-ylmethyl)amino)ethyl acrylate), and POA-ran-P(MA-Ln) is designed as the macroligand, and heptane/ethanol is selected as the biphasic solvent. Copper(II) bromide (CuBr2 ) is employed as the catalyst, PEG-bound 2-bromo-2-methylpropanoate (PEG350 -Br) as the water-soluble ATRP initiator and 2,2'-azobis(isobutyronitrile) (AIBN) as the azo-initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP system. Importantly, well-defined water-soluble polymers are obtained even though the recyclable catalyst is used for sixth times.
Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Xiaowu
X
Jiang
Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Jian
J
Wu
Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Lifen
L
Zhang
Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Zhenping
Z
Cheng
Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Xiulin
X
Zhu
D000179:Acrylates / Q000737:chemistry; D001965:Bromides / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D017743:Equipment Reuse; D000431:Ethanol; D005609:Free Radicals / Q000737:chemistry; D006536:Heptanes; D057927:Hydrophobic and Hydrophilic Interactions; D007700:Kinetics; D008689:Methacrylates / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry; D011092:Polyethylene Glycols / Q000737:chemistry*; D058105:Polymerization; D012996:Solutions; D012997:Solvents; D013696:Temperature; D014867:Water / Q000737:chemistry*
D000179:Acrylates; D001965:Bromides; D005609:Free Radicals; D006536:Heptanes; D008689:Methacrylates; D009570:Nitriles; D012996:Solutions; D012997:Solvents; C524499:polyethylene glycol methacrylate; D014867:Water; C408079:cupric bromide; D000431:Ethanol; D011092:Polyethylene Glycols; C005044:hydroxyethyl methacrylate; D003300:Copper; C004526:azobis(isobutyronitrile); C049840:2-(dimethylamino)ethyl methacrylate
atom transfer radical polymerization (ATRP); catalyst recycling; catalyst separation; hydrophilic monomer; latent-biphasic catalysis