title: Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.
abstract: The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h.
authors.affiliation: University of Warwick, Library Road, CV4 7AL, Coventry, UK.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Simula
authors.affiliation: University of Warwick, Library Road, CV4 7AL, Coventry, UK.|Monash Institute of Pharmaceutical Sciences, Monash University, Parksville, VIC, 3052, Australia.
authors.forename: Athina
authors.initials: A
authors.lastname: Anastasaki
authors.affiliation: University of Warwick, Library Road, CV4 7AL, Coventry, UK.|Monash Institute of Pharmaceutical Sciences, Monash University, Parksville, VIC, 3052, Australia.
authors.forename: David M
authors.initials: DM
authors.lastname: Haddleton
mesh_terms: D005021:Ethylamines / Q000138:chemical synthesis / Q000737:chemistry; D006358:Hot Temperature; D057927:Hydrophobic and Hydrophilic Interactions; D008689:Methacrylates / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D008970:Molecular Weight; D011092:Polyethylene Glycols / Q000138:chemical synthesis / Q000737:chemistry; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: C510335:2-dimethylaminoethyl methacrylate; D005021:Ethylamines; D008689:Methacrylates; D011108:Polymers; C524499:polyethylene glycol methacrylate; D011092:Polyethylene Glycols
keywords: block copolymers; living polymerization; telechelics; transition-metal chemistry; water-soluble polymers