title: Universal Conditions for the Controlled Polymerization of Acrylates, Methacrylates, and Styrene via Cu(0)-RDRP.
abstract: Atom transfer radical polymerization (ATRP) typically requires various parameters to be optimized in order to achieve a high degree of control over molecular weight and dispersity (such as the type of initiator, transition metal, ligand, solvent, temperature, deactivator, added salts, and reducing agents). These components play a major role when switching monomers, e.g., from acrylic to methacrylic and/or styrenic monomers during the synthesis of homo- and block copolymers as the stability and reactivity of the carbon centered propagating radical dramatically changes. This is a challenge for both "experts" and nonexperts as choosing the appropriate conditions for successful polymerization can be time-consuming and overall an arduous task. In this work, we describe one set of universal conditions for the efficacious polymerization of acrylates, methacrylates and styrene (using an identical initiator, ligand, copper salt, and solvent) based on commercially available and inexpensive reagents (PMDETA, IPA, Cu(0) wire). The versatility of these conditions is demonstrated by the near quantitative polymerization of these monomer families to yield well-defined materials over a range of molecular weights with low dispersities (∼1.1-1.2). The control and high end group fidelity is further exemplified by in situ block copolymerization upon sequential monomer addition for the case of methacrylates and styrene furnishing higher molecular weight copolymers with minimal termination. The facile nature of these conditions, combined with readily available reagents, will greatly expand the access and availability of tailored polymeric materials to all researchers.
authors.affiliation: University of Warwick , Chemistry Department, Library Road, CV4 7AL, Coventry, United Kingdom.
authors.forename: Richard
authors.identifier: 0000-0003-4787-2060
authors.initials: R
authors.lastname: Whitfield
authors.affiliation: Materials Research Laboratory, University of California , Santa Barbara, California 93106, United States.
authors.forename: Athina
authors.initials: A
authors.lastname: Anastasaki
authors.affiliation: University of Warwick , Chemistry Department, Library Road, CV4 7AL, Coventry, United Kingdom.
authors.forename: Vasiliki
authors.initials: V
authors.lastname: Nikolaou
authors.affiliation: University of Warwick , Chemistry Department, Library Road, CV4 7AL, Coventry, United Kingdom.
authors.forename: Glen R
authors.initials: GR
authors.lastname: Jones
authors.affiliation: University of Warwick , Chemistry Department, Library Road, CV4 7AL, Coventry, United Kingdom.
authors.forename: Nikolaos G
authors.initials: NG
authors.lastname: Engelis
authors.affiliation: Materials Research Laboratory, University of California , Santa Barbara, California 93106, United States.
authors.forename: Emre H
authors.initials: EH
authors.lastname: Discekici
authors.affiliation: Materials Research Laboratory, University of California , Santa Barbara, California 93106, United States.
authors.forename: Carolin
authors.initials: C
authors.lastname: Fleischmann
authors.affiliation: Materials Research Laboratory, University of California , Santa Barbara, California 93106, United States.
authors.forename: Johannes
authors.initials: J
authors.lastname: Willenbacher
authors.affiliation: Materials Research Laboratory, University of California , Santa Barbara, California 93106, United States.
authors.forename: Craig J
authors.identifier: 0000-0001-9951-851X
authors.initials: CJ
authors.lastname: Hawker
authors.affiliation: University of Warwick , Chemistry Department, Library Road, CV4 7AL, Coventry, United Kingdom.
authors.forename: David M
authors.identifier: 0000-0002-4965-0827
authors.initials: DM
authors.lastname: Haddleton