title: Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization.
abstract: Control over polymer sequence and architecture is crucial to both understanding structure-property relationships and designing functional materials. In pursuit of these goals, we developed a new synthetic approach that enables facile manipulation of the density and distribution of grafts in polymers via living ring-opening metathesis polymerization (ROMP). Discrete endo,exo-norbornenyl dialkylesters (dimethyl DME, diethyl DEE, di-n-butyl DBE) were strategically designed to copolymerize with a norbornene-functionalized polystyrene (PS), polylactide (PLA), or polydimethylsiloxane (PDMS) macromonomer mediated by the third-generation metathesis catalyst (G3). The small-molecule diesters act as diluents that increase the average distance between grafted side chains, generating polymers with variable grafting density. The grafting density (number of side chains/number of norbornene backbone repeats) could be straightforwardly controlled by the macromonomer/diluent feed ratio. To gain insight into the copolymer sequence and architecture, self-propagation and cross-propagation rate constants were determined according to a terminal copolymerization model. These kinetic analyses suggest that copolymerizing a macromonomer/diluent pair with evenly matched self-propagation rate constants favors randomly distributed side chains. As the disparity between macromonomer and diluent homopolymerization rates increases, the reactivity ratios depart from unity, leading to an increase in gradient tendency. To demonstrate the effectiveness of our method, an array of monodisperse polymers (PLAx-ran-DME1-x)nbearing variable grafting densities (x = 1.0, 0.75, 0.5, 0.25) and total backbone degrees of polymerization (n = 167, 133, 100, 67, 33) were synthesized. The approach disclosed in this work therefore constitutes a powerful strategy for the synthesis of polymers spanning the linear-to-bottlebrush regimes with controlled grafting density and side chain distribution, molecular attributes that dictate micro- and macroscopic properties.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Tzu-Pin
authors.identifier: 0000-0001-7041-7213
authors.initials: TP
authors.lastname: Lin
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Alice B
authors.initials: AB
authors.lastname: Chang
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Hsiang-Yun
authors.initials: HY
authors.lastname: Chen
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Allegra L
authors.initials: AL
authors.lastname: Liberman-Martin
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Bates
authors.affiliation: Department of Chemistry, Whittier College , Whittier, California 90608, United States.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Voegtle
authors.affiliation: Department of Chemistry, Whittier College , Whittier, California 90608, United States.
authors.forename: Christina A
authors.initials: CA
authors.lastname: Bauer
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Robert H
authors.identifier: 0000-0002-0057-7817
authors.initials: RH
authors.lastname: Grubbs