Impact of Macromonomer Molar Mass and Feed Composition on Branch Distributions in Model Graft Copolymerizations

Graft polymers are useful in a versatile range of material applications. Understanding how changes to the grafted architecture, such as the grafting density (z), the side-chain degree of polymerization (N_sc), and the backbone degree of polymerization (N_bb), affect polymer properties is critical for accurately tuning material performance. For graft-through copolymerizations, changes to N_sc and z are controlled by the macromonomer degree of polymerization (N_MM) and the initial fraction of the macromonomer in the feed (f_MM⁰), respectively. We show that changes to these parameters can influence the copolymerization reactivity ratios and, in turn, impact the side-chain distribution along a graft polymer backbone. Poly((±)-lactide) macromonomers with N_MM values as low as ca. 1 and as high as 72 were copolymerized with a small-molecule dimethyl ester norbornene comonomer over a range of f_MM⁰ values (0.1 ≤ f_MM⁰ ≤ 0.8) using ring-opening metathesis polymerization (ROMP). Monomer conversion was determined using ¹H nuclear magnetic resonance spectroscopy, and the data were fit with terminal and nonterminal copolymerization models. The results from this work provide essential information for manipulating N_sc and z while maintaining synthetic control over the side-chain distribution for graft-through copolymerizations.