No abstract

In typical cyclic polymer synthesis via ring‐closure, chain growth and cyclization events are competing with each other, thus affording cyclic polymers with uncontrolled molecular weight or ring size and high dispersity. Here we uncover a mechanism by which Lewis pair polymerization (LPP) operates on polar vinyl monomers that allows the control of where and when cyclization takes place, thereby achieving spatial and temporal control to afford precision cyclic vinyl polymers or block copolymers with predictable molecular weight and low dispersity (≈1.03). A combined experimental and theoretical study demonstrates that cyclization occurs only after all monomers have been consumed (when) via conjugate addition of the propagating chain end to the specific site of the initiating chain end (where), allowing the cyclic polymer formation steps to be regulated and executed with precision in space and time.

Current search for more sustainable plastics seeks to redesign polymers possessing both chemical recyclability to monomer for a circular plastics economy and desirable performance that can rival or even exceed today's nonrecyclable or hard-to-recycle petroleum-based incumbents. However, within a traditional monomer framework it is challenging to optimize, concurrently, contrasting polymerizability/depolymerizability and recyclability/performance properties. Here, we highlight the emerging hybrid monomer design strategy to develop intrinsically circular polymers with tunable performance properties, aiming to unify desired, but otherwise conflicting, properties in a single monomer. Conceptually, this design hybridizes parent monomer pairs of contrasting, mismatching, or matching properties into offspring monomers that not only unify the above-described conflicting properties but also radically alter the resultant polymer properties far beyond the limits of what either parent homopolymers or their copolymers can achieve.

The design of facile synthetic routes to well-defined block copolymers (BCPs) from direct polymerization of one-pot comonomer mixtures, rather than traditional sequential additions, is both fundamentally and technologically important. Such synthetic methodologies often leverage relative monomer reactivity toward propagating species exclusively and therefore are rather limited in monomer scope and control over copolymer structure. The recently developed compounded sequence control (CSC) by Lewis pair polymerization (LPP) utilizes synergistically both thermodynamic (K eq ) and kinetic (k p ) differentiation to precisely control BCP sequences and suppress tapering and misincorporation errors. Here, we present an in-depth study of CSC by LPP, focusing on the complex interplay of the fundamental K eq and k p parameters, which enable the unique ability of CSC-LPP to precisely control comonomer sequences across a variety of polar vinyl monomer classes. Individual Lewis acid equilibrium and polymerization rate parameters of a range of commercially relevant monomers were experimentally quantified, computationally validated, and rationalized. These values allowed for the judicious design of copolymerizations which probed multiple hypotheses regarding the constructive vs conflicting nature of the relationship between K eq and k p biases, which arise during CSC-LPP of comonomer mixtures. These relationships were thoroughly explored and directly correlated with resultant copolymer microstructures. Several examples of higher-order BCPs are presented, further demonstrating the potential for materials innovation offered by this methodology.

Current search for more sustainable plastics seeks to redesign polymers possessing both chemical recyclability to monomer for a circular plastics economy and desirable performance that can rival or even exceed today's nonrecyclable or hard-to-recycle petroleum-based incumbents. However, within a traditional monomer framework it is challenging to optimize, concurrently, contrasting polymerizability/depolymerizability and recyclability/performance properties. Here, we highlight the emerging hybrid monomer design strategy to develop intrinsically circular polymers with tunable performance properties, aiming to unify desired, but otherwise conflicting, properties in a single monomer. Conceptually, this design hybridizes parent monomer pairs of contrasting, mismatching, or matching properties into offspring monomers that not only unify the above-described conflicting properties but also radically alter the resultant polymer properties far beyond the limits of what either parent homopolymers or their copolymers can achieve.