Proton-triggered topological transformation in superbase-mediated selective polymerization enables access to ultrahigh-molar-mass cyclic polymers.

The selective synthesis of ultrahigh-molar-mass (UHMM, >2 million Da) cyclic polymers is challenging as an exceptional degree of spatiotemporal control is required to overcome the possible undesired reactions that can compete with the desired intramolecular cyclization. Here we present a counterintuitive synthetic methodology for cyclic polymers, represented here by polythioesters, which proceeds via superbase-mediated ring-opening polymerization of gem-dimethylated thiopropiolactone, followed by macromolecular cyclization triggered by protic quenching. This proton-triggered linear-to-cyclic topological transformation enables selective, linear polymer-like access to desired cyclic polythioesters, including those with UHMM surpassing 2 MDa. In addition, this method eliminates the need for stringent conditions such as high dilution to prevent or suppress linear polymer contaminants and presents the opposite scenario in which protic-free conditions are required to prevent cyclic polymer formation, which is capitalized to produce cyclic polymers on demand. Furthermore, such UHMM cyclic polythioester exhibits not only much enhanced thermostability and mechanical toughness, but it can also be quantitatively recycled back to monomer under mild conditions due to its gem-disubstitution.

Cyclic and Linear Tetrablock Copolymers Synthesized at Speed and Scale by Lewis Pair Polymerization of a One-Pot (Meth)acrylic Mixture and Characterized at Multiple Levels.

Cyclic block copolymers (cBCP) are fundamentally intriguing materials, but their synthetic challenges that demand precision in controlling both the monomer sequence and polymer topology limit access to AB and ABC block architectures. Here, we show that cyclic ABAB tetra-BCPs (cABAB) and their linear counterpart (lABAB) can be readily obtained at a speed and scale from one-pot (meth)acrylic monomer mixtures, through coupling the Lewis pair polymerization's unique compounded-sequence control with its precision in topology control. This approach achieves fast (<15 min) and quantitative (>99%) conversion to tetra-BCPs of predesignated linear or cyclic topology at scale (40 g) in a one-pot procedure, precluding the needs for repeated chain extensions, stoichiometric addition steps, dilute conditions, and postsynthetic modifications, and/or postsynthetic ring-closure steps. The resulting lABAB and cABAB have essentially identical molecular weights (Mn = 165-168 kg mol-1) and block degrees/symmetry, allowing for direct behavioral comparisons in solution (hydrodynamic volume, intrinsic viscosity, elution time, and refractive indices), bulk (thermal transitions), and film (thermomechanical and rheometric properties and X-ray scattering patterns) states. To further the morphological characterizations, allylic side-chain functionality is exploited via the thiol-ene click chemistry to install crystalline octadecane side chains and promote phase separation between the A and B blocks, allowing visualization of microdomain formation.

Hybrid Monomer Design Synergizing Property Trade-offs in Developing Polymers for Circularity and Performance.

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 non-recyclable 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.

Compounded Interplay of Kinetic and Thermodynamic Control over Comonomer Sequences by Lewis Pair Polymerization.

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 (Keq) and kinetic (kp) 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 Keq and kp 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 Keq and kp 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.

Mechanism of Spatial and Temporal Control in Precision Cyclic Vinyl Polymer Synthesis by Lewis Pair Polymerization.

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.