Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces

Abstract

We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region between copolymer blocks in triblock copolymers providing control over the interfacial interactions in our nanoscale phase-separated materials independent of molecular weight and block constituents. Additionally, we show the ability to retain a desirous and complex multiply-continuous network structure (alternating gyroid) in our dual-tapered triblock material.

Block copolymer electrolytes for rechargeable lithium batteries

“…However, high‐molecular‐weight materials, which provide high ionic conductivity and mechanical strength in BCP systems, decrease the overall materials' processability. From the standpoint of reducing T ODT (increasing processability), recent efforts on tapered BCPs deserve attention . Manipulating the interfacial composition in BCP systems provides a way to decouple the segregation strength ( χ eff N ) between blocks from the copolymer molecular weight; thus, the T ODT can be controlled independently from the molecular weight .…”

“…From the standpoint of reducing T ODT (increasing processability), recent efforts on tapered BCPs deserve attention. [129][130][131] Manipulating the interfacial composition in BCP systems provides a way to decouple the segregation strength (v eff N) between blocks from the copolymer molecular weight; thus, the T ODT can be controlled independently from the molecular weight. 132,133 Moreover, the effects of domain orientations on transport in a polymer electrolyte are notable.…”

RAFT polymerization and associated reactivity ratios of methacrylate-functionalized mixed bio-oil constituents

“…This tactic (albeit with single-component monomer streams) is employed regularly for synthesizing polymers with predetermined compositional profiles in tapered block copolymers and gradient copolymers. [22][23][24][70][71][72][73][74] Extension of these methods to multicomponent bio-oils would allow for the synthesis of renewable heteropolymers with precise compositions and properties, greatly enhancing the feasibility of numerous bio-oil-based plastics for commercialization.…”

Controlled ionic conductivity via tapered block polymer electrolytes

“…1. [25][26][27][28][29] This architecture differs from gradient copolymers, which have a graded compositional prole extending along the entire polymer chain. [30][31][32][33][34][35] Previous studies have demonstrated that manipulating the segment distribution in BP systems can decrease the effective segregation strength between blocks by reducing the effective c; in other words, the processing temperatures can be tuned independent of the chemical constituents and the molecular weight (i.e., mechanical properties) using tapered interfaces.…”