Construction of Versatile and Functional Nanostructures Derived from CO₂‐based Polycarbonates

Abstract

The construction of amphiphilic polycarbonates through epoxides/CO2 coupling is a challenging aim to provide more diverse CO2 -based functional materials. In this report, we demonstrate the facile preparation of diverse and functional nanoparticles derived from a CO2 -based triblock polycarbonate system. By the judicious use of water as chain-transfer reagent in the propylene oxide/CO2 polymerization, poly(propylene carbonate (PPC) diols are successfully produced and serve as macroinitiators in the subsequent allyl glycidyl ether/CO2 coupling reaction. The resulting ABA triblock polycarbonate can be further functionalized with various thiols by radical mediated thiol-ene click chemistry, followed by self-assembly in deionized water to construct a versatile and functional nanostructure system. This class of amphiphilic polycarbonates could embody a powerful platform for biomedical applications.

Changes in Phase Behavior from the Substitution of Ethylene Oxide with Carbon Dioxide in the Head Group of Nonionic Surfactants

“…The process itself has been known for over 40 years but has seen substantial catalytic improvements in recent years . Application of such synthetic schemes, for instance, led to the formation of nanostructures from CO 2 ‐based polycarbonates or functional copolymers based on CO 2 and glycidyl ethers …”

A One‐Step Route to CO2‐Based Block Copolymers by Simultaneous ROCOP of CO2/Epoxides and RAFT Polymerization of Vinyl Monomers

“…[6] Nonetheless,ROCOP of CO 2 /epoxides is extremely sensitive to catalyst and reaction temperature because of the quite small energy barrier between polycarbonates and corresponding cyclic by-products, [2c,d] making it difficult to meet the harsh requirements mentioned above; thus,o ne-step synthesis of CO 2 -based block copolymers remains ag reat challenge that has been rarely achieved. [10] Herein we report the unprecedented terpolymerization of CO 2 ,epoxides,and vinyl monomers for the one-step synthesis of various CO 2 -based block copolymers with completely alternating polycarbonate segments using ac arboxy/trithiocarbonate bifunctional chain transfer agent (TTC-COOH; Scheme 1). [10] Herein we report the unprecedented terpolymerization of CO 2 ,epoxides,and vinyl monomers for the one-step synthesis of various CO 2 -based block copolymers with completely alternating polycarbonate segments using ac arboxy/trithiocarbonate bifunctional chain transfer agent (TTC-COOH; Scheme 1).…”

Click Chemistry in Functional Aliphatic Polycarbonates

“…In the presence of dithiols, double‐bond‐containing polycarbonates were able to yield crosslinked polymers with improved thermal properties . Propylene oxide/CO 2 polymerization and subsequent allyl glycidyl ether/CO 2 coupling reaction as well as further modification with various thiols including mercaptoacetic acid, 2‐(Boc‐amino)ethanethiol and Boc‐ l ‐cysteine by thiol‐ene reaction constructed amphiphilic block polycarbonates . Allyl‐functional polycarbonates were modified with 3‐mercaptopropionic acid via thiol‐ene reaction, followed by reacting with lithium hydroxide, to generate single‐ion‐conducting polycarbonate electrolyte that showed high ionic conductivity and high lithium ion transference number .…”