One‐Pot Structure‐Controlled Synthesis of Hyperbranched Polymers by a “Latent” Inimer Strategy Based on Diels–Alder Chemistry

Abstract

An efficient "one-pot" strategy for the structure-controlled synthesis of hyperbranched polymers (HBPs) based on a "latent" inimer (LI-Br), containing a furan-protected maleimide monomer and a haloalkane initiator, is presented. At high temperatures, the "latent" inimer is converted to a "real" inimer after releasing maleimide (MI) via a retro-Diels-Alder (r-DA) reaction and then copolymerized with methyl methacrylate by self-condensing vinyl copolymerization. Due to the dynamic characteristic of the r-DA reaction, the release of naked MI and the subsequent copolymerization can be regulated by the temperature or stereochemistry of Diels-Alder (DA) adducts. Thus, the "onepot" structure-controlled synthesis of HBPs with various degrees of branching was achieved. By further implementation of a programmable temperature change, some valuable hyperbranched topologies such as star-shaped and long-chain hyperbranched polymers can be constructed avoiding sophisticated synthetic routes.

Controlled Diels–Alder “Click” Strategy to Access Mechanically Aligned Main‐Chain Liquid Crystal Networks

“…To provide a dormant reactive group, maleimide can be protected through the cycloaddition of furan forming the thermally labile endo ‐furan‐maleimide (fu‐mal) DA adduct. This Cp‐mal DA based chemistry provides a fast, metal free, selective, and quantitative step‐growth polymerization for the first step [20,21] while the fu‐mal DA adduct can be deprotected at 60 °C via a retro DA ( r DA) cycloreversion to regenerate maleimide in situ [22–24] . Importantly, the by‐product from the deprotection is furan, which is volatile and easily removed from the LCN.…”

Cryogenic efficient phase separation of oil–water emulsions with amphiphilic hyperbranched poly(amido-amine)

“…23 Hyperbranched polymer-based materials with tailorable structures and correspondingly unique properties have been highly desirable candidates in various elds over the past few years. 24,25 Hyperbranched poly(amido-amine) (HPAMAM) has been utilized in the area of polymer materials due to its unique globular and dendritic structure combined with abundant functional groups. 26,27 Due to its modiable potential, HPAMAM is expected to be enriched with new physicochemical properties of molecule structure regulation on synthesis to meet the actual demand of low-temperature demulsication.…”

Intracellular Hyperbranched Polymerization for Circumventing Cancer Drug Resistance

“…Hyperbranched polymers (HBPs) are important topological polymers that have attracted increasing research attention due to their structures and distinctive properties, including improved physicochemical properties, excellent multifunctionalities, and special three-dimensional globular structures. − On the basis of their excellent water solubility, biodegradability, and potential functionalization as well as their simple one-pot synthesis, HBPs have fascinating biomedical applications, especially for drug delivery in cancer treatment. − However, HBPs synthesized under nonphysiological conditions in laboratory flasks may hinder their therapeutic effects as for the inefficiency across cellular membranes. − Furthermore, most HBPs are typically inert excipients that only serve as carriers. The free anticancer agents released from HBPs can be easily recognized and removed by active efflux-pumping, resulting in low intracellular drug accumulation and ultimately therapeutic failure. − Therefore, moving hyperbranched polymerization from the laboratory flask into living cells is believed to be an inspiring strategy to overcome the above limitations.…”