Synthesis of Aliphatic Hyperbranched Polycarbonates via Organo-Catalyzed “A₁+B₂”-Ring-Opening Polymerization

Abstract

Hyperbranched aliphatic polycarbonates (HBPCs) have attracted significant attention in the field of biomedical application owing to their abundant end groups, biocompatibility, and nontoxic degradation products. However, their practical application is hampered by tedious synthesis procedures. The present work described a novel organo-catalyzed “A1+B2”-ring-opening polymerization (ROP) using a monofunctional primary alcohol (A1) as an initiator and a bicyclic carbonate monomer (B2) for the straightforward synthesis of HBPCs under mild conditions. No gelation was observed up to 90% conversion of the cyclic carbonate ring. HBPCs with molar masses in the range from 7 to 20 kg/mol were obtained. Based on the “A1+B2”-ROP, HBPCs bearing a variety of functionalities including alkene, alkyne, aldehyde, furan, azide, and mPEG groups, which are of great significance in the field of click chemistry, have been successfully prepared by using functional alcoholic initiators. This polymerization strategy allowed for precise control over the HBPC structure: (1) the hyperbranched polymer (HBP) backbone can be adjusted by design of a bicyclic carbonate monomer with various linkages; (2) the use of an appropriate initiator leads to the introduction of functional end groups. Overall, the “A1+B2”-ROP provides an efficient method for preparing a variety of HBPs like hyperbranched polyester, polyether, polyphosphate, and poly­(amino acid) with complex architectures in a single step.

Aliphatic Hyperbranched Polycarbonates Solid Polymer Electrolytes with High Li‐Ion Transference Number for Lithium Metal Batteries

“…The successful synthesis of hyperbranched structures requires the use of an equimolar quantity of primary alcohol as an initiator. [ 26 ] In the realm of polymer electrolytes, polyethylene glycol monomethyl ether (mPEG) undeniably emerges as the most suitable choice, widely acknowledged as the optimal material for polymer electrolytes. The influence of mPEG chain length on the ionic conductivity of polymer electrolytes was investigated.…”

“…[3] Hyperbranched polymers (HBPs), a classic representative of topological polymer with a history dating back to the late 19th century, are characterized by highly branched 3D structures encompassing both side chains and terminal functional groups. [25][26][27] The unique 3D architecture of these polymers contributes to their low crystallinity. [27][28][29] Furthermore, the molecules of HBP exhibit significantly distinct properties from their corresponding linear counterparts, such as low viscosity, excellent solubility, and a plethora of modifiable functional groups.…”

“…[27][28][29] Furthermore, the molecules of HBP exhibit significantly distinct properties from their corresponding linear counterparts, such as low viscosity, excellent solubility, and a plethora of modifiable functional groups. [26,[30][31][32] As a result, HBPs have garnered significant research attention and are considered one of the most promising matrices for SPEs. Su et al [33] conducted pioneering work by synthesizing a 21-arm fluoropolymer using atom transfer radical polymerization.…”

Metal-free polycyclotrimerization of trimethylsilyl-protected diynes: a facile strategy toward regioregular hyperbranched polyarylenes

“…1 Hyperbranched polymers (HBPs) have attracted much attention during the past decades due to their three-dimensional globular architectures, unique properties, and wide applications in optoelectronic and biomedical materials, supramolecular chemistry, and so on. [2][3][4][5][6][7][8] Thanks to the unremitting efforts of polymer chemists, numerous synthetic strategies, such as polycondensation, [9][10][11][12] self-condensation vinyl polymerization, [13][14][15] ring-opening polymerization, [16][17][18][19] polycycloaddition, 20,21 controlled/living polymerization, 22,23 and click polymerization, [24][25][26][27] have been developed for the synthesis of HBPs with diverse structures and functional properties.…”

Synthesis, Characterization and UV‐Crosslinking of Aromatic (Co)polycarbonates Bearing Pendant Azido Groups

“…[5][6][7] For the synthesis of aliphatic polycarbonates, a range of difunctional and ROP monomers containing functional groups have been reported in the literature. [8][9][10] The pendant clickable functional groups which have been incorporated in to aliphatic polycarbonates include: allyl, [11][12][13][14][15][16][17] alkyne, [9,[18][19][20][21] norbornenyl, [22,23] furyl, [24,25] anthryl, [26] active ester, [27,28] aldehyde, [29] azido, [8,30,31] and maleimido. [32][33][34] These functional groups have been further modified by appropriate click reactions to obtain aliphatic polycarbonates with a desirable set of properties.…”