Rigid Hyperbranched Polycarbonate Polyols from CO2 and Cyclohexene-Based Epoxides

Hyperbranched, multifunctional polycarbonate polyols based on CO2, cyclohexene oxide (CHO), and the “inimer” (initiator–monomer) (4-hydroxymethyl)cyclohexene oxide (HCHO) were prepared in one-pot syntheses. The related linear poly(hydroxymethyl cyclohexene carbonate) structures based on protected HCHO and postpolymerization deprotection were also synthesized as model compounds. The content of hydroxyl functionalities was adjustable for both linear and hyperbranched terpolymer systems. All CO2/epoxide polymerizations were catalyzed by the (R,R)-(salcy)-Co(III)Cl complex. The polycarbonates obtained were comprehensively investigated using various 1D and 2D NMR techniques, SEC, FT-IR, UV–vis s…

Aliphatic polycarbonates based on carbon dioxide, furfuryl glycidyl ether, and glycidyl methyl ether: reversible functionalization and cross-linking.

Well-defined poly((furfuryl glycidyl ether)-co-(glycidyl methyl ether) carbonate) (P((FGE-co-GME)C)) copolymers with varying furfuryl glycidyl ether (FGE) content in the range of 26% to 100% are prepared directly from CO2 and the respective epoxides in a solvent-free synthesis. All materials are characterized by size-exclusion chromatography (SEC), (1)H NMR spectroscopy, and differential scanning calorimetry (DSC). The furfuryl-functional samples exhibit monomodal molecular weight distributions with Mw/Mn in the range of 1.16 to 1.43 and molecular weights (Mn) between 2300 and 4300 g mol(-1). Thermal properties reflect the amorphous structure of the polymers. Both post-functionalization and…

Multiarm Polycarbonate Star Polymers with a Hyperbranched Polyether Core from CO2 and Common Epoxides

Multiarm star copolymers, consisting of hyperbranched poly(ethylene oxide) (hbPEO) or poly(butylene oxide) (hbPBO) polyether copolymers with glycerol branching points as a core, and linear aliphatic polycarbonate arms generated from carbon dioxide (CO2) and epoxide monomers, were synthesized via a “core-first” approach in two steps. First, hyperbranched polyether polyols were prepared by anionic copolymerization of ethylene oxide or 1,2-butylene oxide with 8–35% glycidol with molecular weights between 800 and 389,000 g·mol–1. Second, multiple arms were grown via immortal copolymerization of CO2 with propylene oxide or 1,2-butylene oxide using the polyether polyols as macroinitiators and (R,…

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

Acid-Labile Surfactants Based on Poly(ethylene glycol), Carbon Dioxide and Propylene Oxide: Miniemulsion Polymerization and Degradation Studies

Partially degradable, nonionic AB and ABA type di- and triblock copolymers based on poly(propylene carbonate) and poly(ethylene glycol) blocks were synthesized via immortal copolymerization of carbon dioxide and propylene oxide, using mPEG or PEG as a macroinitiator, and (R,R)-(salcy)-CoOBzF5 as a catalyst in a solvent-free one-pot procedure. The amphiphilic surfactants were prepared with molecular weights (Mn) between 2800 and 10,000 g·mol−1 with narrow molecular weight distributions (1.03–1.09). The copolymers were characterized using 1H-, 13C- and DOSY-NMR spectroscopy and size exclusion chromatography (SEC). Surface-active properties were determined by surface tension measurements (crit…