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…

Controlled Synthesis of Multi-Arm Star Polyether-Polycarbonate Polyols Based on Propylene Oxide and CO2

Multi-arm star copolymers based on a hyperbranched poly(propylene oxide) polyether-polyol (hbPPO) as a core and poly(propylene carbonate) (PPC) arms are synthesized in two steps from propylene oxide (PO), a small amount of glycidol and CO2 . The PPC arms are prepared via carbon dioxide (CO2 )/PO copolymerization, using hbPPO as a multifunctional macroinitiator and the (R,R)-(salcy)CoOBzF5 catalyst. Star copolymers with 14 and 28 PPC arms, respectively, and controlled molecular weights in the range of 2700-8800 g mol(-1) are prepared (Mw /Mn = 1.23-1.61). Thermal analysis reveals lowered glass transition temperatures in the range of -8 to 10 °C for the PPC star polymers compared with linear …

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…

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

Poly(carbonate) copolymers with a tailored number of hydroxyl groups from glycidyl ethers and CO2

Functional poly(carbonate)s with multiple hydroxyl functionalities have been prepared by copolymerization of carbon dioxide (CO2) with glycidyl methyl ether (GME) and benzyl glycidyl ether (BGE) in various ratios, using a diethylzinc–pyrogallol catalyst system. Subsequent catalytic hydrogenation was employed for removal of the benzyl protecting groups at the polymer backbone. A series of copolymers with varying comonomer fractions from 0 to 100% was obtained. The copolymers possessed a broad range of molecular weights from 9000 to 30 000 g mol−1 and showed polydispersities Mw/Mn between 2.4 and 3.6. The materials were characterized via1H and 13C NMR, SEC and differential scanning calorimetr…

CO2-Based Non-ionic Surfactants: Solvent-Free Synthesis of Poly(ethylene glycol)-block-Poly(propylene carbonate) Block Copolymers

Copolymerization of carbon dioxide (CO2) and propylene oxide (PO) is employed to generate amphiphilic polycarbonate block copolymers with a hydrophilic poly(ethylene glycol) (PEG) block and a nonpolar poly(propylene carbonate) (PPC) block. A series of poly(propylene carbonate) (PPC) di- and triblock copolymers, PPC-b-PEG and PPC-b-PEG-b-PPC, respectively, with narrow molecular weight distributions (PDIs in the range of 1.05–1.12) and tailored molecular weights (1500–4500 g mol−1) is synthesized via an alternating CO2/propylene oxide copolymerization, using PEG or mPEG as an initiator. Critical micelle concentrations (CMCs) are determined, ranging from 3 to 30 mg L−1. Non-ionic poly(propylen…

Propargyl-functional aliphatic polycarbonate obtained from carbon dioxide and glycidyl propargyl ether.

The synthesis of propargyl-functional poly(carbonate)s with different content of glycidyl propargyl ether (GPE) units is achieved via the copolymerization of propargyl glycidyl ether and carbon dioxide. A new type of functional poly(carbonate) synthesized directly from CO(2) and the glycidyl ether is obtained. The resulting polymers show moderate polydispersities in the range of 1.6-2.5 and molecular weights in the range of 7000-10 500 g mol(-1). The synthesized copolymers with varying number of alkyne functionalities and benzyl azide are used for the copper-catalyzed Huisgen-1,3-dipolar addition. Moreover, the presence of vicinal alkyne groups opens a general pathway to produce functional …