Poly(Propylene Carbonate) from Carbon Dioxide: Challenges for Large‐Scale Application

A novel strategy for the incorporation of carbon dioxide into polymers is introduced. For this purpose, the Ugi five-component condensation (Ugi-5CC) of an alcohol, CO2 , an amine, an aldehyde, and an isocyanide is used to obtain step-growth monomers. Polymerization via thiol-ene reaction or polycondensation with diphenyl carbonate gives diversely substituted polyurethanes or alternating polyurethane-polycarbonates, respectively. Furthermore, the application of 1,12-diaminododecane and 1,6-diisocyanohexane as bifunctional components in the Ugi-5CC directly results in the corresponding polyamide bearing methyl carbamate side chains (M¯n = 19 850 g mol(-1) ). The latter polymer is further converted into the corresponding polyhydantoin in a highly straightforward fashion.

Section: Introductionmentioning

confidence: 99%

Ugi Reactions with CO₂: Access to Functionalized Polyurethanes, Polycarbonates, Polyamides, and Polyhydantoins

Sehlinger

Schneider

Meier

2014

“…Carbon dioxide (CO 2 ) is an attractive carbon source for materials synthesis with respect to resource utilization, as it is nontoxic, renewable, and readily available in large quantities and high purity . The alternating copolymerization of epoxides with CO 2 , first reported by Inoue and co‐workers in the 1960s, has been considered to be one of the most promising processes for its utilization.…”

Section: Introductionmentioning

confidence: 99%

Aliphatic Polycarbonates Based on Carbon Dioxide, Furfuryl Glycidyl Ether, and Glycidyl Methyl Ether: Reversible Functionalization and Cross‐Linking

Hilf

Scharfenberg

Poon

et al. 2014

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 cross-linking are performed via Diels-Alder chemistry using maleimide derivatives, leading to reversible network formation. This transformation is shown to be thermally reversible at 110 °C.

“…The growing recent interest of organic and bioorganic chemists in CO 2 has led to the development of a variety of synthetic reactions using CO 2 directly as a raw material, especially in the field of polymer chemistry . Since the seminal discovery of the copolymerization of CO 2 and epoxide monomers by Inoue et al in 1969, numerous works on different heterogeneous and homogeneous catalyst systems have been reported, and mostly propylene oxide (PO) and cyclohexene oxide have been polymerized to poly(propylene carbonate) (PPC) and poly(cyclohexene carbonate) (PCHO) . The commercialization of PPC has recently reached a modest volume of approximately 1000 t per year and is gaining increasing attention .…”

Section: Introductionmentioning

confidence: 99%

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

Hilf

Schulze

Seiwert

et al. 2013

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 PPC, which is due to the influence of the flexible polyether core. Successful conversion of the terminal hydroxyl groups with phenylisocyanate demonstrates the potential of the polycarbonate polyols for polyurethane synthesis.