Mild organobases and Et3B constitute an operationally simple, user-friendly catalyst setup for polymerizing propylene oxide.

Conventional approaches for polymerizing substituted epoxides, especially propylene oxide, suffer from side reactions, severely limiting molar masses and control over the end groups of the resulting poly(propylene oxide) (PPO). This has not only complicated the incorporation of PPO moieties into complex defined polymer architectures, but has also hampered consideration of PPO as an interesting material in its own right. In this context, a concise summary of strategies for creating truly high-molecular-mass polyethers is provided, with a focus on a recently developed dual catalytic setup that permits access to PPO molar masses of 106 g/mol and beyond. Based on these advances in the catalytic preparation of polyethers, future perspectives for ultrahigh-molecular-weight (UHMW) PPO as a performance material are identified.

Using an organocatalytic polymerization method for the preparation of well-defined, amphiphilic block copolyethers of the type PPO n/2 -PEO m -PPO n/2 ("Reverse Pluronics", M n up to 50 000 g/mol, Đ M = 1.01−1.08, >100 examples), it is demonstrated that the application of these polymers as structure-directing agents (SDAs) in a standard softtemplating process delivers ordered mesoporous carbons (OMCs), whereby the resulting pore diameters are monomodal and narrowly distributed. Moreover, by the judicious choice of the SDA properties (total molar mass, ratio of n and m, and PPO block length), pore diameters in the range of 6−18 nm can be selectively addressed, notably within the same arrangement pattern (2D hexagonal, p6mm). This provides a rational, operationally simple method to tailor pore properties of otherwise uniform carbons, also significantly reducing the effort necessary to obtain systematically altered materials. Ready access to such quick screenings is assumed to be immensely useful for pore size-dependent applications from numerous disciplines such as sensing, catalysis, or energy storage and conversion. Surprisingly, it is not only found that a minimum of M n = 13 000 g/mol is required to deliver ordered (nondistorted) materials under these conditions but also that very high-molar-mass SDAs are best suited to achieve optimum results, potentially providing an explanation for why "Reverse Pluronics" are frequently, and wrongly, thought to be per se unsuitable for the preparation of well-ordered mesoporous carbons.

Tailor-made PPOn/2–PEOm–PPOn/2 polyethers are used to prepare ordered mesoporous silica materials with rationally addressable pore diameters between 4.5 and 21.5 nm.