115152-71-1Relevant academic research and scientific papers
Controlled preparation of amphiphilic triblock-copolyether in a metal- and solvent-free approach for tailored structure-directing agents
Balint, Alexander,Papendick, Marius,Clauss, Manuel,Müller, Carsten,Giesselmann, Frank,Naumann, Stefan
, p. 2220 - 2223 (2018)
Under mild conditions, PPO-PEO-PPO ("reverse Pluronics") and PBO-PEO-PBO copolyether were generated by way of N-heterocyclic olefin-based organocatalysis. Reverse Pluronics with molar masses > 20 000 g mol-1 could be synthesized with excellent control (DM ≤ 1.03) and were converted into (ordered) mesoporous carbons via organic self-assembly to showcase the need for tailor-made copolymer as structure-directing agent.
Lewis Pair Polymerization of Epoxides via Zwitterionic Species as a Route to High-Molar-Mass Polyethers
Walther, Patrick,Krau?, Annabelle,Naumann, Stefan
, p. 10737 - 10741 (2019)
A dual catalytic setup based on N-heterocyclic olefins (NHOs) and magnesium bis(hexamethyldisilazide) (Mg(HMDS)2) was used to prepare poly(propylene oxide) with a molar mass (Mn) >500 000 g mol?1, in some cases even >106 g mol?1, as determined by GPC/light scattering. This is achieved by combining the rapid polymerization characteristics of a zwitterionic, Lewis pair type mechanism with the efficient epoxide activation by the MgII species. Transfer-to-monomer, traditionally frustrating attempts at synthesizing polyethers with a high degree of polymerization, is practically removed as a limiting factor by this approach. NMR and MALDI-ToF MS experiments reveal key aspects of the proposed mechanism, whereby the polymerization is initiated via nucleophilic attack by the NHO on the activated monomer, generating a zwitterionic species. This strategy can also be extended to other epoxides, including functionalized monomers.
N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide)
Naumann, Stefan,Thomas, Anthony W.,Dove, Andrew P.
, p. 9550 - 9554 (2015)
The metal-free polymerization of propylene oxide (PO) using a special class of alkene - N-heterocyclic olefins (NHOs) - as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (D strok signM1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions. One carbon makes a difference: The efficient and controlled formation of poly(propylene oxide) (PPO) at a very low catalyst loading of N-heterocyclic olefins showcases the use of this group of highly polarized alkenes as catalysts for organopolymerization. A strong structure-activity relationship is found, which is fundamentally different from the reactivity of N-heterocyclic carbenes (TON=turnover number, PDI=polydispersity index).
Synthesis and properties of alkoxy- and alkenyl-substituted peralkylated imidazolium ionic liquids
Maton, Cedric,Brooks, Neil R.,Van Meervelt, Luc,Binnemans, Koen,Schaltin, Stijn,Fransaer, Jan,Stevens, Christian V.
, p. 3503 - 3516 (2013)
Novel peralkylated imidazolium ionic liquids bearing alkoxy and/or alkenyl side chains have been synthesized and studied. Different synthetic routes towards the imidazoles and the ionic liquids comprising bromide, iodide, methanesulfonate, bis(trifluoromethylsulfonyl)imide ([NTf2] -), and dicyanamide {[N(CN)2]-} as the anion were evaluated, and this led to a library of analogues, for which the melting points, viscosities, and electrochemical windows were determined. Incorporation of alkenyl moieties hindered solidification, except for cations with high symmetry. The alkoxy-derivatized ionic liquids are often crystalline; however, room-temperature ionic liquids (RTILs) were obtained with the weakly coordinating anions [NTf2]- and [N(CN)2] -. For the viscosities of the peralkylated RTILs, an opposite trend was found, that is, the alkoxy derivatives are less viscous than their alkenyl-substituted analogues. Of the crystalline compounds, X-ray diffraction data were recorded and related to their molecular properties. Upon alkoxy substitution, the electrochemical cathodic limit potential was found to be more positive, whereas the complete electrochemical window of the alkenyl-substituted imidazolium salts was shifted to somewhat more positive potentials. Im melting! A library of fully substituted imidazolium ionic liquids is synthesized. The cations are provided with alkenyl or alkoxy moieties. The alkenyl-substituted analogues with low symmetry undercool very well, whereas the alkoxy-substituted compounds are readily crystallizable but have lower viscosities. Single-crystal X-ray diffraction analysis shows a relationship between the intermolecular interactions and the melting points of the solid compounds.
Unexpected oxidative C-C cleavage in the metallation of 2-substituted imidazolium salts to give N-heterocyclic carbene complexes
Chianese, Anthony R.,Zeglis, Brian M.,Crabtree, Robert H.
, p. 2176 - 2177 (2007/10/03)
Imidazolium salts blocked at C2 with methyl or benzyl groups unexpectedly react with silver oxide to give N-heterocyclic carbene complexes of silver via an oxidative carbon-carbon bond cleavage.
