Long‐Chain Alkyl Epoxides and Glycidyl Ethers: An Underrated Class of Monomers

Abstract

Long‐chain epoxides and specifically alkyl glycidyl ethers represent a class of highly hydrophobic monomers for anionic ring‐opening polymerization (AROP), resulting in apolar aliphatic polyethers. In contrast, poly(ethylene glycol) is known for its high solubility in water. The combination of hydrophobic and hydrophilic monomers in block and statistical copolymerization reactions enables the synthesis of amphiphilic polyethers for a wide range of purposes, utilizing micellar interactions in aqueous solutions, e.g., viscosity enhancement of aqueous solutions, formation of supramolecular hydrogels, or for polymeric surfactants. Controlled polymerization of these highly hydrophobic long‐chain epoxide monomers via different synthesis strategies, AROP, monomer‐activated anionic ring‐opening polymerization, catalytic polymerization, or via postmodification, enables precise control of the hydrophilic/lipophilic balance. This renders amphiphilic polymers highly interesting candidates for specialized applications, e.g., as co‐surfactants in microemulsion systems. Amphiphilic polyethers based on propylene oxide and ethylene oxide, such as poloxamers are already utilized in many established applications due to the high biocompatibility of the polyether backbone. Long alkyl chain epoxides add an interesting perspective to this area and permit structural tailoring. This review gives an overview of the recent developments regarding the synthesis of amphiphilic polyethers bearing long alkyl chains and their applications.

“Dumb” pH-Independent and Biocompatible Hydrogels Formed by Copolymers of Long-Chain Alkyl Glycidyl Ethers and Ethylene Oxide

“…Synthesis of ABA triblock copolymers using deprotonated PEG as a bifunctional macroinitiator (hydrophilic midblock) and long-chain alkyl glycidyl ethers (AlkGE) C12-AlkGE and C16-AlkGE copolymerized with ethylene oxide (EO) for the A-blocks.…”

Mercarbide Catalyst for Alcohol Ethoxylation

“…(Reaction was studied in excess of the alcohol, but it is known [2][3][4][5] that the ethoxylation reaction is first order to alcohol). The kinetic equation is the followed: where C eo is the concentration of ethylene oxide, mol/l; C alc -the concentration of alcohol, mol/l.…”

“…In the ethoxylation of aliphatic alcohols, homogeneous basic catalysts, such as NaOH, KOH or NaOCH 3 , are generally used to facilitate ethylene oxide (hereafter abbreviated as EO) insertion to the alcohols at relatively low temperature and pressure [3][4]. In this homogeneous type of alcohol ethoxylation, distributions of oxyethylene units (-CH 2 -CH 2 -O-) in the ethoxylated product mixture are much broader than the statistical Poisson-type distribution [4][5] which can be calculated by Eq.…”

Ethoxylation of Phenols Catalyzed by Metal‐Free Lewis Pairs: Living/Controlled Polymerization in a Slow‐Initiation Mode†

“…[ 1‐2 ] For an entire century, tremendous amounts of efforts have been devoted, both in industry and academia, to optimizing the ROP‐based synthetic methods and enriching the structures/functions of the polyether products. [ 3‐4 ] The chain‐ growth character of epoxide ROP determines that the chain structures, topological structures, and main‐chain/end‐group functionalities of these polyethers are strongly dependent on the initiators, which also frequently appear as chain transfer agents. [ 5‐9 ] Therefore, expanding the scope of viable initiators has become an indispensable section of this research area.…”