Highly Active Heterogeneous Double Metal Cyanide Catalysts for Ring-Opening Polymerization of Cyclic Monomers

Abstract

A series of heterogeneous Zn-Co double metal cyanide (DMC) catalysts were investigated for ring-opening polymerization (ROP) of various cyclic monomers. Notably, inexpensive and commonly used organic solvents such as acetone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, nitromethane, and 1-methylpyrrolidin-2-one were very effective complexing agents for the preparation of DMC catalysts, showing high catalytic activity for the ROP of propylene oxide, ε-caprolactone, and δ-valerolactone. The chemical structures and compositions of the resultant catalysts were determined using various techniques such as FT-IR, X-ray photoelectron spectroscopy, powder X-ray diffraction, and elemental analysis. α,ω-Hydroxyl-functionalized polyether and polyester polyols with high yields and tunable molecular weights were synthesized in the presence of various initiators to control functionality. Kinetic studies of the ROP of δ-valerolactone were also performed to confirm the reaction mechanism.

Enhanced Double Metal Cyanide Catalysts for Modulating the Rheological Properties of Poly(propylene carbonate) Polyols by Modifying Carbonate Contents

“…Figure B presents the four stages of weight loss observed from the derivative thermogravimetry (DTG) curves. Loss of physically adsorbed water molecules initially occurred at 40–180 °C (first stage), followed by removal of chemically bonded water molecules at 180–320 °C (second stage). The weight loss at 320–370 °C (third stage) was due to the loss of the organic complexing agent, P123, and that at 370–550 °C (fourth stage) was induced by the decomposition of cyanide moieties .…”

Synthesis of Polyether, Poly(Ether Carbonate) and Poly(Ether Ester) Polyols Using Double Metal Cyanide Catalysts Bearing Organophosphorus Complexing Agents

“…DMC catalysts are prepared in the presence of organic additives or complexing agents (CAs), which result in more amorphous structures than conventional PBAs. To date, DMC catalysts have been widely used for numerous organic reactions such as the copolymerization and cycloaddition of CO 2 and epoxides, epoxide ring-opening using amines, esterification and transesterification, synthesis of hyperbranched polymers, hydrogen amination reactions, and Prins reactions [ 12 , 13 , 14 , 15 , 16 , 17 , 18 ]. Notably, the DMC method has tremendous potential for commercialization of CO 2 utilization processes.…”

Facile preparation of biodegradable poly(γ-butyrolactone) via base-assisted ring-opening polymerization

“…Traditionally, γ-butyrolactone was considered as non-polymerizable 8 due to the low strain energy 9 of the five-membered ring compared to other readily polymerizable lactones such as ε-caprolactone, 10 δ-valerolactone 11 or lactide. 12 Extreme pressure was used for the first homo-polymerization of γ-butyrolactone.…”