Ring‐opening polymerization of epichlorohydrin and its copolymerization with other alkylene oxides by quaternary catalyst system

Abstract

An effective quaternary catalyst consisting of trialkyl aluminum, phosphoric acid, electron donor, and water for ring-opening polymerization of epichlorohydrin (ECH), as well as its copolymerization with ethylene oxide (EO), propylene oxide (PO), and allyl glycidyl ether (AGE) to obtain elastomers, were studied. We investigated the optimum composition for the quaternary catalyst; the character of the catalyst; the reactivity of the four alkylene oxides during homopolymerization and copolymerization; the behavior of ECH, EO, and PO during terpolymerization; and glass transition temperatures of the copolymer and terpolymers. The results showed that the nitrogencontaining electron donors are suitable as the third component, whereas oxygencontaining electron donors are not. Water as the fourth component can increase the molecular weight of the homopolymer and copolymers of ECH. According to the polymerizability of tetrahydrofuran with the quaternary catalyst and the reactivity ratios of the four alkylene oxides, the quaternary catalyst was assumed to be of a coordinated anionic type. The reactivity ratios for these four alkylene oxides were determined to be EO Ͼ PO Ͼ AGE Ͼ ECH. They were verified by terpolymerization of ECH, EO, and PO. The glass transition temperature of the terpolymer exhibits a minimum value at nearly 3:1 molar ratio of PO to EO, when the molar ratio of ECH used is constant at the beginning of terpolymerization.

Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate‐free polyurethane networks

“…Glycerol, a byproduct of both the biodiesel production and the saponification of animal fats is obtained in large amount (400,000 tons in 2005) and needs to be better valorized as raw material. Their transformations into glycerol carbonate, aldehydes, ketones, and carboxylic acids,10 as well as epichlorohydrin11 (ECH) and allyl glycidyl ether12 (AGE), were reported. Production of ECH from glycerol via dichlorination and deshydrochlorination has been recently industrialized 13, 14.…”

“…Production of ECH from glycerol via dichlorination and deshydrochlorination has been recently industrialized 13, 14. AGE can be synthesized by the reaction of ECH with allyl alcohol,12 the latter being obtained by heating glycerol in presence of formic acid. ECH and AGE possess two functional groups, which make these monomers of interest for the preparation of reactive polymers even if the first one is toxic.…”

Synthesis and degradation of biomedical materials based on linear and star shaped polyglycidols

“…AGE, t BGE, and EEGE can be considered as protected glycidol monomers; from polymers containing these repeating units the acetal or side chain ether group can be selectively cleaved leaving the in chain ether group unaffected. Although copolymers of all three protected glycidol monomers, AGE, t BuGE, and EEGE with oxirane monomers such as ethylene oxide and propylene oxide were synthesized25, 44 binary copolymers of the protected glycidol monomers have not been reported, until recently. Thus block and random copolymers were prepared, the kinetics of copolymerization was studied and the possibility of selective deprotecting of one of the repeating units was tested 45…”

Functional amphiphilic block copolyethers as carriers of caffeic acid phenethyl ester

“…PAGE‐based copolyethers as functional platforms for micellar drug delivery systems, soft microgel particles, multiple bioconjugation and modification, and polymer electrolytes have recently been reported. Ethylene oxide, propylene oxide as well as glycidyl ethers such as ethoxyethyl glycidyl ether (EEGE), tert ‐butyl glycidyl ether and furfuryl glycidyl ether were the commonly used comonomers, whereas the most typical chain architecture was the linear one.…”