Cationic Homo- and Co-polymerizations of Ethyl Glycidate

Abstract

ABSTRACT:Cationic homo-and co-polymerizations of ethyl glycidate (EG) have been studied with triethyloxonium tetrafluoroborate (TEOFB) and superacid ester catalysts. The homopolymerization of EG gave a paste-like material of low molecular weight with TEOFB catalyst. A superacid ester catalyst such as ethyl trifluoromethanesulfonate underwent only the initiation process with EG and the propagation was negligibly slow in this system. Copolymerization of EG with tetrahydrofuran (THF) gave a copolymer with TEOFB. When THF remained unreacted after the completion of copolymerization, the copolymer composition was in all cases EG: THF = I : 2. These results were understood in terms of the penultimate effect. The same copolymerization by a superacid ester catalyst, however, always yielded copolymers of the EGITHF= 112 composition. This result was explained in the same way as the TEOFB case, taking the EG polymerizability by a superacid ester into account.KEY WORDS Ethyl Glycidate Cationic PolymerizationCopolymerization I Tetrahydrofuran I Oxonium Salt I Superacid Ester I Penultimate Effect I Cyclic ethers and particularly epoxides have been known for a long time to polymerize to polyethers even of very high molecular weight. 1 • 2 While cyclic ethers polymerize primarily with classical cationic initiators and aluminum and zinc organic compounds by what is often referred to as coordinative anionic polymerization, 3 epoxides undergo polymerization by classical cationic and anionic mechanisms and also by the above mentioned coordinative mechanism. 1 • 2 Most of the work has been done on unsubstituted and methyl-substituted compounds, namely ethylene oxide and propylene oxide; substitutent groups with higher polarity and the functionality have not been studied to any extent. The monomers with the most reactive groups were those with a chloromethyl substitution as, for example, in epichlorohydrin 4 and 3,3-bis(chloromethyl)oxetane. 5 agent, which in turn must be prepared from 90 % H 2 0 2 and trifluoroacetic acid. Glycidaldehyde, 7 glycidyl esters, 8 and glycidonitrile 7 have been prepared; glycidaldehyde was polymerized via both the epoxide group and the aldehyde group, depending on the reaction conditions. 9 These monomers have been copolymerized with trioxane 10 and the properties of co-and ter-polymers with 1,3-dioxolane with a relatively low percentage of glycidate incorporated were investigated. 11 These polymers were then hydrolyzed to the corresponding poly( oxymethylene)ionomers and their free acids. The co-and terpolymerizations were accomplished with classical cationic initiators, both in bulk solution 11 and by a process in which the monomers were mixed in the vapor phase. 12 Epoxides which have functional groups directly attached to the epoxide rings have been already known. 6 Their synthesis is not particularly easy as it requires trifluoroperacetic acid as the oxidizing It was the. purpose of this work to study the cationic homo-' and co-polymerization of ethyl glycidate, especially the investigation of suitab...

Copolymerization of Ethyl Glycidate with Cyclic Ethers by Organometallic Initiators

“…9 These results indicate unfavorable copolymerizations of EG with ECH and PGE. The compositions of the other EG/PO copolymers were then determined from their infrared spectra, and a similar procedure was used for BO and oxetane copolymers.…”

“…[4][5][6][7][8][9] Ethyl glycidate was previously shown to polymerize with an aluminum alkyl/water initiator system to a crystalline homopolymer.1° The initiator system which was the basis of this paper was reported in detail i n a separate communication." Particularly successful has been the preparation of polyolefin ionomers containing pendant metal carboxylate groups.…”

“…Primary attention was focused on copolymerizations with PO or BO with EG (experiments[2][3][4][5][6][7][8][9], for which a range of monomer feed compositions was investigated; column 6 of 1) used to provide a initiator activity and polymerization technique.…”

Polyethylenimine–polyepichlorohydrin interpolymer for chelating ion-exchange membrane

“…The preparation of the elastic materials can be performed by the following two methods: 1. graft polymerization onto an elastomer, and 2. blending PEI with an elastomer followed by crosslinking the two polymers with each other. Graft polymerization of 2-methyl-2-oxazoline onto poly( 1,3-butadiene-co-l-chloro-1,3-butadiene) was carried out as an example of method l. 3 The present paper describes an example of method 2, in which polyepichlorohydrin (PECH) was used as an elastomer. Since PECH possesses moderately active chloromethyl groups, the method seems to be convenient to prepare anion-exchange materials by reacting this group with amines such as PEL When the elastic ion-exchange materials containing PEI is used as a membrane, specific ion-selective transfer characteristics might be expected for the PEI membrane.…”

Poly(alkylene oxide) ionomers VIII. Synthesis of methyl ω‐alkenoates and methyl ω‐epoxyalkanoates

“…The infrared spectrum (NaC1 plates) showed absorptions centered at 1742 cm-l (C= 0 stretching), 1641 cm-' (C=C stretching), and 995 cm-' and 912 cm-l (vinyl C-H bending). The 13C NMR spectrum (neat) showed peaks at 24 c. Methyl 6,7-epoxyheptanoate. A solution of methyl 6-heptenoate (10 g, 70 mmol) and dichloromethane (36 mL) was added to a solution of m-chloroperoxybenzoic acid (14 g, 82 mmol) and dichloromethane (100 mL), at 0°C.…”