Polyaddition of bifunctional spiro orthoesters with bifunctional acid chlorides accompanying double ring-opening isomerization

Abstract

Polyaddition of bifunctional spiro orthoesters (SOEs) with bifunctional acid chlorides was examined to develop zero‐shrinkage polymerization. The polyaddition afforded the corresponding polyether‐esters by repeating the addition reaction accompanying the double ring‐opening isomerization of the SOE moiety in a manner similar to the reaction of monofunctional SOEs with acid chlorides. The polyaddition accompanied a slight shrinkage or expansion in volume. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 68–73, 2000

Phosphorus-containing thermosets obtained by cationic copolymerisation of glycidyl compounds with a spiroorthoester or γ-butyrolactone

“…The synthesis of bisSOE was carried out following a described method [29]. EGeGly and g-BL were reacted with BF 3 $OEt 2 as a catalyst, but introducing some modifications in the work-up that allowed us to improve the reached yield.…”

“…All solvents were purified by standard procedures [28]. (1,4,6-trioxaspiro[4.4] nonan-2-yl)-methyloxy] ethane (bisSOE) [29] A mixture of 25 g (0.14 mol) of ethylene glycol diglycidyl ether (EGeGly) with 37 g (0.43 mol) of g-BL were added dropwise over a period of 30 min at a temperature below 10 C in argon atmosphere to a mixture of 37 g (0.43 mol) of g-BL and 1.5 mL (11.8 mmol) of BF 3 $OEt 2 as a catalyst. After the addition was completed, the mixture was stirred for 4 h at the same temperature.…”

Catalytic double ring-opening polyaddition of spiro orthoester with acid chloride for shrinkage-controlled molding

“…All catalysts listed in Table 2 including Lewis acids, onium salts, and phosphine derivatives were commercially purchased and used without further purification. SOEs (SOE-I-VII, IX, XI-XV) in Table 1 were prepared according to the literature in 11-66% yields [13,14]. Almost all the acid chlorides, acetic anhydride, and benzyl chloride listed in Table 4 were reagent grade, and used without further purification.…”

“…In our previous report [13,14], we succeeded in a selective polyaddition of bifunctional SOEs with bifunctional acid chlorides, in which the double ring-opening reaction of SOEs occurred repeatedly to obtain the corresponding copolymers with very little volume change in a range of 0.2% expansion to 1.3% shrinkage (Scheme 2). This double ring-opening polyaddition proceeded at lower temperatures (w60 8C) than those required for the homopolymerization of SOEs.…”

Formulación de imprimaciones epoxi en polvo de curado a bajas temperaturas basadas en triflatos de lantánido. Desarrollo de una técnica electroquímica para la evaluación acelerada de la protección anticorrosiva de recubrimientos orgánicos:...

“…[133,137,[187][188][189][190]. Los SOEs, esquema 2.4.9., se obtienen a partir de la reacción directa de una lactona y un grupo epoxi en presencia de un iniciador ácido de Lewis [126,[191][192][193][194]. De esta forma se consigue la polimerización con una cierta expansión.…”