Synthesis of polyphosphonates containing pendant chloromethyl groups by the polyaddition of bis(oxetane)s with phosphonic dichlorides

Abstract

The polyaddition of 4,4′‐bis[(3‐ethyl‐3‐oxetanyl)methoxy]biphenyl (4,4′‐BEOBP) and phenylphosphonic dichloride (PPDC) with quaternary onium salts as catalysts proceeded under mild reaction conditions to afford a polymer containing phosphorous atoms in its main chain. A polyphosphonate with a high number‐average molecular weight (10,300) was obtained by the reaction of 4,4′‐BEOBP and PPDC in the presence of tetraphenylphosphonium chloride (TPPC) in o‐dichlorobenzene at 130 °C for 24 h. The structure of the resulting polymer was confirmed with IR, 1H NMR, and 31P NMR spectroscopy. Furthermore, it was proved that the polyaddition of certain bis(oxetane)s with phosphonic dichlorides proceeded smoothly to give corresponding polyphosphonates with TPPC as the catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3835–3846, 2002

Catalytic reactions of oxetanes with protonic reagents and aprotic reagents leading to novel polymers

“…24,25 The resulting cured materials are expected to have high hydrophobicity because of their structures without any pendant hydroxy groups. From consideration of these reaction systems, we examined the reaction of oxetanes with aprotic reagents such as acyl chloride, 51,52 thioester, 16 phosphonyl chloride, 53 silyl chloride, 54 and chloroformate 55 (Scheme 3).…”

“…Polyadditions of bis(oxetane)s with aprotic reagents such as carboxyl dichloride, 53,54,72 silyl dichloride, 41 phosphonyl dichloride, 53 bischloroformate, 55 and active diesters 73 were carried out using quaternary onium salts as catalysts at 90 8C to afford the corresponding polymers with pendant chloromethyl groups in high yields (Scheme 10).…”

Synthesis of Hyperbranched Poly(ester)s with Pendant Hydroxy Groups by the Polyaddition of Bis(oxetane)s with 1,3,5-Benzenetricarboxylic Acid

“…6 Since more than 15 years ago, my research group have studied the development of new ring-opening addition reaction of oxetane and succeeded in finding new reactions of oxetanes such as ringopening addition reactions with acyl chlorides, 7 phosphonyl chlorides, 8 silyl chloride, 9 active esters, 7 carboxylic acids, 10 phenols, 11,12 and thiols 13 using appropriate quaternary onium salts or crown ether complexes as catalysts. These reactions can be applied practically to the polyadditions of bis(oxetane)s with above reagents such as diacyl chlorides, [14][15][16][17] phosphonyl dichlorides, 8 active diesters, 18,19 dicarboxylic acids, 10 bisphenols, 11,12 and dithiols 13 to afford corresponding polymers with high molecular weights. Recently, we also found that an anionic ring-opening polymerization of 2-(hydroxymethyl)oxetanes produced corresponding hyperbranched poly(ether)s containing one terminal oxetanyl groups and many pendant primary hydroxy groups using the complex of potassium t-buthoxide with crown ether as a catalyst system, [20][21][22] and an anionic ring-opening alternating copolymerization 23 of oxetanes with cyclic carboxylic anhydrides using certain quaternary onium salts as catalysts.…”

A Novel Thermal Curing Reaction of Oxetane Resin with Active Diester

“…From these scientific backgrounds, the authors examined to develop new organic reactions of oxetane compounds, and succeeded to develop certain new addition reactions of oxetane compounds with acyl chloride, 7 silyl chloride, 8 phosphonyl chloride, 9 phenol, 10 thiol, 11 carboxylic acid, 12 and active ester 13 using certain quaternary onium salts as catalysts, a novel anionic ring-opening polymerization 2-hydroxymethyl oxetanes 14 using potassium tert-butoxide/18-crown-6 as a catalyst, and an anionic ring-opening alternating copolymerization of oxetane with carboxylic anhydride 15 using quaternary onium salts as catalysts. All these reactions proceeded smoothly under suitable reaction conditions to give the corresponding adducts and polymers in satisfactory yields.…”