Synthesis of poly(silyl ether)s containing pendant chloromethyl groups by the polyaddition of bis(oxetane)s with dichlorosilanes

Abstract

ABSTRACT:The polyaddition of bis (3-ethyl-3-oxetanylmethyl) terephthalate (BEOT) with dichlorodiphenylsilane (CPS) using tetrabutylammonium bromide (TBAB) as a catalyst proceeded under mild reaction conditions to afford a polymer containing silicon atoms in the polymer main chain. A poly(silyl ether) (P-1) with a high molecular weight (M n ϭ 53,200) was obtained by the reaction of BEOT with CPS in the presence of 5 mol % of TBAB in toluene at 0°C for 1 h and then at 50°C for 24 h. The structure of the resulting polymer was confirmed by IR and 1 H NMR spectra. Furthermore, it was proved that the polyaddition of certain bis(oxetane)s with dichlorosilanes proceeds smoothly to give corresponding poly(silyl ether)s with TBAB as the catalyst.

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

“…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).…”

“…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).…”

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

“…We have found22–24 a new polyaddition reaction of bis(oxetane)s and diacyl chlorides that proceeded smoothly with quaternary onium salts or crown ether complexes as the catalysts, as well as the polyaddition25 of bis(epoxide)s and diacyl chlorides. More recently, we reported26 that the polyaddition of bis(oxetane)s and dichlorosilanes produced corresponding high molecular weight poly(silyl ether)s with pendant reactive chloromethyl groups with the same catalyst system.…”

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.…”