Synthesis, thermal analysis, and linear and nonlinear optical characterization of substituted polyphosphonates derived from 1,12-dodecanediol

Abstract

The syntheses of a series of substituted polyphosphonates of the type [OP(X)(Ar)O(CH2)12]n (X = O, S, Se; Ar = phenyl, 2,2′‐bithienyl‐5‐yl) are reported. The trueM¯ns for the polyphosphonates range from 1.1 to 4.6 × 104 Da and are significantly higher than those previously reported for polyphosphonates synthesized via polycondensation reactions. Thermal characterization indicates that all of the polymers are in the rubbery state at room temperature and have thermal stabilities as high as 290 °C. The linear absorption spectra, emission spectra, and emission quantum yields of the 2,2′‐bithenyl‐5‐yl substituted polyphosphonates show distinct trends with respect to the chalcogen attached to the phosphorus. Solutions of these polymers show emission at wavelengths ranging from 380 to 400 nm and, depending on the choice of X, the quantum yields are considerably larger than that of 2,2′‐bithiophene. Nonlinear optical measurements of the polyphosphonates with 2,2′‐bithenyl‐5‐yl substituents show that nonlinear absorbance increases with increasing molecular weight of X. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3663–3674

Polyphosphonates as ionic conducting polymers

“…While polyphosphonates have previously been investigated by our group for their modular structures and roles in the field of optical limiting, 1,2 no work had yet been done exploring the ability of polyphosphonates derived from polyethylene glycols to serve as SPEs.…”

“…While polyphosphonates have previously been investigated by our group for their modular structures and roles in the field of optical limiting, 1,2 no work had yet been done exploring the ability of polyphosphonates derived from polyethylene glycols to serve as SPEs. The polyphosphonates reported in this manuscript not only show conductivity higher than that of similar PEO systems but offer unique insight into the ionic binding behavior of these materials that may help in understanding how to further improve their conductivity.…”

“…Polyphosphonates were prepared by a polycondensation reaction between tetraethylene glycol and bis(diethylamino) phenylphosphine, followed by chalcogenation with S or Se. 1,2 Excess S or Se was removed from solutions of the polymers by filtration through Celite. Finally the polymers were precipitated from hexanes before vacuum drying at 90 C and 0.5 mbar.…”

“…We recently reported that polyphosphonates with a range of X (O, S, Se) and R (phenyl, 2-bithiophenyl) are readily prepared in a two-step process that involves the polycondensation of PR(NEt 2 ) 2 with 1,12-dodecanediol followed by oxidation with a chalcogen. 1,2 The polyphosphonates derived from 1,12-dodecanediol and having 2-biothiophenyl R groups exhibit blue fluorescence and optical limiting materials in the blue region of the visible spectrum. The intensity of the fluorescence and the efficiency of the optical limiting were both found to depend on the nature of the chalcogen.…”

“…Both the nature of the diol and its arrangement in the polyphosphonate backbone has significant effects on the thermal properties of the polyphosphonates. The presence of phosphorus in the polymer backbone also allows 31 P{ 1 H} NMR spectroscopy to be use to probe the microstructure of the polymer backbone and in some cases study the thermal properties of the polymers.…”