29710-98-3Relevant articles and documents
Ion Pairs in Macroreticular Polystyrene Resins. 1. EPR Study Using an Anion Spin Label
Hwang, Jimmy S.,Lyle, Samuel J.
, p. 8727 - 8731 (2007/10/02)
Macroreticular resins based on cross-linked polystyrene, XAD-2 and XAD-4, have been "coated" with tri-n-dodecylmethylammonium iodide (TLMAI) and n-hexadecyltrimethylammonium bromide (CTAB) along with a polystyrene (PS) sample.The anions on the quaterny ammonium salts have been labeled with the anion label 1-oxyl-2,2,5,5-tetramethylpyrrolidine-3-carboxylate (label 517).EPR spectra were taken as a function of temperature.The nitrogen hyperfine coupling constant along the z direction, Az were determined from the rigid limit spectra at 77 K.Rotational correlation times used in Arrhenius plots were calculated from the empirical formula τR = a(1-S)b for the Brownian model (a and b are constants and S = A'z/Az, the ratio of the outer EPR hyperfine extrema separation at a given correlation time to the rigid limit separation).From a consideration of other published systems, the Az values can be attributed to variations in polarity and hydrogen bonding within the host matrix.The Arrhenius plots were not linear; they consisted of two linear regions for XAD-4(CTAB) and XAD-4(TLMAI) and three linear regions for XAD-2(CTAB), XAD-2(TLMAI), and PS(TLMAI).The low-temperature regions correspond to energy barriers to rotational motion about covalent bonds while the middle range (roughly 120-250 K) corresponds to breaking of hydrogen bonds such as would be involved in the presence of water.Information of anisotropy of rotational diffusion obtained from the high-temperature spectra in the temperature region 370-480 K revealed that motion was highly anisotropic for the XAD-4(CTAB) and moderately so for XAD-2(TLMAI) and XAD-2(CTAB), while it was isotropic for PS(TLMAI).A model is developed to explain qualitatively the anion behavior, taking into consideration the resin pore structures, interaction of the hydrocarbon chains of the cations with the resin framework, the degree of ordering of the charged heads, and their interaction with and retention of water.