Spectroscopic evidence for an amine coordination to the Cu ions in ethylene/methacrylic acid copolymers neutralized with Cu(II)

Abstract

In most ionomers, pendant acid groups are neutralized by an addition of metal cations. The presence of these ionic groups strongly affects the polymer properties such as mechanical strength, elasticity and dielectric relaxation'). Therefore, attention has been recently focused on their morphological characterization*).For ionomers containing paramagnetic entities, the electron paramagnetic resonance (EPR) technique may provide important information about the structure and the molecular motions of the polymers. So far extensive studies on Cu(I1)-containing ionomers have been p e r f~r m e d~-~) .One of the valuable conclusions is that a Cu(I1)-Cu(I1) pair is stabilized under some condition^^^^) and there exist several types of Cu(II)-cu(II) interactionss).Recently, we prepared ionomers neutralized by organic mines, and reported a study of several complex salts of Zn(I1) ionomers in ethylene/methacrylic acid copolymers (E-MAA) with 1,3-bis(aminomethyl)cyclohexane (BAC)@. In order to see more clearly the effect of such an amine-addition to ionomers, Cu(I1)-containing copolymers were investigated by means of EPR. In this communication, we report some characteristic effects clarified in E-MAA copolymer neutralized with Cu(I1) and its amine (BAC) complex.The sample used here was manufactured by Du Pont-Mitsui Polychemicals Co. Ltd. The content of MAA was 5,4 mol-% referring to the constitutional repeating unit in the copolymer. The Cu(ll)/BAC complex was prepared by a melt reaction of E-MAA and Cu(lI)/BAC in an extruder at 170°C. The pellet samples thus obtained were reformed into sheets by a compression molding at about I6OoC, and then cooled rapidly to room temperature by circulating cold water outside the sheet-container. The complex salts of Cu(I1) salts with BAC were prepared by a melt reaction of a mixture of Cu(l1) ionomers and BAC by the same procedure as described above.Details of the EPR measurements were described previouslys). The U V absorption speclra of' the sheeted samples were recorded between 200 and 900 nm with a Shimadzu double-beam spectrophotometer (UV-2 10A).

Preparation and structure of copper nanoparticle/poly(acrylic acid) composite films

“…18,19 The latter, isotropic, band is assigned to a binuclear complex of the dimeric copper(II) acetate monohydrate type. 19,20 It is considered that most of the Cu 2z in PAA±Cu 2z is in the state of mononuclear Cu 2z type, because the relative intensity of the band at 310 mT is somewhat larger than that at 455 mT.…”

Introduction of copper iodide fine particles into a poly(acrylic acid) matrix via a complex of polymer–polyiodide ions

“…840 nm is attributed to the d-d transition of the Cu 2+ ion. 30,31 The existence of Cu 2+ ion was also confirmed by electron spin resonance (ESR) measurement, because an ESR spectrum having a g-value of 2.180 was detected, and the shape of the spectrum and the g-value were completely consistent with those of CuCl 2 aqueous solution having almost same Cu 2+ and Cl 2 concentrations. 32 Although CuCl is colorless and exhibits no d-d transition, the peak at 840 nm was originally observed even before immersion of iodinated PAA.…”