Polymere charge‐transfer‐komplexe auf der basis von polyvinylalkoholacetalen, 2

Abstract

Sonderforschungsbereich 41, Chemie und Physik der Makromolekille" (Eingangsdatum: 22. Mai 1979) SUMMARY: Poly[2-(l-naphthyl)-l,3-dioxan-4,6-diylmethylene] (3), poly[2-(2-naphthyl)-l,3-dioxan-4,6-diylmethylene] (5). 1-naphthalenecarbaldehydetrimethyleneacetal (7) and 2-naphthalenecarbaldehydetrimethyleneacetal (8) were synthesized and characterized by UVand fluorescencespectroscopy. In addition triplet-triplet absorption maxima and triplet-lifetimes were determined by flash technique. The naphthalene derivates were found to act as donors in the charge-transfer complex formation with such electron acceptors as tetracyanoethylene, 2,5-cyclohexadien-l,4-diylidenedimalonodinitrile and 2,4,5,7-tetranitro-9-fluorenone. The equilibrium constants of the charge-transfer complexes were determined spectrophotometrically by the methods of Benesi-Hildebrand, Benesi-Hildebrand-Scott and Foster-Hammick-Wardley. Einleitung Die Frage nach den optischen, elektrischen und photoelektrischen Eigenschaften polymerer CT-Komplexe hat in den letzten Jahren an Interesse gewonnen. Zusammenfassende Darstellungen stammen von Peredereeva et al.') und von Pearson, Turner und Ledwithz). AuBerdem sei auf die fhersichtsartikel von Goodings') und von Pearson4) iiber Leitfilhigkeit in Polymeren hingewiesen.Es liegen bisher nur sehr wenige Arbeiten iiber die Bestimmung von Gleichgewichtskonstanten an CT-Komplexen polymerer Naphthalinderivate vor5-'). Am diesem Grunde haben wir Polyvinylacetale mit seitenstudigen 1-bzw. 2-Naphthylgruppen sowie die entsprechenden Madellverbindungen synthetisiert. Es wird iiber die Charakterisierung der niedermolekularen und polymeren Naphthalinderivate durch UV-, Fluoreszenz-und Blitzlichtspektroskopie berichtet. AuBerdem wurden die CT-Komplexe mit Tetracyanoethylen (TCNE), Tetracyano-l,4chindmethan(TCNQ) *) und 2,4,5,7-Tetranitro-9-fluorenon (TENF) in Losung untersucht. Die Polymeren und ihre ModellverbindungenDie Synthese der polymeren Naphthalincarbaldehydacetale mit den Repetiereinheiten 3 bzw. 5 erfolgte durch Reaktion von Polyvinylalkohol (1) (M, = 26OOO) mit *)

Polymere charge‐transfer‐komplexe auf der basis von polyvinylalkoholacetalen, 5

“…wurden an anderer Stelle beschrieben 14,15 Synthese von 4,5,7-Trinitro-9-oxo-fluoren-2-carbomdurechlorid (2): 14,3 g (0,040 mol) [2-(2-naphthyl)-I,3-dioxan-4,6-diylmethylen Ber.…”

Poly(vinyl alcohol) functionalization with aldehydes in organic solvents: Shining properties of poly(vinyl acetals)

“…A large number of applications of PVA and its derivatives can be found in several fields, in particular for the development of biomedical, cosmetic, textiles, paper, and adhesives. [46][47][48][49] Several other aldehydes have been grafted on PVA [49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65] and poly(vinyl acetals) have been utilized, among others, to obtain Langmuir-Boldgett films, 50,51 membranes for ultrafiltration, 66 fluorescent polymers for biomedical uses, 67 or anti-corrosions agents for material science. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] Thus, PVA acetalization with aldehydes has also been reported 45 and some of the resulting poly(vinyl acetals) are commercially available.…”

“…1 Poly(vinyl butyral) is used in particular for its coating and adhesive properties. [46][47][48][49] Several other aldehydes have been grafted on PVA [49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65] and poly(vinyl acetals) have been utilized, among others, to obtain Langmuir-Boldgett films, 50,51 membranes for ultrafiltration, 66 fluorescent polymers for biomedical uses, 67 or anti-corrosions agents for material science. 68 Concerning the cosmetic field, only few applications of poly(vinyl acetals) have been reported and concern the formation of cosmetic sponges 69,70 and their use in masks 71 or in nail polishing, by improving their resistance and their thermal stability.…”