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Nanocomposites of Phosphonic‐Acid‐Functionalized Polyethylenes with Inorganic Quantum Dots
Author(s) -
Rünzi Thomas,
Baier Moritz C.,
Negele Carla,
Krumova Marina,
Mecking Stefan
Publication year - 2015
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201400441
Subject(s) - phosphonate , materials science , polymer chemistry , monomer , copolymer , nanocomposite , polymer , chemistry , organic chemistry , nanotechnology , composite material
Insertion of diethyl vinyl phosphonates and free vinyl phosphonic acid, respectively, into [(P^O)Pd(Me)(dmso)] ((P^O) = κ 2 ‐ P , O ‐Ar 2 P C 6 H 4 SO 2 O with Ar = 2‐MeOC 6 H 4 ) (1‐dmso) occurs in a 2,1‐ as well as 1,2‐fashion, to form a four‐and a five‐membered chelate [(P^O)Pd{κ 2 ‐ C,O ‐ C H(P( O )(OR) 2 )CH 2 CH 3 }] and [(P^O)Pd{κ 2 ‐ C,O ‐ C H 2 CH(P( O )(OR) 2 )CH 3 }] (R = H, Et). No decomposition or other reactions of 1 by free phosphonic acid moieties occur. Copolymerization in a pressure reactor by 1‐dmso yields linear random poly(ethylene‐ co ‐diethyl vinyl phosphonate) and poly(ethylene‐ co ‐vinyl phosphonic acid). In these copolymerizations, reversible coordination of the phosphonate moieties of free monomer as well as chelate formation by incorporated monomer retards chain growth as also evidenced by relative binding studies of diethyl phosphonate towards 1. Post‐polymerization emulsification of poly(ethylene‐ co ‐vinyl phosphonic acid) together with CdSe/CdS quantum dots (QDs) yields submicron (ca. 50 nm from dynamic light scattering (DLS) and transmission electron microscopy (TEM)) polymer particles with the QDs embedded in the functionalized polyethylene in a nonaggregated fashion. This embedding benefits the fluorescence behavior in terms of continuous emission and life‐time as revealed by wide‐field fluorescence measurements. These composite particle dispersions are employed as a ″masterbatch” together with an aqueous high density polyethylene (HDPE) dispersion to generate thin films (by spin‐coating) and bulk materials (from the melt), respectively, in which the inorganic nanoparticles remain highly disperse.