In:
Polymer International, Wiley, Vol. 63, No. 5 ( 2014-05), p. 876-886
Abstract:
The preparation of a symmetrically disubstituted 1,1‐diphenylethylene derivative, 1,1‐bis(4‐aminophenyl)ethylene, by the Wittig reaction as well as the preparation of primary amine chain‐end‐functionalized polymers using that derivative in atom transfer radical polymerization ( ATRP ) reactions are reported. A new primary diamine initiator system was generated in situ by the atom transfer radical addition reaction of (1‐bromoethyl)benzene with 1,1‐bis(4‐aminophenyl)ethylene in the presence of copper(I) bromide/2,2′‐bipyridyl as the catalyst system and employed as the primary diamine‐functionalized initiator for the polymerization of styrene by ATRP methods to produce well‐defined α ‐bis(4‐aminophenyl)‐functionalized polystyrene. The polymerization kinetic data for the synthesis of α ‐bis(4‐aminophenyl)‐functionalized polystyrene shows that the polymerization process followed first‐order rate kinetics with respect to monomer consumption. The number‐average molecular weights ( M n = 1.1 × 10 3 to 13.14 × 10 3 g mol −1 ) of the α ‐bis(4‐aminophenyl)‐functionalized polymers increased linearly with percentage monomer conversion and polymers with narrow molecular weight distributions ( M w / M n = 1.1–1.25) were obtained. The polymerization processes were monitored using gas chromatographic analyses to determine the extent of monomer consumption as a function of time. In addition, α , ω ‐tetrakis(4‐aminophenyl)‐functionalized polystyrene was prepared by a new, controlled/living, in situ post‐ ATRP chain‐end functionalization reaction which involved the direct addition of 1,1‐bis(4‐aminophenyl)ethylene to the ω ‐terminus of α ‐bis(4‐aminophenyl)‐functionalized polystyrene, without the need for the isolation and purification of the polymeric precursor. The organic precursor compounds, the primary diamine‐functionalized 1,1‐diphenylethylene derivative and the functionalized polymers were characterized using 1 H NMR , 13 C NMR and Fourier transform infrared spectroscopy, size exclusion chromatography, thin‐layer chromatography and non‐aqueous titration measurements. © 2013 Society of Chemical Industry
Type of Medium:
Online Resource
ISSN:
0959-8103
,
1097-0126
DOI:
10.1002/pi.2014.63.issue-5
Language:
English
Publisher:
Wiley
Publication Date:
2014
detail.hit.zdb_id:
2004753-8
Permalink