[EN] GROUP 4 METAL COMPLEXES CONTAINING 4-ARYL-SUBSTITUTED, TRICYCLIC INDENYL DERIVATIVES [FR] COMPLEXES DE METAUX DU GROUPE 4 CONTENANT DES DERIVES INDENYLES TRICYCLIQUES 4-ARYLE-SUBSTITUES
[EN] ORGANOMETALLIC TRANSITION METAL COMPOUND, BISCYCLOPENTADIENYL LIGAND SYSTEM, CATALYST SYSTEM AND PREPARATION OF POLYOLEFINS<br/>[FR] COMPOSE DE METAL DE TRANSITION ORGANOMETALLIQUE, SYSTEME DE LIGAND BISCYCLOPENTADIENYL, SYSTEME CATALYTIQUE ET FABRICATION DE POLYOLEFINES
Impact of Initiator Spacer Length on Grafting Polystyrene from Silica Nanoparticles
作者:Daniel Sunday、Sara Curras-Medina、David L. Green
DOI:10.1021/ma1004259
日期:2010.6.8
Using atom transfer radical polymerization (ATRP), we synthesized hybrid organic/inorganic nanoparticles consisting of a silica core and a polystyrene brush. The brushes were grafted from the nanoparticles with three different initiators, termed 3-BIDS, 11-BIDS, and 15-BIDS, consisting respectively of a 3-, 11-, or 15-carbon spacer separating an ethoxylated silane from a brominated initiator end group. The initiators were characterized using H-1 NMR and C-13 NMR. Surface modification studies with all three initiators were performed to optimize their attachment, producing particles with dense covalently attached initiator monolayers with up to 2.6 initiators/nm(2). Polymers were then grafted from the particles using ATRP, the polymerization kinetics were characterized using gas chromatography (GC), and the final products were characterized using thermogravimetric analysis (TGA) and gel permeation chromatography (GPC). Analysis of the kinetics show an approximately identical rate of styrene conversion from all three initiators while GPC results show that the molecular weight of the polymers grown from the 11-BIDS monolayer increases faster than that grown from 3-BIDS or 15-BIDS. We also found that the graft densities of polystyrene are on average 0.5 chains/nm(2) greater for particles modified with 3-BIDS or 15-BIDS at 0.7 chains/nm(2) than for 11-BIDS at 0.2 chains/nm(2). Our results indicate that the roughly 3-fold drop in graft density for the particles modified with the 11-BIDS is most likely due to a change in the conformation of the 11-BIDS monolayer.