Latent cationic palladium(II) phosphine carboxylate complexes for norbornene polymerization |
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Authors: | Natesan Thirupathi Dino Amoroso Andrew Bell John D. Protasiewicz |
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Affiliation: | 1. Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106‐7078;2. Promerus LLC, Cleveland, Ohio 44141‐3829 |
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Abstract: | The catalytic efficacy of trans‐[(R3P)2Pd(O2CR′)(LB)][B(C6F5)4] ( 1 ) (LB = Lewis base) and [(R3P)2Pd(κ2‐O,O‐O2CR′)][B(C6F5)4] ( 2 ) for mass polymerization of 5‐n‐butyl‐2‐norbornene (Butyl‐NB) was investigated. The nature of PR3 and LB in 1 and 2 are the most critical components influencing catalytic activity/latency for the mass polymerization of Butyl‐NB. Further, it was shown that 1 is in general more latent than 2 in mass polymerization of Butyl‐NB. 5‐n‐Decyl‐2‐norbornene (Decyl‐NB) was subjected to solution polymerization in toluene at 63(±3) °C in the presence of several of the aforementioned palladium complexes as catalysts and the polymers obtained were characterized by gel permeation chromatography. Cationic trans‐[(R3P)2PdMe(MeCN)][B(C6F5)4] [R = Cy ( 3a ), and iPr ( 3b )] and trans‐[(R3P)2PdH (MeCN)][B(C6F5)4] [R = Cy ( 4a ), and iPr ( 4b )], possible products from thermolysis of trans‐[(R3P)2Pd(O2CMe)(MeCN)][B(C6F5)4] [R = Cy ( 1a ) and iPr ( 1g )], as well as trans‐[(R3P)2Pd(η3‐C3H5)][B(C6F5)4] [R = Cy ( 5a ), and iPr ( 5b )], were also examined as catalysts for solution polymerization of Decyl‐NB. A maximum activity of 5360 kg/(molPd h) of 2a was achieved at a Decyl‐NB/Pd: 26,700 ratio which is slightly better than that achieved with 5a [activity: 5030 kg/(molPd h)] but far less compared with 4a [activity: 6110 kg/(molPd h)]. Polydispersity values indicate a single highly homogeneous character of the active catalyst species. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 103–110, 2009 |
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Keywords: | catalysts cationic polymerization norbornene norbornene polymerization polymerization polyolefins |
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