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Keywords = titanocene-containing polymers

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12 pages, 1210 KB  
Communication
Synthesis of New Phenoxide-Modified Half-Titanocene Catalysts for Ethylene Polymerization
by Jiahao Gao, Wen-Hua Sun and Kotohiro Nomura
Catalysts 2025, 15(9), 840; https://doi.org/10.3390/catal15090840 - 2 Sep 2025
Viewed by 690
Abstract
A series of half-titanocenes containing different trialkylsilyl para-phenoxy substituents, Cp*TiCl2(O-2,6-iPr2-4-R-C6H2) [Cp* = C5Me5; R = Si(n-Bu)3 (5), SiMe2(n-C8 [...] Read more.
A series of half-titanocenes containing different trialkylsilyl para-phenoxy substituents, Cp*TiCl2(O-2,6-iPr2-4-R-C6H2) [Cp* = C5Me5; R = Si(n-Bu)3 (5), SiMe2(n-C8H17) (6), SiMe2(t-Bu) (7)], were prepared and identified. Catalytic activity in ethylene polymerization by Cp*TiCl2(O-2,6-iPr2-4-R-C6H2) [R = H (1), SiMe3 (2), SiEt3 (3), Si(i-Pr)3 (4), 5–7]–MAO (methylaluminoxane) catalysts increased in the following order (in toluene at 25 °C, ethylene 4 atm): R = H (1) < SiMe3 (2), SiEt3 (3), Si(i-Pr)3 (4) < SiMe2(t-Bu) (7) < SiMe2(n-C8H17) (6) < Si(n-Bu)3 (5, activity = 6.56 × 104 kg-PE/mol-Ti·h). The results thus suggest that the introduction of an alkyl group into a silyl substituent led to an increase in activity. The activities of 5 were affected by the Al/Ti molar ratio (amount of MAO charged), and the highest activity (7.00 × 105 kg-PE/mol-Ti·h) was observed under optimized conditions at 50 °C, whereas the activity decreased at 80 °C. In ethylene copolymerization with 1-dodecene, the Si(n-Bu)3 analog (5) exhibited remarkable catalytic activity (4.32 × 106 kg-polymer/mol-Ti·h at 25 °C), which was higher than those of the reported catalysts (1–3), affording poly(ethylene-co-1-dodecene)s with efficient comonomer incorporation as observed in 3 [rE = 3.77 (5) vs. 3.58 (3)]. Full article
(This article belongs to the Special Issue Innovative Catalytic Approaches in Polymerization)
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13 pages, 198 KB  
Article
Effect of Electrical Conductivity Through the Bulk Doping of the Product of Titanocene Dichloride and 2-Nitro-1,4-phenylenediamine
by Charles E. Carraher, Amitabh J. Battin and Michael R. Roner
J. Funct. Biomater. 2011, 2(1), 18-30; https://doi.org/10.3390/jfb2010018 - 17 Mar 2011
Cited by 9 | Viewed by 6769
Abstract
The condensation polymer derived from reaction between titanocene dichloride and 2-nitro-1,4-phenylenediamine was doped by mixing the polymer with different amounts of iodine. This bulk doping of the titanocene polyamine resulted in an increase in bulk conductivity from 10 to over 1,000 fold. Conductivity [...] Read more.
The condensation polymer derived from reaction between titanocene dichloride and 2-nitro-1,4-phenylenediamine was doped by mixing the polymer with different amounts of iodine. This bulk doping of the titanocene polyamine resulted in an increase in bulk conductivity from 10 to over 1,000 fold. Conductivity increased to a doping level of about 10 to 15% iodine. Conductivity decreased as the sample discs were heated returning to pre-doped levels after the samples were heated for eight minutes. It is believed that this decrease in conductivity is due to the surface evaporation of iodine as the samples were heated. MALDI MS and IR results are consistent with the formation of C-I compounds for doped materials. Full article
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