0000000000246876
AUTHOR
Kittichote Musikabhumma
showing 4 related works from this author
Synthesis of branched polyethylenes by the tandem catalysis of silica-supported linked cyclopentadienyl-amido titanium catalysts and a homogeneous di…
2003
The synthesis of branched polyethylenes by ethylene polymerization with new tandem catalyst systems consisting of methylaluminoxane-preactivated linked cyclopentadienyl-amido titanium catalysts [Ti(η5:η1-C5Me4SiMe2NR)Cl2 (R = Me or tBu)] supported on pyridylethylsilane-modified silica (PySTiNMe and PySTiNtBu) and homogeneous dibromo nickel catalyst having a pyridyl-2,6-diisopropylphenylimine ligand (PyminNiBr2) in the presence of modified methylaluminoxane was investigated. Ethylene polymerization with only PyminNiBr2 yielded a mixture of 1- and 2-olefin oligomers with methyl branches [weight-average molecular weight (Mw) ∼ 460)] with a ratio of about 1:7. By the combination of this nickel …
The Kinetic Stability of Cationic Benzyl Titanium Complexes that Contain a Linked Amido-Cyclopentadienyl Ligand: The Influence of the Amido-Substitue…
2002
Cationic benzyl titanium complexes [Ti(η 5 : η 1 -C 5 Me 4 SiMe 2 NR')-(CH 2 Ph)] + were cleanly formed by the reaction of the dibenzyl titanium complexes [Ti(η 5 : η 1 -C 5 Me 4 SiMe 2 NR')(CH 2 Ph) 2 with B(C 6 F 5 ) 3 and [Ph 3 C][B(C 6 F 5 ) 4 ] in bromobenzene. NMR spectroscopic studies suggest that the benzyl titanium cations contain a fluxional η 2 -coordinated benzyl ligand. Kinetic analysis showed that the benzyl titanium cations decompose according to first-order kinetics and that the amido substituents R' (R' = Me, i Pr, t Bu) in the linked amido-cyclopentadienyl ligand influence the lability of these benzyl titanium cations. The order of the kinetic stability of the benzyl titan…
Linked cyclopentadienyl-amido titanium catalysts supported on pyridylethylsilane-modified silica for heterogeneous ethylene homo- and copolymerization
2003
Abstract Linked cyclopentadienyl-amido titanium dimethyl and dichloro complexes, Ti(η 5 :η 1 -C 5 Me 4 SiMe 2 N t Bu)X 2 (X=Me, Cl), were reacted with trityl tetrakis(pentafluorophenyl)borate (TB), Ph 3 C + [B(C 6 F 5 ) 4 ] − , and methylaluminoxane (MAO), followed by treatment with toluene suspension of pyridylethylsilane-modified silica, to give two new supported-type titanium catalysts, PySTiTB and PySTiMAO. PySTiTB polymerized ethylene in the presence of triisobutylaluminum (TIBA) in hexane at 60 °C and 5 bar with slightly higher activity than the corresponding homogeneous system under the same conditions. PySTiMAO showed relatively high activity even without any use of alkylaluminum co…
Tritylpyridinium tetrakis(pentafluorophenyl)borate as an efficient activator for “constrained-geometry” catalysts in ethylene polymerization
2004
Abstract Ethylene polymerization with linked amido-cyclopentadienyl or “constrained-geometry” titanium catalysts, Ti(η 5 :η 1 -C 5 Me 4 SiMe 2 N t Bu)X 2 (X=Me, Bz, Cl), activated by tritylpyridinium tetrakis(entafluorophenyl)borate, [Ph 3 C(NC 5 H 5 )] [B(C 6 F 5 ) 4 ], and silica-supported tritylpyridinium tetrakis(entafluorophenyl)borate (PySTB) was found to proceed with high activity. 1 H NMR spectra in CD 2 Cl 2 suggest that ([Ti(η 5 :η 1 -C 5 Me 4 ,SiMe 2 N t Bu)Me (NC 5 H 5 )] + is formed as the main cationic species. Using the heterogeneous cocatalyst PySTB in hexane, unexpectedly high ethylene polymerization activity was achieved, giving high molecular weight polyethylenes with exc…