Effect of Substituent on Titanocene/MMAO Catalyst for Ethylene/1-Hexene Copolymerization
Copolymerization of ethylene with 1-hexene was carried out using two ansa-fluorenyl titanium derivative complexes. The substituent effect on the catalytic activity, monomer reactivity ratio and polymer property was investigated. It was found that the presence of t-Bu groups on fluorenyl ring exhibited remarkable catalytic activity and produced polymer with high molecular weight. However, these catalysts produce polymer with narrow molecular weight distribution, indicating the characteristic of single-site metallocene catalyst. Based on C NMR, we can observe that monomer reactivity ratio was affected by catalyst structure. The rH values of complex 2 were lower than that of complex 1 which might be result from the higher steric hindrance leading to a reduction of 1hexene insertion step. Keywords—Constrained geometry catalyst, linear low density polyethylene, copolymerization, reactivity ratio
SUBSTITUENT EFFECTS OF tert-BUTYL GROUPS ON FLUORENYL LIGAND OF [t-BuNSiMe2FLu] ZrMe2
[t-BuNSiMe2(2,7-t-Bu2Flu)]ZrMe2 and [t-BuNSiMe2(3,6-t-Bu2Flu)]ZrMe2 were synthesized, and the solid structure of complex [t-BuNSiMe2(2,7-t-2Flu)]ZrMe2 was elucidated by single crystal X-ray analysis. These complexes were applied for propylene polymerization using dried modified methylaluminoxane as a cocatalyst at 0°C and 20°C in toluene. Both systems did not show activity at 0°C, but they conducted the polymerization at 20°C. The introduction of t-butyl substituents to the fluorenyl ligand improved the activity more than six times regardless of the position of the substituents, and both systems gave low molecular weight polypropylenes (PP) with narrow molecular weight distribution. The introduction of t-butyl substituents also improved the syndiospecificity and [t-BuNSiMe2(3,6-t-Bu2Flu)]ZrMe2 gave highly syndiotactic PP with the syndiotactic pentad of 0.91 and the melting point of 145°C.
United Nations Convention on the Law of the Sea 1982, A Commentary
Volume VI is the sixth substantive volume to be published in the series. It deals with the work of the First Committee at the Third UN Conference on the Law of the Sea, namely the international seabed area. The volume thus embraces the deep seabed mining regime set out in Part XI of the 1982 Convention on the Law of the Sea together with the 1994 Agreement on its implementation. Completion of this commentary was delayed first by the consultations and negotiations that commenced in 1990 and led to the 1994 Agreement and the entry into force of the Convention. It was further delayed until the Assembly of the International Seabed Authority approved the detailed mining regulations in 2000. Additional supplementary material can be found at UNCLOS 1982 Commentary: Supplementary Documents.