The complex [Pd(κ2‐P,O‐{2‐(2‐MeOC6H4)2P}C6H4SO3)Me(dmso)] ( 1 ) is investigated for the copolymerization of (E) with norbornene (N) and functionalized N derivatives affording P(E‐co‐N) in excellent yields. Copolymer molar masses are higher than those of PE and increase with N concentration. In addition, the complex [Ti(κ2‐N,O‐{2,6‐F2C6H3N = C(Me)C(H) = C(CF3)O})2Cl2] ( 2 ) is evaluated as catalyst for living E‐co‐N copolymerization upon activation with dried methylaluminoxane between 25 and 90 °C. Copolymerization at different [N]/[E] feed ratios affords stereoirregular alternating high molar mass P(E‐co‐N) with narrow molar mass distribution. P(E‐co‐N) living copolymerization is demonstrated by kinetics at 50 °C. Block copolymers are synthesized and fully characterized.
The reaction equilibria of Cp2Ti13CH3Cl and Cp2Ti(CH3)2 with AlMe3 (TMA) and/or methylaluminoxane (MAO) have been investigated by 13C NMR. Several adducts have been identified. A study of the 13C 90% enriched ethylene polymerization in an NMR tube in the presence of the above catalytic systems, in the most experimentally significant conditions, and a comparison of the NMR data with the catalytic activity have been made as well. It has been shown that: i) some species are side products, inactive for addition ethylene polymerization; ii) active cation-like species such as Cp2TiMe+Cl·[AlMeO]n- and Cp2TiMe+Me·[AlMeO]n- are formed in titanocene-MAO systems. Concerning the role of AlMe3, contained in MAO solutions, it has been shown that: a) AlMe3 is mainly bound to MAO; b) if some “free” AlMe3 exists in solution it is not the actual cocatalyst in the metallocene-MAO based catalytic systems; c) the amount of AlMe3 influences either active or inactive species. 相似文献
Homogeneous surface coating of multi‐walled carbon nanotubes is achieved for the first time by in situ copolymerization of ethylene (E) and 2‐norbornene (N) as catalyzed directly from the nanotube surface previously treated by a highly active metallocene‐based complex, i.e., rac‐Et(Ind)2ZrCl2/MMAO‐3A. The copolymerization reaction allows for the destructuration of the native nanotube bundles, which upon further melt blending with an ethylene–vinyl acetate copolymer (27 wt.‐% vinyl acetate) matrix, leads to high‐performance polyolefinic nanocomposites. The microstructural analysis of the surface‐coating copolymer was carried out by 13C NMR spectroscopy and allowed determination of the actual N content incorporated along the chains. Depending on the experimental conditions used (e.g., E pressure, solvent, feed N concentration) the relative quantity of E–N copolymer can be tuned, as well as the N content in the formed copolymers and accordingly their glass transition temperature.
Propylene was polymerized in the presence of the isospecific Et(Ind)2ZrCl2 (Et: ethylene, Ind: indenyl) and the aspecific (Ind)2ZrCl2 complexes in solution and anchored to SiO2 and SiO2/MAO (MAO: methylaluminoxane) supports. From the stereochemical analysis of the polypropene samples obtained it can be deduced that (i) the same active species is formed when a metallocene is in solution and when it is anchored to the SiO2/MAO support and (ii) a completely different active species is formed when the metallocene is anchored to the silica. The fact that both systems Et(Ind)2ZrCl2 SiO2 and (Ind)2ZrCl2 SiO2 produce the same prevailingly isospecific polymer suggests that only isospecific centers are formed in this case, independently of the metallocene stereochemical structure. 相似文献