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Ziegler-Natta catalytic systems

Calorimetric and DFT study on TiCl4-Lewis base interactions

Journal of Thermal Analysis and Calorimetry
Authors: L. Cavallo, J. Ducéré, Rosalisa Fedele, A. Melchior, Maria Mimmi, G. Morini, F. Piemontesi, and Marilena Tolazzi


A calorimetric investigation on the reactions of TiCl4 with phthalates in 1,1,2,2-tetrachloroethane (TCE) is presented in order to better understand the complex interactions present in Ziegler-Natta catalytic systems. The Lewis bases diethyl isophthalate (L1), diethyl terephthalate (L2) and the ortho-isomer diethylphthalate (L3), have been chosen to study how the substituent positions could influence the energy and the stoichiometry of the complexation reactions. FTIR spectroscopy was used to obtain information on the coordination mode of the ligands and diffusion measurements by NMR was carried out to verify the presence of oligo-or polymeric species. Experimental results were compared with theoretical calculations based on Density Functional Theory (DFT).

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6 ) was supplied from Aldrich; titanium tetrachloride (TiCl 4 ) and hydrogen peroxide were from Merck. Ethanol (96%, 0.78 g/cm 3 ) was purchased from the Institute of Pure Substances, University of Sofia. The organic dye Malachite Green oxalate

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.1063/1.1490410 . 6. Matero , R , Rahtu , A , Ritala , M . In situ quadrupole mass spectrometry and quartz crystal microbalance studies on the atomic layer deposition of titanium dioxide from titanium tetrachloride and water . Chem

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method. However, the challenge to prepare metal substituted SBA-15 materials directly via the usual hydrothermal method remains. Chen et al. [ 6 ] synthesized Ti-substituted SBA-15 under conventional hydrothermal conditions using titanium tetrachloride

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shown in Fig. 1 . Titanium tetrachloride (TiCl 4 , 99%, Merck) was selected as a titanium source. 15 mL ethanol and 0.75 mL ethyl acetoacetate (EAcAc, Merck) were mixed, and then 2.5 mL TiCl 4 was added by the rate of 1 mL/min to the mixture at ambient

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, PH , Heeg , MJ , Rheingold , AL , Winter , CH 1994 Terminal and bridging imido complexes from titanium tetrachloride and primary amines. Implications for the chemical vapor deposition of titanium nitride films . Inorg Chem 33 : 5879 – 5889 10

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. Coordination complexes of titanium (IV) halides 111 . Preparation and infrared spectra of the complexes of titanium, tetrachloride with urea, thiourea, and some of their derivatives. Can J Chem. 1962 ; 40 : 2234 – 42

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