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Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C₁-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes.

ABSTRACT: A C₁-symmetric (methylphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (1) and (diphenyl)silylene-bridged (fluorenyl)(naphthylamido) titanium complex (2) were synthesized and characterized by ¹H NMR, element analysis, and X-ray crystal analysis. The coordination mode of the fluorenyl ligand to the titanium metal is an η³ manner in each complex. These complexes were applied for propylene polymerization using dried modified methyaluminoxane (dMMAO) as a cocatalyst under different propylene pressures in a semi batch-type method. The catalytic activity was strongly dependent on the structure of the complex and the propylene pressure, where complex 1 exhibited the highest activity (600 kg mol^-1·h^-1) under a propylene pressure of 8.0 atm to produce high molecular weight polypropylene. The polypropylenes obtained were syndiotactic-rich with an rr value of 0.50, indicating that the silylene bridge was not efficient for the isospecificity of a constrained geometry catalyst (CGC). The mechanical properties of the resulting polymers depended on their microstructure.

SUBMITTER: Wang H

PROVIDER: S-EPMC6403971 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The kinetics of ethylene and propylene polymerization catalyzed by homogeneous metallocene were investigated using 2-thiophenecarbonyl chloride followed by quenched-flow methods. The studied metallocene catalysts are: rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (Mt-I), rac-Et(Ind)2ZrCl2 (Mt-II) activated with ([Me2NPh][B(C6F5)4] (Borate-I), [Ph3C][B(C6F5)4] (Borate-II), and were co-catalyzed with different molar ratios of alkylaluminum such as triethylaluminium (TEA) and triisobutylaluminium (TIBA). The change in molecular weight, molecular weight distribution, microstructure and thermal properties of the synthesized polymer are discussed in detail. Interestingly, both Mt-I and Mt-II showed high activity in polyethylene with productivities between 3.17 × 106 g/molMt·h to 5.06 × 106 g/molMt·h, activities were very close to each other with 100% TIBA, but Mt-II/borate-II became more active when TEA was more than 50% in cocatalyst. Similarly, Polypropylene showed the highest activity of 11.07 106 g /molMt·h with Mt-I/Borate-I/TIBA. The effects of alkylaluminum on PE molecular weight were much more complicated; MWD curve changed from mono-modal in Mt-I/borate-I/TIBA to bimodal type when TIBA was replaced by different amounts of TEA. In PE, the active center fractions [C*]/[Zr] of Mt-I/borate were higher than that of Mt-II/borate and average chain propagation rate constant (kp) value slightly decreased with the increase of TEA/TIBA ratio, but the Mt-II/borate systems showed higher kp 1007 kp (L/mol·s). In PP, the Mt-I/borate presented much higher [C*]/[Zr] and kp value than the Mt-II. This work also extend to investigate the mechanistic features of zirconocenes catalyzed olefin polymerizations that addressed the largely unknown issues in zirconocenes in the distribution of the catalyst, between species involved in polymer chain growth and dormant state. In both metallocene systems, chain transfer with alkylaluminum is the dominant way of chain termination. To understand the mechanism of cocatalyst effects on PE Mw and (MWD), the unsaturated chain ends formed via ?-H transfer have been investigated by 1H NMR analysis.

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Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C₁-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes.

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