Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure

Polymers

Ghulam Rasool¹  MuhammadKhurram Tufail¹  Nadeem Muhammad¹  Zhiqiang Fan²  Yintian Guo²  Azim Uddin²  MuhammadImran Jamil²  Tariq Aziz²  Shahid Hussain³  Tiantian Wei³  Amjad Ali³  Li Guo³ 

[1] Department of Enviromental Engineering, Wuhan University of Technology, Wuhan 430223, China;MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China;Research School of Polymeric Materials, School of Material Science & Engineering, Jiangsu University, Zhenjiang 202113, China;

关键词: metallocene;    borate;    ethylene;    propylene;    polymerization;    kinetics;   

DOI  :  10.3390/polym13020268

来源: DOAJ

【 摘 要 】

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/mol_Mt·h to 5.06 × 10⁶ g/mol_Mt·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 /mol_Mt·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 (k_p) value slightly decreased with the increase of TEA/TIBA ratio, but the Mt-II/borate systems showed higher k_p 1007 k_p (L/mol·s). In PP, the Mt-I/borate presented much higher [C*]/[Zr] and k_p 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 M_w and (MWD), the unsaturated chain ends formed via β-H transfer have been investigated by ¹H NMR analysis.

【 授权许可】

Unknown