Citation: Zhen Zhang, Bai-Yu Jiang, Biao Zhang, Zhi-Sheng Fu, Zhi-Qiang Fan. Deactivation Effect Caused by Catalyst-Cocatalyst Pre-contact in Propylene Polymerization with MgCl₂-supported Ziegler-Natta Catalyst[J]. Chinese Journal of Polymer Science, ;2019, 37(10): 1023-1030. doi: 10.1007/s10118-019-2319-8 shu

Deactivation Effect Caused by Catalyst-Cocatalyst Pre-contact in Propylene Polymerization with MgCl₂-supported Ziegler-Natta Catalyst

Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding author: Zhi-Qiang Fan, fanzq@zju.edu.cn
Received Date: 26 April 2019
Revised Date: 13 June 2019
Available Online: 16 August 2019

Propylene slurry polymerization with a MgCl₂-supported Ziegler-Natta catalyst containing internal electron donor was conducted after different durations of pre-contact of the catalyst with triethylaluminum cocatalyst. The number of active centers ([C^*]/[Ti]) was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and measuring sulfur content in the polymer. The pre-contact treatment caused selective deactivation of a part of active centers with low stereoselectivity and much lower activity in the initial stage of polymerization as compared with the polymerization run without the pre-contact stage. The active center concentration and polymerization activity decreased with prolonging of the pre-contact stage. The proportion of stereoselective active centers was increased by prolonging the pre-contact stage, so the isotacticity of produced polypropylene was enhanced. Release of active centers through catalyst particle fragmentation was significantly retarded, and the polymerization rate curve changed from decay type to induction type by the pre-contact treatment. In the induction period both non-stereoselective and stereoselective active centers were released and activated, resulting in gradual reduction of the polymer’s isotacticity in the first 5−10 min of polymerization. Selective deactivation of non-stereoselective active centers also took place in propylene polymerization using the catalyst without pre-contacting with the cocatalyst. In this case, the polymerization rate decayed with time after a short induction period of 2−5 min. Over reduction of the active center precursors with low stereoselectivity by triethylaluminum was considered as the reason for their deactivation during the pre-contact or the polymerization processes.
- Propylene,
- Polymerization,
- Supported Ziegler-Natta catalyst,
- Cocatalyst,
- Pre-contact
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Deactivation Effect Caused by Catalyst-Cocatalyst Pre-contact in Propylene Polymerization with MgCl2-supported Ziegler-Natta Catalyst

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通讯作者: 陈斌, bchen63@163.com

Deactivation Effect Caused by Catalyst-Cocatalyst Pre-contact in Propylene Polymerization with MgCl₂-supported Ziegler-Natta Catalyst