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硅二醇酯作为用于丙烯聚合的MgCl负载齐格勒-纳塔体系中的新型选择性控制剂:催化剂结构与聚合物性能

Silyl diol ester as a new selectivity control agent in MgCl-supported Ziegler-Natta systems for propylene polymerization: catalyst structure and polymer properties.

作者信息

Poorsank Fatemeh, Arabi Hassan, Ghasemi Hamedani Nona

机构信息

Department of Polymerization Engineering, Iran Polymer and Petrochemical Institute P.O. Box: 14965/115 Tehran Iran

出版信息

RSC Adv. 2019 Mar 6;9(13):7420-7431. doi: 10.1039/c9ra00715f. eCollection 2019 Mar 1.

Abstract

In this study, bis(benzoyloxy)dimethylsilane (SDE) was developed as a non-phthalate selectivity control agent (internal donor (ID) and external donor (ED)) in MgCl-supported Ziegler-Natta (ZN) systems. The impact of SDE as an ID was investigated in regards to chemical composition, morphology, adsorption behavior (using FTIR spectroscopy, WAXD and SEM studies) and the propylene polymerization performance of the catalyst. The results of the adsorption behavior of SDE revealed that SDE, while able to stabilize the electronically unsaturated surfaces of MgCl [(104) and (110)], has a rather high tendency to be absorbed on strongly acidic Mg ions at the corners of these crystals. The catalyst with optimum SDE content as an ID afforded a system with reasonable activity and isotacticity (even in the absence of ED) along with broader molecular weight distribution (PDI: 6.2-10) and greater flexural modulus than phthalate-based ZN systems. SDE was also used as a new ED in most widely used fourth- and fifth-generation catalyst systems. The results revealed that in fifth-generation catalyst systems, there was an increase in hydrogen response (>40%) along with an increase of activity without any change in the thermal properties of the final polymer in comparison to a conventional ED (alkoxy silane).

摘要

在本研究中,双(苯甲酰氧基)二甲基硅烷(SDE)被开发为MgCl负载的齐格勒-纳塔(ZN)体系中的一种非邻苯二甲酸酯选择性控制剂(内给体(ID)和外给体(ED))。研究了SDE作为内给体对催化剂的化学组成、形态、吸附行为(采用傅里叶变换红外光谱、广角X射线衍射和扫描电子显微镜研究)以及丙烯聚合性能的影响。SDE吸附行为的结果表明,SDE虽然能够稳定MgCl[(104)和(110)]的电子不饱和表面,但在这些晶体角落处具有相当高被强酸性Mg离子吸附的倾向。具有最佳SDE含量作为内给体的催化剂提供了一个具有合理活性和等规度的体系(即使在没有外给体的情况下),同时具有比基于邻苯二甲酸酯类的ZN体系更宽的分子量分布(PDI:6.2 - 10)和更高的弯曲模量。SDE还被用作最广泛使用的第四代和第五代催化剂体系中的新型外给体。结果表明,在第五代催化剂体系中,与传统外给体(烷氧基硅烷)相比,氢气响应增加(>40%),同时活性增加,而最终聚合物的热性能没有任何变化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0211/9061220/4ae27b105d78/c9ra00715f-f1.jpg

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