Assessing 1,9-Decadiene/Propylene Copolymerization with Ziegler-Natta Catalysts to Long-Chain-Branched Polypropylene,Industrial & Engineering Chemistry Research

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Assessing 1,9-Decadiene/Propylene Copolymerization with Ziegler-Natta Catalysts to Long-Chain-Branched Polypropylene
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2020-06-07 , DOI: 10.1021/acs.iecr.0c02087
Yang Liu _{1,

2} , Yawei Qin _{1,

2} , Jin-Yong Dong _{1,

2}

Affiliation

1,9-Decadiene/propylene copolymerization is assessed as a way for Ziegler-Natta catalysts to access long-chain-branched polypropylene (LCB-PP). A MgCl₂/9,9-bis-(methoxymethyl)fluorine/TiCl₄ catalyst with triethylaluminum as a cocatalyst, which is celebrated as a higher α-olefin-capable Ziegler-Natta catalyst system, is exemplified for the task. It is found that the catalyst system incorporates 1,9-decadiene forming LCB structures only at greatly increased 1,9-decadiene concentrations. The LCB structure formation lags much behind 1,9-decadiene incorporation, leaving a narrow window to access gel-free LCB-PP. Rheological properties of the copolymers are well correspondent with their structures. The gel-free LCB sample exhibits the characteristic rheological behavior of LCB-PP including increased elasticity (G′) and enhanced shear thinning. Because of the low LCB efficiency for 1,9-decadiene, the copolymers are substantially reduced in melting temperature (T_m) due to the redundant vinyl structures acting as short-chain branching.

中文翻译：

用Ziegler-Natta催化剂评估1,9-癸二烯/丙烯共聚成长链支化聚丙烯

1,9-癸二烯/丙烯共聚被评估为齐格勒-纳塔催化剂接触长支链聚丙烯（LCB-PP）的一种方式。MgCl ₂ / 9,9-双-（甲氧基甲基）氟/ TiCl ₄以三乙基铝为助催化剂的这种催化剂为例，该催化剂以具有更高α-烯烃能力的齐格勒-纳塔催化剂体系而著称。发现该催化剂体系仅在大大增加的1，9-癸二烯浓度下掺入1，9-癸二烯形成LCB结构。LCB结构的形成远远滞后于1,9-癸二烯的掺入，从而留下了狭窄的窗口以接触无凝胶的LCB-PP。共聚物的流变性质与其结构很好地对应。无凝胶的LCB样品表现出LCB-PP的特征流变行为，包括增加的弹性（G '）和增强的剪切稀化。由于1,9-癸二烯的LCB效率低，因此共聚物的熔融温度（T _m）是由于多余的乙烯基结构充当了短链分支。

更新日期：2020-07-01

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