Synthesis of Polypropylene Diblock Copolymers Via Metallocene And Borane Chemistry

利用Metallocene觸媒及硼化學方法合成聚丙烯之段式共聚物

江彰吉(George J. Jiang) ； 徐昊聰(Ming-Tsung Hsu) ； 李曉芳(Sheau-Fang Lee)

《中原學報》 25卷3期 (1997/08) Pp. 11-20

https://doi.org/10.6358/JCYU.199708.0011

摘要

本篇是利用新世代高效率Metallocene觸媒：Et(Ind)(下標 2)ZrCl(下標 2)及助觸媒MAO聚合丙烯，此一觸媒系統具有合成立體規則性及末端未飽和聚丙烯的特性，再將硼燒試劑導入聚丙烯之末端未飽和雙鍵，形成含硼聚丙烯，並將其官能化成經基化聚丙烯，分子量則可隨意控制。
末端羥基化的聚丙烯以TDI反應成巨活化物，再進行陰離子開環計Є-己內醯胺反應，合成聚丙烯與聚烯6，PP-b-NY6，兩段式共聚物。另一方面，含硼聚丙烯加MMA單體，再打入氧氣，會進行選擇性的自氣化反應，在聚丙烯鏈末端產生自由基可當巨起始劑，以進行 MMA 單體之聚合形成聚丙烯與聚甲慕丙烯酸甲醋， PP-b-PMMA，之兩段式共聚物。末端帶羥基之聚丙烯，也可使用TDI及MDI之肢基單體進行官能化為異氰酸醋再進行膠基甲酸醋的聚合，形成聚丙烯與聚胺基甲酸酯，PP-b-PU，之共聚物。
合成之兩段式共聚物以IR及NMR來鑑定其結構，並以GPC測其分子量，熱性質則以DSC測定之。在應用性研究方面，以兩段式共聚物作為聚丙烯和聚烯肢6或PMMA混摻時的調和劑，由偏光顯微鏡中可直接觀察出共聚物對混摻的調和作用。

關鍵字

聚丙烯 ； 兩段式共聚物 ； 過渡金屬觸媒

並列摘要

A homogeneous metallocene Et(Ind)2ZrCl2 with MAO were used in the polymerization of polypropylene. This catalyst system produced a isotactic, and chain end unsaturated polypropylene. Borane was employed added to polypropylene to prepare a borane-containing polypropylene which can be transformed to hydroxyl-terminated polypropylene.
Telechelic hydroxyl-terminated polypropylene, PPOH, can react with toluene diisocyanatc (TDI) to form a prepolymer-containing chain-end NCO functional group, PP-NCO. By using the resulting materials as macroactivators for anionic-ring-opening polymerization of caprolactam, a polypropylene-nylon 6 diblock copolymer was obtained. On the other hand, borane-containing polypropylene can react with oxygen to produce the free radicals located at the chain end on polypropylene. The free radical is effective initiator for the polymerization of methylmethacrylate to produce diblock copolymer of PP-b-PMMA. A diblock copolymer of PP-b-PU was also prepared. The block copolymers have been characterized by IR, NMR, and DSC. The diblock copolymer is a compatibilizer for various polypropylene blends with other polymers.

並列關鍵字

polypropylene ； diblock copolymer ； metallocene catalyst