新型Ti系FI催化剂的合成及其催化乙烯“活性”聚合的研究

摘要

Based on the ligand design-oriented research idea, a new FI-Ti complex bis[N-(3-tert-butyl salicylidene)-2,6-difluoro-4-styrylanilinato]titanium (IV) dichloride(2F-BSFI) was designed and synthesized as catalyst for living polymerization of ethylene. The ligand N-(3-tert-butyl salicylidene)-2,6-difluoro-4-styrylaniline(2F-BS) was characterized by 1H Nuclear Magnetic Resonance (1H-NMR), 13C-NMR and Fourier Transform Infrared Spectroscopy (FTIR). 2F-BSFI was characterized by 1H-NMR, 13C-NMR, Elemental Analysis (EA) and Electrospray Ionization Mass Spectrometry (ESI-MS). The effects of temperature, time and amount of cocatalyst on the polymerization behavior of 2F-BSFI/d-MAO was studied. With the increase of polymerization time, the product polydispersity index (PDI) stabilized at a low level and Number Average Molecular Weight (Mn) of the product almost kept a liner growth, indicating that the catalyst has a“living”polymerization characteristic in ethylene polymerization.%采用以配体为中心的催化剂设计理念，设计并合成了一种新型 Ti 系 FI 催化剂双[N-(3-叔丁基水杨醛)-2,6-二氟苯胺-4-苯乙烯基苯胺]二氯化钛(IV)(2F-BSFI)。采用核磁氢谱（1H-NMR）、核磁碳谱（13C-NMR）和傅里叶红外（FTIR）对催化剂配体N-(3-叔丁基水杨醛)-2,6-二氟苯胺-4-苯乙烯基苯胺(2F-BS)进行了表征。用1H-NMR、13C-NMR、元素分析（EA）和电喷雾电离质谱（ESI-MS）表征了催化剂结构。以2F-BSFI 和助催化剂甲基铝氧烷（2F-BSFI/d-MAO）为催化体系催化乙烯聚合，考察了聚合时间、温度、助催化剂用量对催化性能的影响。结果表明，随着聚合时间的增加，产物分子量分布指数（PDI）稳定在较低水平，产物数均分子量Mn几乎呈线性增长，说明该催化剂催化乙烯聚合具有拟活性聚合特征。