[ONX]钛配合物的设计、合成及其催化丙烯立构选择性(共)聚合研究

聚丙烯作为一种半结晶热塑性塑料，具有良好的耐受化学品和极端条件的性能，广泛应用于日常生活和工业生产。高立构规整度的聚丙烯具有高熔点、低密度、高弹性模量、优异的化学耐受性等突出性能，成为商业化生产和应用的主导材料。具有不同微观结构的聚丙烯通常表现出不同的性能，从而满足不同领域日益多样化的需求。此外，官能化聚丙烯赋予材料更多优异性能，如粘附性、韧性、导电性、可染性、相容性和流变性等。因此，开发新型催化剂和高效的催化工艺，以实现丙烯与极性单体的立构选择性共聚，一直是学术界和工业界共同致力的目标。相比于后过渡金属，前过渡金属催化剂更利于合成iPP，但由于其较强的亲氧性，通常对极性单体杂原子的耐受性差。在此，我们设计并合成了一系列水杨醛类三齿[ONX]型Ti配合物，并探讨了它们在催化丙烯均聚和共聚中的反应性能，其中边臂基团有助于调整聚合物规整度并提高对极性单体的容忍度。

  本论文内容主要包括三部分：1）利用边臂策略设计合成了一系列水杨醛亚胺/饱和胺类ONX型三齿配体及相应的钛配合物。这些配体具有不同的桥联方式、边臂基团和骨架修饰。通过核磁共振、高分辨质谱或X-Ray单晶衍射等分析方法对化合物进行了表征和分析。2）在优化的聚合条件（MMAO作为助催化剂，3 atm的丙烯压力）下，将此类配合物用于丙烯均聚研究。研究结果表明，经过对配体骨架的调整，实现了丙烯的高立构选择性均聚，获得了等规度（[mmmm]）高达80% 的聚丙烯。通过催化剂结构催化性能关系研究，初步总结了催化剂结构对催化活性、聚合物分子量及立构规整度的调控规律。3）研究了[O-NXR]TiBn2配合物催化丙烯与烯醇单体（经Al(iBu)3预处理）的共聚合。除了关注规整度和催化活性外，我们发现极性单体的插入率与其链长相关，链长越长，其插入率越高。此外，我们还确定了催化剂结构中调控烯醇单体插入的潜在位点，获得了单体插入率高达9.45 mol% 的官能化聚丙烯。

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