A Ti-based diamine bis(phenolate) catalyst, [Ti{2,2′-(OC₆H₂-4,6-tBu₂)₂NHMePhMeNH}Cl₂], was synthesized and fully characterized by elemental analysis and NMR spectroscopy. Very effective, fast, and reversible chain transfer was achieved between an active transition metal-based propagating center and diethylzinc, which acted as a chain transfer agent, in the coordinative chain transfer polymerization (CCTP) of 1-decene. The molecular weight of the obtained oligomers was efficiently regulated and decreased by the addition of ZnEt₂ to the oligomerization system. The kinetic results disclosed that ZnEt₂, besides its primary role as a chain transfer agent, also significantly reduced the catalyst consumption. DFT calculations were performed to reveal the reaction mechanism. Notably, the CCTP technique led to the occurrence of fast and reversible chain transfer, bypassing the β-H termination pathway, so oligomer chains without any unsaturated bonds were obtained. Finally, a linear relationship between the ZnEt₂ content and the tacticity characteristic of the resulting oligomers was detected. The viscosity results showed that the obtained oligomers had a viscosity index in the range of 131.7–159.7 and pour point values less than −48 °C, which were comparable with the properties of commercial polyalfaolefin-based oils. Our proposed green approach for producing low viscosity polyalphaolefins (PAO4 and PAO6) can replace the industrially-used and hazardous BF₃ catalyst system with great success.

中文翻译：

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钛基二胺双酚盐催化剂存在下1-癸烯的配位链转移聚合：生产低粘度PAO的可持续方法

合成了钛基二胺双酚盐催化剂[Ti {2,2'-（OC ₆ H ₂ -4,6- t Bu ₂）₂ NHMePhMeNH} Cl ₂ ]，并通过元素分析和NMR进行了全面表征光谱学。在1-癸烯的配位链转移聚合（CCTP）中，基于活性过渡金属的繁殖中心与充当链转移剂的二乙基锌之间实现了非常有效，快速和可逆的链转移。通过向低聚体系中添加ZnEt ₂，有效地调节和降低了所获得的低聚物的分子量。动力学结果表明，ZnEt ₂除了作为链转移剂的主要作用外，还大大减少了催化剂的消耗。进行DFT计算以揭示反应机理。值得注意的是，CCTP技术导致发生快速且可逆的链转移，绕过了β-H终止途径，因此获得了没有任何不饱和键的低聚物链。最后，ZnEt ₂之间的线性关系检测得到的低聚物的含量和立构规整度。粘度结果表明，所获得的低聚物的粘度指数在131.7–159.7范围内，倾点值小于-48°C，与市售的基于聚烯烃的油的性能相当。我们提出的用于生产低粘度聚α烯烃（PAO4和PAO6）的绿色方法可以成功替代工业上使用的危险BF ₃催化剂体系。