含季碳中心的聚α-烯烃的结构和性能。,ACS Omega

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含季碳中心的聚α-烯烃的结构和性能。
ACS Omega ( IF 3.7 ) Pub Date : 2020-04-13 , DOI: 10.1021/acsomega.9b04361
Ruida Zhao ₁ , Puke Mi ₁ , Sheng Xu ₂ , Suqin Dong ₁

Affiliation

在本文中，通过使用茂金属催化剂和齐格勒-纳塔催化剂的两步低聚反应，制备了包含季碳中心的聚α-烯烃（PAO）。首先，将1-癸烯二聚体用[t-BuN（Me）2C（η5-C5H4）] ZrCl2进行低聚，并研究了低聚温度，Al / Zr摩尔比和催化剂用量对低聚的影响。在第二步中，将获得的1-癸烯二聚体与1-癸烯与TiCl4 / Et2AlCl共聚，并研究了催化剂，单体/二聚体比例和α-烯烃种类对共聚的影响。二聚体和共聚产物的组成和结构通过气相色谱法（GC），1 H NMR和13 C NMR谱表征。GC和13C NMR分析的结果表明，茂金属催化了1-癸烯低聚产物的形成，导致支链烯烃二聚体成为主要产物，并且在1-癸烯/ 1-癸烯二聚体中存在季碳。共聚产物也可以找到。提出了形成季碳中心的聚合机理。含有季碳中心的1-癸烯/ 1-癸烯二聚物共聚产物在100℃下的运动粘度为10.8mm2 / s，粘度指数为165，倾点为-52℃。因此，具有季碳中心的产物比1-癸烯低聚产物和典型的PAO产物具有更好的粘度-温度性能和低温流动性，但是运动粘度相似。

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Structure and Properties of Poly-α-olefins Containing Quaternary Carbon Centers.

In this paper, poly-α-olefins (PAO) containing quaternary carbon centers were prepared by two-step oligomerization using a metallocene catalyst followed by a Ziegler-Natta catalyst. First, the 1-decene dimer was oligomerized with [t-BuN(Me)2C(η5-C5H4)]ZrCl2, and the effects of the oligomerization temperature, Al/Zr molar ratio, and catalyst loading on the oligomerization were investigated. In the second step, the obtained 1-decene dimers were copolymerized with 1-decene with TiCl4/Et2AlCl, and the effects of the catalysts, monomer/dimer ratio, and α-olefin species on the copolymerization were investigated. The composition and structure of the dimers and copolymerization products were characterized by gas chromatography (GC) and 1H NMR and 13C NMR spectroscopy. The results of GC and 13C NMR analyses indicated that the metallocene catalyzed the formation of the 1-decene oligomerization product, resulting in the branched olefin dimer being the major product, and the existence of quaternary carbons in the 1-decene/1-decene dimer copolymerization product could also be found. The polymerization mechanism for the formation of the quaternary carbon centers is proposed. The 1-decene/1-decene dimer copolymerization product containing quaternary carbon centers has a kinematic viscosity of 10.8 mm2/s at 100 °C, a viscosity index of 165, and a pour point of -52 °C; thus, the product with quaternary carbon centers has a better viscosity-temperature performance and low-temperature fluidity than those of the 1-decene oligomerization product and typical PAO products, but the kinematic viscosity is similar.

更新日期：2020-04-23

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