Abstract
The catalytic activity of electrochemically synthesized zirconium carboxylates was studied in the process of ethylene oligomerization. Zirconium carboxylates were electrochemically synthesized directly from metallic zirconium and corresponding carboxylic acids (acetic, octanoic and lauric). A comprehensive study (element analysis, nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, powder X-ray diffraction (PXRD)) of the synthesized zirconium carboxylates showed that these species contain bidentate carboxylate moieties. It was shown that obtained zirconium carboxylates, in combination with Et3Al2Cl3 (Al/Zr = 20), have a moderate activity of (7.6–9.9) × 103 molC2H4⋅molZr−1⋅h−1 in terms of ethylene oligomerization (at T = 80 °C, p = 20 bar), leading to even-numbered C4–C10 linear alpha-olefins.
Highlights
The continuous growth of global polymer production leads to the development of new methods and catalysts for obtaining of olefin monomers; for example, alkane dehydrogenation, methanol-to-olefins, metathesis and olefin oligomerization [1,2,3,4,5]
We have tried to use a similar approach for the synthesis of zirconium carboxylates with a variety of carboxylic acids bearing a wide range of carbon atoms in hydrocarbon chain
The choice of these compounds was based on their usage as a pre-catalyst in an important industrial process of linear alpha-olefins (LAO) synthesis—Alpha–Sablin (SABIC-Linde) [11]—as well as due to their use for the synthesis of materials with unique properties, such as metal–organic frameworks and catalysts [24,25,26]
Summary
The continuous growth of global polymer production leads to the development of new methods and catalysts for obtaining of olefin monomers; for example, alkane dehydrogenation, methanol-to-olefins, metathesis and olefin oligomerization [1,2,3,4,5]. Ethylene oligomerization aimed to obtain linear alpha-olefins (LAO), which are used as co-monomers in the production of the demanded types of polyethylene (linear low-density polyethylene, high-density polyethylene), as well as for the production of a wide range of unique chemicals, such as lubricants and additives, plasticizers, surfactants and so forth [6]. Zirconium pre-catalysts are used in many industrial processes of homogeneous ethylene oligomerization, such as Alphaselect Ltd (Tokyo, Japan) [10,11,12] The products of these processes are even-numbered LAOs with a wide distribution regarding the number of carbon atoms (from 4 to 30–40)
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