Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation

Ultra-high molecular weight poly-α-olefins are widely used as drag reducing agents (DRAs) for pipeline transportation of oil and refined petroleum products. The synthesis of polyolefin DRAs is based on low-temperature Ziegler–Natta (ZN) polymerization of higher α-olefins. 1-Hexene based DRAs, the mo...

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Autores principales:	Ilya E. Nifant’ev, Alexander N. Tavtorkin, Alexey A. Vinogradov, Sofia A. Korchagina, Maria S. Chinova, Roman S. Borisov, Grigory A. Artem’ev, Pavel V. Ivchenko
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	chromium PNP catalysts drag reducing ethylene oligomerization internal donor linear α-olefins branched α-olefins Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/91610f57e3d84bf39d0016c44f4d904b
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spelling	oai:doaj.org-article:91610f57e3d84bf39d0016c44f4d904b2021-11-25T18:48:25ZTandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation10.3390/polym132239302073-4360https://doaj.org/article/91610f57e3d84bf39d0016c44f4d904b2021-11-01T00:00:00Zhttps://www.mdpi.com/2073-4360/13/22/3930https://doaj.org/toc/2073-4360Ultra-high molecular weight poly-α-olefins are widely used as drag reducing agents (DRAs) for pipeline transportation of oil and refined petroleum products. The synthesis of polyolefin DRAs is based on low-temperature Ziegler–Natta (ZN) polymerization of higher α-olefins. 1-Hexene based DRAs, the most effective at room temperature, typically lose DR activity at low temperatures. The use of 1-hexene copolymers with C8–C12 linear α-olefins appears to offer a solution to the problem of low-temperature drag reducing. The present work aims to develop two-stage synthesis of polyolefin DRAs that is based on selective oligomerization of ethylene in the presence of efficient chromium/aminodiphosphine catalysts (Cr-PNP), followed by polymerization of the olefin mixtures, formed at oligomerization stage, using efficient titanium–magnesium ZN catalyst. We have shown that oligomerization of ethylene in α-olefin reaction media proceeds faster than in saturated hydrocarbons, providing the formation of 1-hexene, 1-octene, and branched C10 and C12 olefins; the composition and the ratio of the reaction products depended on the nature of PNP ligand. Oligomerizates were used in ZN polymerization ‘as is’, without additional treatment. Due to branched character of C10+ hydrocarbons, formed during oligomerization of ethylene, resulting polyolefins demonstrate higher low-temperature DR efficiency at low polymer concentrations (~1 ppm) in comparison with benchmark polymers prepared from the mixtures of linear α-olefins and from pure 1-hexene. We assume that faster solubility and more efficient solvation of the polyolefins, prepared using ‘tandem’ ethylene-based process, represent an advantage of these type polymers over conventional poly(1-hexene) and linear α-olefin-based polymers when used as ‘winter’ DRAs.Ilya E. Nifant’evAlexander N. TavtorkinAlexey A. VinogradovSofia A. KorchaginaMaria S. ChinovaRoman S. BorisovGrigory A. Artem’evPavel V. IvchenkoMDPI AGarticlechromium PNP catalystsdrag reducingethylene oligomerizationinternal donorlinear α-olefinsbranched α-olefinsOrganic chemistryQD241-441ENPolymers, Vol 13, Iss 3930, p 3930 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	chromium PNP catalysts drag reducing ethylene oligomerization internal donor linear α-olefins branched α-olefins Organic chemistry QD241-441
spellingShingle	chromium PNP catalysts drag reducing ethylene oligomerization internal donor linear α-olefins branched α-olefins Organic chemistry QD241-441 Ilya E. Nifant’ev Alexander N. Tavtorkin Alexey A. Vinogradov Sofia A. Korchagina Maria S. Chinova Roman S. Borisov Grigory A. Artem’ev Pavel V. Ivchenko Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation
description	Ultra-high molecular weight poly-α-olefins are widely used as drag reducing agents (DRAs) for pipeline transportation of oil and refined petroleum products. The synthesis of polyolefin DRAs is based on low-temperature Ziegler–Natta (ZN) polymerization of higher α-olefins. 1-Hexene based DRAs, the most effective at room temperature, typically lose DR activity at low temperatures. The use of 1-hexene copolymers with C8–C12 linear α-olefins appears to offer a solution to the problem of low-temperature drag reducing. The present work aims to develop two-stage synthesis of polyolefin DRAs that is based on selective oligomerization of ethylene in the presence of efficient chromium/aminodiphosphine catalysts (Cr-PNP), followed by polymerization of the olefin mixtures, formed at oligomerization stage, using efficient titanium–magnesium ZN catalyst. We have shown that oligomerization of ethylene in α-olefin reaction media proceeds faster than in saturated hydrocarbons, providing the formation of 1-hexene, 1-octene, and branched C10 and C12 olefins; the composition and the ratio of the reaction products depended on the nature of PNP ligand. Oligomerizates were used in ZN polymerization ‘as is’, without additional treatment. Due to branched character of C10+ hydrocarbons, formed during oligomerization of ethylene, resulting polyolefins demonstrate higher low-temperature DR efficiency at low polymer concentrations (~1 ppm) in comparison with benchmark polymers prepared from the mixtures of linear α-olefins and from pure 1-hexene. We assume that faster solubility and more efficient solvation of the polyolefins, prepared using ‘tandem’ ethylene-based process, represent an advantage of these type polymers over conventional poly(1-hexene) and linear α-olefin-based polymers when used as ‘winter’ DRAs.
format	article
author	Ilya E. Nifant’ev Alexander N. Tavtorkin Alexey A. Vinogradov Sofia A. Korchagina Maria S. Chinova Roman S. Borisov Grigory A. Artem’ev Pavel V. Ivchenko
author_facet	Ilya E. Nifant’ev Alexander N. Tavtorkin Alexey A. Vinogradov Sofia A. Korchagina Maria S. Chinova Roman S. Borisov Grigory A. Artem’ev Pavel V. Ivchenko
author_sort	Ilya E. Nifant’ev
title	Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation
title_short	Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation
title_full	Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation
title_fullStr	Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation
title_full_unstemmed	Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation
title_sort	tandem synthesis of ultra-high molecular weight drag reducing poly-α-olefins for low-temperature pipeline transportation
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/91610f57e3d84bf39d0016c44f4d904b
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Tandem Synthesis of Ultra-High Molecular Weight Drag Reducing Poly-α-Olefins for Low-Temperature Pipeline Transportation

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