Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe2(O-2,6-iPr2C6H3)–Borate Catalyst

Polymerizations of 1-decene (DC), 1-dodecene (DD), and 1-tetradecene (TD) by Cp*TiMe2(O-2,6-iPr2C6H3) (1)−[Ph3C][B...

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Main Authors:	Kotohiro Nomura, Sarntamon Pengoubol, Wannida Apisuk
Format:	Article
Language:	English
Published:	MDPI AG 2019-04-01
Series:	Molecules
Subjects:	polymerization titanium complex catalyst α-olefin half-titanocene borate
Online Access:	https://www.mdpi.com/1420-3049/24/8/1634

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spelling	doaj-c59976a5b27a4cfcaf9a8d73458d99ff2020-11-24T21:30:57ZengMDPI AGMolecules1420-30492019-04-01248163410.3390/molecules24081634molecules24081634Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by CpTiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate CatalystKotohiro Nomura0Sarntamon Pengoubol1Wannida Apisuk2Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, JapanDepartment of Chemistry, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, JapanDepartment of Chemistry, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, JapanPolymerizations of 1-decene (DC), 1-dodecene (DD), and 1-tetradecene (TD) by CpTiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) (<b>1</b>)−[Ph<sub>3</sub>C][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (borate) catalyst have been explored in the presence of Al cocatalyst. The polymerizations of DC and DD, in <i>n</i>-hexane containing a mixture of Al<i><sup>i</sup></i>Bu<sub>3</sub> and Al(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>3</sub>, proceeded with high catalytic activities in a quasi-living manner, affording high molecular weight polymers (activity 4120−5860 kg-poly(DC)/mol-Ti·h, <i>M</i><sub>n</sub> for poly(DC) = 7.04−7.82 × 10<sup>5</sup>, after 20 min at −30 °C). The PDI (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub>) values in the resultant polymers decreased upon increasing the ratio of Al(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>3</sub>/Al<i><sup>i</sup></i>Bu<sub>3</sub> with decreasing the activities at −30 °C. The PDI values also became low when these polymerizations were conducted at low temperatures (−40 or −50 °C); high molecular weight poly(DD) with low PDI (<i>M</i><sub>n</sub> = 5.26 × 10<sup>5</sup>, <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> = 1.16) was obtained at −50 °C. The TD polymerization using <b>1</b>−borate−Al<i><sup>i</sup></i>Bu<sub>3</sub> catalyst (conducted in <i>n</i>-hexane at −30 °C) afforded ultrahigh molecular weight poly(TD) (<i>M</i><sub>n</sub> = 1.02 × 10<sup>6</sup>, <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> = 1.38), and the PDI values also decreased with increasing the Al(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>3</sub>/Al<i><sup>i</sup></i>Bu<sub>3</sub> ratio.https://www.mdpi.com/1420-3049/24/8/1634polymerizationtitanium complexcatalystα-olefinhalf-titanoceneborate
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Kotohiro Nomura Sarntamon Pengoubol Wannida Apisuk
spellingShingle	Kotohiro Nomura Sarntamon Pengoubol Wannida Apisuk Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate Catalyst Molecules polymerization titanium complex catalyst α-olefin half-titanocene borate
author_facet	Kotohiro Nomura Sarntamon Pengoubol Wannida Apisuk
author_sort	Kotohiro Nomura
title	Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate Catalyst
title_short	Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate Catalyst
title_full	Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate Catalyst
title_fullStr	Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate Catalyst
title_full_unstemmed	Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate Catalyst
title_sort	synthesis of ultrahigh molecular weight polymers with low pdis by polymerizations of 1-decene, 1-dodecene, and 1-tetradecene by cp*time<sub>2</sub>(o-2,6-<i><sup>i</sup></i>pr<sub>2</sub>c<sub>6</sub>h<sub>3</sub>)–borate catalyst
publisher	MDPI AG
series	Molecules
issn	1420-3049
publishDate	2019-04-01
description	Polymerizations of 1-decene (DC), 1-dodecene (DD), and 1-tetradecene (TD) by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) (<b>1</b>)−[Ph<sub>3</sub>C][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (borate) catalyst have been explored in the presence of Al cocatalyst. The polymerizations of DC and DD, in <i>n</i>-hexane containing a mixture of Al<i><sup>i</sup></i>Bu<sub>3</sub> and Al(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>3</sub>, proceeded with high catalytic activities in a quasi-living manner, affording high molecular weight polymers (activity 4120−5860 kg-poly(DC)/mol-Ti·h, <i>M</i><sub>n</sub> for poly(DC) = 7.04−7.82 × 10<sup>5</sup>, after 20 min at −30 °C). The PDI (<i>M</i><sub>w</sub>/<i>M</i><sub>n</sub>) values in the resultant polymers decreased upon increasing the ratio of Al(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>3</sub>/Al<i><sup>i</sup></i>Bu<sub>3</sub> with decreasing the activities at −30 °C. The PDI values also became low when these polymerizations were conducted at low temperatures (−40 or −50 °C); high molecular weight poly(DD) with low PDI (<i>M</i><sub>n</sub> = 5.26 × 10<sup>5</sup>, <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> = 1.16) was obtained at −50 °C. The TD polymerization using <b>1</b>−borate−Al<i><sup>i</sup></i>Bu<sub>3</sub> catalyst (conducted in <i>n</i>-hexane at −30 °C) afforded ultrahigh molecular weight poly(TD) (<i>M</i><sub>n</sub> = 1.02 × 10<sup>6</sup>, <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> = 1.38), and the PDI values also decreased with increasing the Al(<i>n</i>-C<sub>8</sub>H<sub>17</sub>)<sub>3</sub>/Al<i><sup>i</sup></i>Bu<sub>3</sub> ratio.
topic	polymerization titanium complex catalyst α-olefin half-titanocene borate
url	https://www.mdpi.com/1420-3049/24/8/1634
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_version_	1725960880966860800

Synthesis of Ultrahigh Molecular Weight Polymers with Low PDIs by Polymerizations of 1-Decene, 1-Dodecene, and 1-Tetradecene by Cp*TiMe<sub>2</sub>(O-2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)–Borate Catalyst

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