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Open AccessArticle

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

Department of Chemistry, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, Japan
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Author to whom correspondence should be addressed.
Academic Editor: Giovanni Ricci
Molecules 2019, 24(8), 1634; https://doi.org/10.3390/molecules24081634
Received: 29 March 2019 / Revised: 13 April 2019 / Accepted: 23 April 2019 / Published: 25 April 2019
(This article belongs to the Special Issue Well-Defined Metal Complex Catalysts for Olefin Polymerization)
Polymerizations of 1-decene (DC), 1-dodecene (DD), and 1-tetradecene (TD) by Cp*TiMe2(O-2,6-iPr2C6H3) (1)–[Ph3C][B(C6F5)4] (borate) catalyst have been explored in the presence of Al cocatalyst. The polymerizations of DC and DD, in n-hexane containing a mixture of AliBu3 and Al(n-C8H17)3, proceeded with high catalytic activities in a quasi-living manner, affording high molecular weight polymers (activity 4120–5860 kg-poly(DC)/mol-Ti·h, Mn for poly(DC) = 7.04–7.82 × 105, after 20 min at −30 °C). The PDI (Mw/Mn) values in the resultant polymers decreased upon increasing the ratio of Al(n-C8H17)3/AliBu3 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 (Mn = 5.26 × 105, Mw/Mn = 1.16) was obtained at −50 °C. The TD polymerization using 1–borate–AliBu3 catalyst (conducted in n-hexane at −30 °C) afforded ultrahigh molecular weight poly(TD) (Mn = 1.02 × 106, Mw/Mn = 1.38), and the PDI values also decreased with increasing the Al(n-C8H17)3/AliBu3 ratio. View Full-Text
Keywords: polymerization; titanium complex; catalyst; α-olefin; half-titanocene; borate polymerization; titanium complex; catalyst; α-olefin; half-titanocene; borate
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MDPI and ACS Style

Nomura, K.; Pengoubol, S.; Apisuk, W. 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. Molecules 2019, 24, 1634.

AMA Style

Nomura K, Pengoubol S, Apisuk W. 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. Molecules. 2019; 24(8):1634.

Chicago/Turabian Style

Nomura, Kotohiro; Pengoubol, Sarntamon; Apisuk, Wannida. 2019. "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" Molecules 24, no. 8: 1634.

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