Polar Isotactic and Syndiotactic Polypropylenes by Organozirconium-Catalyzed Masking-Reagent-Free Propylene and Amino–Olefin Copolymerization

Minglu Huang; Jiazhen Chen; Binghao Wang; Wei Huang; Haibo Chen; Yanshan Gao; Tobin J. Marks

doi:10.1002/anie.202005635

Polar Isotactic and Syndiotactic Polypropylenes by Organozirconium-Catalyzed Masking-Reagent-Free Propylene and Amino–Olefin Copolymerization

Minglu Huang, Jiazhen Chen, Binghao Wang, Wei Huang, Haibo Chen, Yanshan Gao, Tobin J. Marks

Northwestern University

Research output: Contribution to journal › Article › peer-review

Abstract

Polar functionalized isotactic and syndiotactic polypropylenes (PPs) are synthesized by direct, masking-reagent-free propylene and amino–olefin (AO, CH₂=CH(CH₂)_xNⁿPr₂, x=2, 3, 6) copolymerizations using the activated precatalysts rac-[Me₂Si(indenyl)₂]ZrMe₂ and [Me₂C(Cp)(fluorenyl)]ZrMe₂, respectively. Polymerization activities at 25 °C are as high as 4208 and 535 kg/(mol h atm) with AO incorporation up to 4.0 mol % and 1.6 mol %, respectively. Remarkably, introducing the amino-olefin comonomers significantly enhances stereoselection for both isotactic (mmmm: 59.5 %→91.0 %) and syndiotactic (rrrr: 66.3 %→81.3 %) products.

Original language	English
Pages (from-to)	20522-20528
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	46
DOIs	https://doi.org/10.1002/anie.202005635
Publication status	Published - Nov 9 2020

Keywords

copolymerization
monomers
polymers
synthetic methods
zirconium

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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Polar Isotactic and Syndiotactic Polypropylenes by Organozirconium-Catalyzed Masking-Reagent-Free Propylene and Amino–Olefin Copolymerization. / Huang, Minglu; Chen, Jiazhen; Wang, Binghao; Huang, Wei; Chen, Haibo; Gao, Yanshan; Marks, Tobin J.

In: Angewandte Chemie - International Edition, Vol. 59, No. 46, 09.11.2020, p. 20522-20528.

Research output: Contribution to journal › Article › peer-review

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abstract = "Polar functionalized isotactic and syndiotactic polypropylenes (PPs) are synthesized by direct, masking-reagent-free propylene and amino–olefin (AO, CH2=CH(CH2)xNnPr2, x=2, 3, 6) copolymerizations using the activated precatalysts rac-[Me2Si(indenyl)2]ZrMe2 and [Me2C(Cp)(fluorenyl)]ZrMe2, respectively. Polymerization activities at 25 °C are as high as 4208 and 535 kg/(mol h atm) with AO incorporation up to 4.0 mol % and 1.6 mol %, respectively. Remarkably, introducing the amino-olefin comonomers significantly enhances stereoselection for both isotactic (mmmm: 59.5 %→91.0 %) and syndiotactic (rrrr: 66.3 %→81.3 %) products.",

keywords = "copolymerization, monomers, polymers, synthetic methods, zirconium",

author = "Minglu Huang and Jiazhen Chen and Binghao Wang and Wei Huang and Haibo Chen and Yanshan Gao and Marks, {Tobin J.}",

note = "Funding Information: Financial support by a gift from Wanhua Chemical Co. and NSF catalysis grant CHE‐1856619 (YG) are gratefully acknowledged. Purchase of NMR instrumentation at the Northwestern U. IMSERC facility was supported by NSF grant CHE‐104877. ",

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AU - Huang, Wei

AU - Chen, Haibo

AU - Gao, Yanshan

AU - Marks, Tobin J.

N1 - Funding Information: Financial support by a gift from Wanhua Chemical Co. and NSF catalysis grant CHE‐1856619 (YG) are gratefully acknowledged. Purchase of NMR instrumentation at the Northwestern U. IMSERC facility was supported by NSF grant CHE‐104877.

PY - 2020/11/9

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N2 - Polar functionalized isotactic and syndiotactic polypropylenes (PPs) are synthesized by direct, masking-reagent-free propylene and amino–olefin (AO, CH2=CH(CH2)xNnPr2, x=2, 3, 6) copolymerizations using the activated precatalysts rac-[Me2Si(indenyl)2]ZrMe2 and [Me2C(Cp)(fluorenyl)]ZrMe2, respectively. Polymerization activities at 25 °C are as high as 4208 and 535 kg/(mol h atm) with AO incorporation up to 4.0 mol % and 1.6 mol %, respectively. Remarkably, introducing the amino-olefin comonomers significantly enhances stereoselection for both isotactic (mmmm: 59.5 %→91.0 %) and syndiotactic (rrrr: 66.3 %→81.3 %) products.

AB - Polar functionalized isotactic and syndiotactic polypropylenes (PPs) are synthesized by direct, masking-reagent-free propylene and amino–olefin (AO, CH2=CH(CH2)xNnPr2, x=2, 3, 6) copolymerizations using the activated precatalysts rac-[Me2Si(indenyl)2]ZrMe2 and [Me2C(Cp)(fluorenyl)]ZrMe2, respectively. Polymerization activities at 25 °C are as high as 4208 and 535 kg/(mol h atm) with AO incorporation up to 4.0 mol % and 1.6 mol %, respectively. Remarkably, introducing the amino-olefin comonomers significantly enhances stereoselection for both isotactic (mmmm: 59.5 %→91.0 %) and syndiotactic (rrrr: 66.3 %→81.3 %) products.

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