Catalyst Nuclearity Effects on Stereo- and Regioinduction in Pyridylamidohafnium-Catalyzed Propylene and 1-Octene Polymerizations

Yanshan Gao, Xia Chen, Jialong Zhang, Jiazhen Chen, Tracy L. Lohr, Tobin J Marks

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

In comparison to monometallic controls, bimetallic olefin polymerization catalysts often exhibit superior performance in terms of higher polyolefin Mw, higher comonomer incorporation, and higher polar comonomer tolerance. However, using cooperating catalyst centers to modulate stereoselectivity in α-olefin polymerizations is relatively unexplored. In this contribution, the monometallic Hf(IV) complex, L1-HfMe2 (catalyst A, L1 = 2,6-diisopropyl-N-{(2-isopropylphenyl)[6-(naphthalen-1-yl)pyridin-2-yl]methyl}aniline), and homo-bimetallic Hf(IV) complexes, L2-Hf2Me5 (catalyst B) and L2-Hf2Me4 (catalyst C) (L2 = N,N′-{[naphthalene-1,4-diylbis(pyridine-6,2-diyl)]bis[(2-isopropylphenyl)methylene)]bis(2,6-diisopropylaniline}), are activated with Ph3C+B(C6F5)4 - and investigated in propylene and 1-octene homopolymerizations. In propylene polymerizations, the conformationally flexible catalyst B-derived bimetallic dicationic catalyst produces higher Mw polypropylene (up to 7.8×), higher total stereo- and regiodefect densities (up to 3.5×), and lower Tm (by as much as ∼14 °C) versus the monometallic catalyst A-derived control. In 1-octene polymerizations, the conformationally flexible catalyst B-derived bimetallic dicationic catalyst induces greatly reduced isotacticity (23% reduction in [mmmm]) versus the catalyst A-derived monometallic control ([mmmm] > 99%). Interestingly, conformationally flexible catalyst B-derived cationic bimetallic Hf catalysts are also known to undergo rapid intramolecular/intermetal methyl exchange and to exhibit strong Hf···Hf cooperative enchainment effects in ethylene homo- and copolymerizations. Steric effects and intramolecular intermetal chain transfer likely both contribute to the increased isotactic polyolefin stereo- and regiodefect content.

Original languageEnglish
Pages (from-to)2401-2410
Number of pages10
JournalMacromolecules
Volume51
Issue number6
DOIs
Publication statusPublished - Mar 27 2018

Fingerprint

Propylene
Polymerization
Catalysts
Polyolefins
Alkenes
Homopolymerization
1-octene
propylene
Olefins
Stereoselectivity
Polypropylenes
Aniline
Naphthalene
Pyridine
Copolymerization
Ethylene

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Catalyst Nuclearity Effects on Stereo- and Regioinduction in Pyridylamidohafnium-Catalyzed Propylene and 1-Octene Polymerizations. / Gao, Yanshan; Chen, Xia; Zhang, Jialong; Chen, Jiazhen; Lohr, Tracy L.; Marks, Tobin J.

In: Macromolecules, Vol. 51, No. 6, 27.03.2018, p. 2401-2410.

Research output: Contribution to journalArticle

Gao, Yanshan ; Chen, Xia ; Zhang, Jialong ; Chen, Jiazhen ; Lohr, Tracy L. ; Marks, Tobin J. / Catalyst Nuclearity Effects on Stereo- and Regioinduction in Pyridylamidohafnium-Catalyzed Propylene and 1-Octene Polymerizations. In: Macromolecules. 2018 ; Vol. 51, No. 6. pp. 2401-2410.
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abstract = "In comparison to monometallic controls, bimetallic olefin polymerization catalysts often exhibit superior performance in terms of higher polyolefin Mw, higher comonomer incorporation, and higher polar comonomer tolerance. However, using cooperating catalyst centers to modulate stereoselectivity in α-olefin polymerizations is relatively unexplored. In this contribution, the monometallic Hf(IV) complex, L1-HfMe2 (catalyst A, L1 = 2,6-diisopropyl-N-{(2-isopropylphenyl)[6-(naphthalen-1-yl)pyridin-2-yl]methyl}aniline), and homo-bimetallic Hf(IV) complexes, L2-Hf2Me5 (catalyst B) and L2-Hf2Me4 (catalyst C) (L2 = N,N′-{[naphthalene-1,4-diylbis(pyridine-6,2-diyl)]bis[(2-isopropylphenyl)methylene)]bis(2,6-diisopropylaniline}), are activated with Ph3C+B(C6F5)4 - and investigated in propylene and 1-octene homopolymerizations. In propylene polymerizations, the conformationally flexible catalyst B-derived bimetallic dicationic catalyst produces higher Mw polypropylene (up to 7.8×), higher total stereo- and regiodefect densities (up to 3.5×), and lower Tm (by as much as ∼14 °C) versus the monometallic catalyst A-derived control. In 1-octene polymerizations, the conformationally flexible catalyst B-derived bimetallic dicationic catalyst induces greatly reduced isotacticity (23{\%} reduction in [mmmm]) versus the catalyst A-derived monometallic control ([mmmm] > 99{\%}). Interestingly, conformationally flexible catalyst B-derived cationic bimetallic Hf catalysts are also known to undergo rapid intramolecular/intermetal methyl exchange and to exhibit strong Hf···Hf cooperative enchainment effects in ethylene homo- and copolymerizations. Steric effects and intramolecular intermetal chain transfer likely both contribute to the increased isotactic polyolefin stereo- and regiodefect content.",
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AU - Marks, Tobin J

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AB - In comparison to monometallic controls, bimetallic olefin polymerization catalysts often exhibit superior performance in terms of higher polyolefin Mw, higher comonomer incorporation, and higher polar comonomer tolerance. However, using cooperating catalyst centers to modulate stereoselectivity in α-olefin polymerizations is relatively unexplored. In this contribution, the monometallic Hf(IV) complex, L1-HfMe2 (catalyst A, L1 = 2,6-diisopropyl-N-{(2-isopropylphenyl)[6-(naphthalen-1-yl)pyridin-2-yl]methyl}aniline), and homo-bimetallic Hf(IV) complexes, L2-Hf2Me5 (catalyst B) and L2-Hf2Me4 (catalyst C) (L2 = N,N′-{[naphthalene-1,4-diylbis(pyridine-6,2-diyl)]bis[(2-isopropylphenyl)methylene)]bis(2,6-diisopropylaniline}), are activated with Ph3C+B(C6F5)4 - and investigated in propylene and 1-octene homopolymerizations. In propylene polymerizations, the conformationally flexible catalyst B-derived bimetallic dicationic catalyst produces higher Mw polypropylene (up to 7.8×), higher total stereo- and regiodefect densities (up to 3.5×), and lower Tm (by as much as ∼14 °C) versus the monometallic catalyst A-derived control. In 1-octene polymerizations, the conformationally flexible catalyst B-derived bimetallic dicationic catalyst induces greatly reduced isotacticity (23% reduction in [mmmm]) versus the catalyst A-derived monometallic control ([mmmm] > 99%). Interestingly, conformationally flexible catalyst B-derived cationic bimetallic Hf catalysts are also known to undergo rapid intramolecular/intermetal methyl exchange and to exhibit strong Hf···Hf cooperative enchainment effects in ethylene homo- and copolymerizations. Steric effects and intramolecular intermetal chain transfer likely both contribute to the increased isotactic polyolefin stereo- and regiodefect content.

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