Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts

Hongbo Li; Liting Li; Tobin J. Marks; Louise Liable-Sands; Arnold L. Rheingold

doi:10.1021/ja036289c

Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts

Hongbo Li, Liting Li, Tobin J. Marks^*, Louise Liable-Sands, Arnold L. Rheingold

^*Corresponding author for this work

Chemistry

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

135 Scopus citations

Abstract

This Communication describes the implementation of a new binuclear homometallic organotitanium "constrained geometry catalyst" (CGC), (μ-CH₂CH₂-3,3′){ (η⁵-indenyl )[1-Me₂Si (^tBuN)](TiMe₂)}₂[EBICGC(TiMe₂)₂; Ti₂], together with the bifunctional activators (Ph₃C⁺)₂[1,4-(C₆F₅)₃BC₆F₄B(C₆F₅)₃]^2- (B₂) and new bisborane 1,4-(C₆F₅)₂BC₆F₄B(C₆F₅)₂ (BN₂) in ethylene + α-olefin copolymerization processes. Specifically examined are the comonomers 1-octene and poorly responsive isobutene. Large increases in comonomer enchainment efficiency into the polyethylene microstructure are observed versus the corresponding mononuclear catalyst [1-Me₂Si(3-ethylindenyl)(^tBuN)]TiMe₂ (Ti₁) + Ph₃C⁺B(C₆F₅)₄^- (B₁) or B(C₆F₅)₃ (BN) under identical polymerization conditions. In ethylene + 1-octene copolymerization, 11 times more 1-octene incorporation is observed for Ti₂ + B₂ vs Ti₁ + B₁. In ethylene + isobutene copolymerization, 5 times more isobutene incorporation is observed for Ti₂ + BN₂ vs Ti₁ + BN.

Original language	English (US)
Pages (from-to)	10788-10789
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	125
Issue number	36
DOIs	https://doi.org/10.1021/ja036289c
State	Published - Sep 10 2003

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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CCDC 221297: Experimental Crystal Structure Determination
Li, H. (Creator), Li, L. (Creator), Marks, T. J. (Creator), Liable-Sands, L. (Creator) & Rheingold, A. L. (Creator), Cambridge Crystallographic Data Centre, 2004
DOI: 10.5517/cc7f8mj, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc7f8mj&sid=DataCite
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Li, H., Li, L., Marks, T. J., Liable-Sands, L., & Rheingold, A. L. (2003). Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts. Journal of the American Chemical Society, 125(36), 10788-10789. https://doi.org/10.1021/ja036289c

@article{56b16b9559a8444095230757eec1c8cb,

title = "Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts",

abstract = "This Communication describes the implementation of a new binuclear homometallic organotitanium {"}constrained geometry catalyst{"} (CGC), (μ-CH2CH2-3,3′){ (η5-indenyl )[1-Me2Si (tBuN)](TiMe2)}2[EBICGC(TiMe2)2; Ti2], together with the bifunctional activators (Ph3C+)2[1,4-(C6F5)3BC6F4B(C6F5)3]2- (B2) and new bisborane 1,4-(C6F5)2BC6F4B(C6F5)2 (BN2) in ethylene + α-olefin copolymerization processes. Specifically examined are the comonomers 1-octene and poorly responsive isobutene. Large increases in comonomer enchainment efficiency into the polyethylene microstructure are observed versus the corresponding mononuclear catalyst [1-Me2Si(3-ethylindenyl)(tBuN)]TiMe2 (Ti1) + Ph3C+B(C6F5)4- (B1) or B(C6F5)3 (BN) under identical polymerization conditions. In ethylene + 1-octene copolymerization, 11 times more 1-octene incorporation is observed for Ti2 + B2 vs Ti1 + B1. In ethylene + isobutene copolymerization, 5 times more isobutene incorporation is observed for Ti2 + BN2 vs Ti1 + BN.",

author = "Hongbo Li and Liting Li and Marks, {Tobin J.} and Louise Liable-Sands and Rheingold, {Arnold L.}",

year = "2003",

month = sep,

day = "10",

doi = "10.1021/ja036289c",

language = "English (US)",

volume = "125",

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Li, H, Li, L, Marks, TJ, Liable-Sands, L & Rheingold, AL 2003, 'Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts', Journal of the American Chemical Society, vol. 125, no. 36, pp. 10788-10789. https://doi.org/10.1021/ja036289c

Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts. / Li, Hongbo; Li, Liting; Marks, Tobin J. et al.
In: Journal of the American Chemical Society, Vol. 125, No. 36, 10.09.2003, p. 10788-10789.

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

TY - JOUR

T1 - Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts

AU - Li, Hongbo

AU - Li, Liting

AU - Marks, Tobin J.

AU - Liable-Sands, Louise

AU - Rheingold, Arnold L.

PY - 2003/9/10

Y1 - 2003/9/10

N2 - This Communication describes the implementation of a new binuclear homometallic organotitanium "constrained geometry catalyst" (CGC), (μ-CH2CH2-3,3′){ (η5-indenyl )[1-Me2Si (tBuN)](TiMe2)}2[EBICGC(TiMe2)2; Ti2], together with the bifunctional activators (Ph3C+)2[1,4-(C6F5)3BC6F4B(C6F5)3]2- (B2) and new bisborane 1,4-(C6F5)2BC6F4B(C6F5)2 (BN2) in ethylene + α-olefin copolymerization processes. Specifically examined are the comonomers 1-octene and poorly responsive isobutene. Large increases in comonomer enchainment efficiency into the polyethylene microstructure are observed versus the corresponding mononuclear catalyst [1-Me2Si(3-ethylindenyl)(tBuN)]TiMe2 (Ti1) + Ph3C+B(C6F5)4- (B1) or B(C6F5)3 (BN) under identical polymerization conditions. In ethylene + 1-octene copolymerization, 11 times more 1-octene incorporation is observed for Ti2 + B2 vs Ti1 + B1. In ethylene + isobutene copolymerization, 5 times more isobutene incorporation is observed for Ti2 + BN2 vs Ti1 + BN.

AB - This Communication describes the implementation of a new binuclear homometallic organotitanium "constrained geometry catalyst" (CGC), (μ-CH2CH2-3,3′){ (η5-indenyl )[1-Me2Si (tBuN)](TiMe2)}2[EBICGC(TiMe2)2; Ti2], together with the bifunctional activators (Ph3C+)2[1,4-(C6F5)3BC6F4B(C6F5)3]2- (B2) and new bisborane 1,4-(C6F5)2BC6F4B(C6F5)2 (BN2) in ethylene + α-olefin copolymerization processes. Specifically examined are the comonomers 1-octene and poorly responsive isobutene. Large increases in comonomer enchainment efficiency into the polyethylene microstructure are observed versus the corresponding mononuclear catalyst [1-Me2Si(3-ethylindenyl)(tBuN)]TiMe2 (Ti1) + Ph3C+B(C6F5)4- (B1) or B(C6F5)3 (BN) under identical polymerization conditions. In ethylene + 1-octene copolymerization, 11 times more 1-octene incorporation is observed for Ti2 + B2 vs Ti1 + B1. In ethylene + isobutene copolymerization, 5 times more isobutene incorporation is observed for Ti2 + BN2 vs Ti1 + BN.

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Li H, Li L, Marks TJ, Liable-Sands L, Rheingold AL. Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts. Journal of the American Chemical Society. 2003 Sep 10;125(36):10788-10789. doi: 10.1021/ja036289c

Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization. Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts

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CCDC 221297: Experimental Crystal Structure Determination

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