Immobilization of η5-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts

Horst Schneider; Gerd T. Puchta; Franz A.R. Kaul; Gabriele Raudaschl-Sieber; Frédéric Lefebvre; Guillaume Saggio; Dimitrios Mihalios; Wolfgang A. Herrmann; Jean Marie Basset

doi:10.1016/S1381-1169(01)00051-6

Immobilization of η⁵-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts

Horst Schneider, Gerd T. Puchta, Franz A.R. Kaul, Gabriele Raudaschl-Sieber, Frédéric Lefebvre, Guillaume Saggio, Dimitrios Mihalios, Wolfgang A. Herrmann^*, Jean Marie Basset

^*Corresponding author for this work

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

32 Scopus citations

Abstract

The modification of a mesoporous silica surface with Si(Ind)(CH₃)₂Cl and the immobilization of CpZr(NMe₂)₃ on this surface was studied via IR-spectroscopy. To reduce side reactions, the indenyl-modified silica was reacted with hexamethyldisilazane (HMDS) under IR-control before the CpZr(NMe₂)₃-immobilization. The role of the hydroxyl group protection with HMDS is discussed. The surface modifications have been repeated via Schlenk technique at the same conditions and the surface modifications were studied with ¹³C CP MAS-NMR, ¹H MAS-NMR, elemental-, SEM- and BET-analysis. The surface species of the resulting catalysts are discussed. The precatalysts have been treated with methylaluminoxane (MAO) (Al:Zr (mol:mol) = 500:1) and the resulting Zr contents (leaching-effect) are discussed. All catalysts have been tested in ethylene and propylene polymerization.

Original language	English (US)
Pages (from-to)	127-141
Number of pages	15
Journal	Journal of Molecular Catalysis A: Chemical
Volume	170
Issue number	1-2
DOIs	https://doi.org/10.1016/S1381-1169(01)00051-6
State	Published - May 14 2001
Externally published	Yes

Keywords

Heterogeneous catalysts
Leaching
Metallocene
Polymerization
Surface chemistry

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

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Schneider, H., Puchta, G. T., Kaul, F. A. R., Raudaschl-Sieber, G., Lefebvre, F., Saggio, G., Mihalios, D., Herrmann, W. A., & Basset, J. M. (2001). Immobilization of η⁵-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts. Journal of Molecular Catalysis A: Chemical, 170(1-2), 127-141. https://doi.org/10.1016/S1381-1169(01)00051-6

Schneider, Horst ; Puchta, Gerd T. ; Kaul, Franz A.R. et al. / Immobilization of η⁵-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface : A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts. In: Journal of Molecular Catalysis A: Chemical. 2001 ; Vol. 170, No. 1-2. pp. 127-141.

@article{be1212c6fff04b45b3f6622b76defea0,

title = "Immobilization of η5-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts",

abstract = "The modification of a mesoporous silica surface with Si(Ind)(CH3)2Cl and the immobilization of CpZr(NMe2)3 on this surface was studied via IR-spectroscopy. To reduce side reactions, the indenyl-modified silica was reacted with hexamethyldisilazane (HMDS) under IR-control before the CpZr(NMe2)3-immobilization. The role of the hydroxyl group protection with HMDS is discussed. The surface modifications have been repeated via Schlenk technique at the same conditions and the surface modifications were studied with 13C CP MAS-NMR, 1H MAS-NMR, elemental-, SEM- and BET-analysis. The surface species of the resulting catalysts are discussed. The precatalysts have been treated with methylaluminoxane (MAO) (Al:Zr (mol:mol) = 500:1) and the resulting Zr contents (leaching-effect) are discussed. All catalysts have been tested in ethylene and propylene polymerization.",

keywords = "Heterogeneous catalysts, Leaching, Metallocene, Polymerization, Surface chemistry",

author = "Horst Schneider and Puchta, {Gerd T.} and Kaul, {Franz A.R.} and Gabriele Raudaschl-Sieber and Fr{\'e}d{\'e}ric Lefebvre and Guillaume Saggio and Dimitrios Mihalios and Herrmann, {Wolfgang A.} and Basset, {Jean Marie}",

year = "2001",

month = may,

day = "14",

doi = "10.1016/S1381-1169(01)00051-6",

language = "English (US)",

volume = "170",

pages = "127--141",

journal = "Journal of Molecular Catalysis A: Chemical",

issn = "1381-1169",

publisher = "Elsevier B.V.",

number = "1-2",

}

Schneider, H, Puchta, GT, Kaul, FAR, Raudaschl-Sieber, G, Lefebvre, F, Saggio, G, Mihalios, D, Herrmann, WA & Basset, JM 2001, 'Immobilization of η⁵-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts', Journal of Molecular Catalysis A: Chemical, vol. 170, no. 1-2, pp. 127-141. https://doi.org/10.1016/S1381-1169(01)00051-6

Immobilization of η⁵-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts. / Schneider, Horst; Puchta, Gerd T.; Kaul, Franz A.R. et al.
In: Journal of Molecular Catalysis A: Chemical, Vol. 170, No. 1-2, 14.05.2001, p. 127-141.

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

TY - JOUR

T1 - Immobilization of η5-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface

T2 - A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts

AU - Schneider, Horst

AU - Puchta, Gerd T.

AU - Kaul, Franz A.R.

AU - Raudaschl-Sieber, Gabriele

AU - Lefebvre, Frédéric

AU - Saggio, Guillaume

AU - Mihalios, Dimitrios

AU - Herrmann, Wolfgang A.

AU - Basset, Jean Marie

PY - 2001/5/14

Y1 - 2001/5/14

N2 - The modification of a mesoporous silica surface with Si(Ind)(CH3)2Cl and the immobilization of CpZr(NMe2)3 on this surface was studied via IR-spectroscopy. To reduce side reactions, the indenyl-modified silica was reacted with hexamethyldisilazane (HMDS) under IR-control before the CpZr(NMe2)3-immobilization. The role of the hydroxyl group protection with HMDS is discussed. The surface modifications have been repeated via Schlenk technique at the same conditions and the surface modifications were studied with 13C CP MAS-NMR, 1H MAS-NMR, elemental-, SEM- and BET-analysis. The surface species of the resulting catalysts are discussed. The precatalysts have been treated with methylaluminoxane (MAO) (Al:Zr (mol:mol) = 500:1) and the resulting Zr contents (leaching-effect) are discussed. All catalysts have been tested in ethylene and propylene polymerization.

AB - The modification of a mesoporous silica surface with Si(Ind)(CH3)2Cl and the immobilization of CpZr(NMe2)3 on this surface was studied via IR-spectroscopy. To reduce side reactions, the indenyl-modified silica was reacted with hexamethyldisilazane (HMDS) under IR-control before the CpZr(NMe2)3-immobilization. The role of the hydroxyl group protection with HMDS is discussed. The surface modifications have been repeated via Schlenk technique at the same conditions and the surface modifications were studied with 13C CP MAS-NMR, 1H MAS-NMR, elemental-, SEM- and BET-analysis. The surface species of the resulting catalysts are discussed. The precatalysts have been treated with methylaluminoxane (MAO) (Al:Zr (mol:mol) = 500:1) and the resulting Zr contents (leaching-effect) are discussed. All catalysts have been tested in ethylene and propylene polymerization.

KW - Heterogeneous catalysts

KW - Leaching

KW - Metallocene

KW - Polymerization

KW - Surface chemistry

UR - http://www.scopus.com/inward/record.url?scp=0035858764&partnerID=8YFLogxK

U2 - 10.1016/S1381-1169(01)00051-6

DO - 10.1016/S1381-1169(01)00051-6

M3 - Article

AN - SCOPUS:0035858764

SN - 1381-1169

VL - 170

SP - 127

EP - 141

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

IS - 1-2

ER -

Schneider H, Puchta GT, Kaul FAR, Raudaschl-Sieber G, Lefebvre F, Saggio G et al. Immobilization of η⁵-cyclopentadienyltris(dimethylamido) zirconium polymerization catalysts on a chlorosilane- and HMDS-modified mesoporous silica surface: A new concept for supporting metallocene amides towards heterogeneous single-site-catalysts. Journal of Molecular Catalysis A: Chemical. 2001 May 14;170(1-2):127-141. doi: 10.1016/S1381-1169(01)00051-6