Ethylene polymerization on a SiH4-modified Phillips catalyst: detection of in situ produced α-olefins by operando FT-IR spectroscopy

被引：26

作者：

Barzan, Caterina ^{[1
,2
]}

Groppo, Elena ^{[1
,2
]}

Quadrelli, Elsje Alessandra ^{[3
]}

Monteil, Vincent ^{[3
]}

Bordiga, Silvia ^{[1
,2
]}

机构：

[1] Univ Turin, NIS Ctr Excellence, Dept Inorgan Phys & Mat Chem, I-10135 Turin, Italy

[2] Univ Turin, INSTM Unita Torino, I-10135 Turin, Italy

[3] Univ Lyon 1, CNRS, CPE Lyon, UMR 5265, F-69616 Villeurbanne, France

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2012年 / 14卷 / 07期

关键词：

OXIDE SURFACES; CR(II) SITES; SILICA; CHROMIUM; MECHANISM; CENTERS; INITIATION; CHEMISTRY; SYSTEM; IONS;

D O I：

10.1039/c2cp23269c

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Ethylene polymerization on a model Cr(II)/SiO2 Phillips catalyst modified with gas phase SiH4 leads to a waxy product containing a bimodal MW distribution of alpha-olefins (M-w < 3000 g mol(-1)) and a highly branched polyethylene, LLDPE (M-w approximate to 10(5) g mol(-1), T-m = 123 degrees C), contrary to the unmodified catalyst which gives a linear and more dense PE, HDPE (M-w = 86 000 g mol(-1) (PDI = 7), Tm = 134 degrees C). Pressure and temperature resolved FT-IR spectroscopy under operando conditions (T = 130-230 K) allows us to detect alpha-olefins, and in particular 1-hexene and 1-butene (characteristic IR absorption bands at 3581-3574, 1638 and 1598 cm(-1)) as intermediate species before their incorporation in the polymer chains. The polymerization rate is estimated, using time resolved FT-IR spectroscopy, to be 7 times higher on the SiH4-modified Phillips catalyst with respect to the unmodified one.

引用

页码：2239 / 2245

页数：7

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