Organolanthanide-Mediated Silanolytic Chain Transfer Processes. Scope and Mechanism of Single Reactor Catalytic Routes to Silapolyolefins

Organolanthanide-Mediated Silanolytic Chain Transfer Processes. Scope and Mechanism of Single Reactor Catalytic Routes to Silapolyolefins

This paper reports efficient and selective silanolytic (PhSiH3, n-BuSiH3, C6H5CH2SiH3) chain transfer in organolanthanide-catalyzed homogeneous ethylene polymerization and ethylene copolymerization with several α-olefins. The result is a series of silyl-capped polyolefins which have been characteriz...

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Veröffentlicht in:Macromolecules 1999-02, Vol.32 (4), p.981-988
Hauptverfasser: Koo, Kwangmo, Fu, Peng-Fei, Marks, Tobin J
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Sprache:eng
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Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
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container_title Macromolecules
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creator Koo, Kwangmo
Fu, Peng-Fei
Marks, Tobin J
description This paper reports efficient and selective silanolytic (PhSiH3, n-BuSiH3, C6H5CH2SiH3) chain transfer in organolanthanide-catalyzed homogeneous ethylene polymerization and ethylene copolymerization with several α-olefins. The result is a series of silyl-capped polyolefins which have been characterized by 1H/13C NMR and IR spectroscopy as well as by GPC. In [(Me5C5)2LnH]2/[Me2Si(Me4C5)2LnH]2-mediated ethylene homopolymerization and ethylene copolymerization, both primary arylsilanes (PhSiH3) and alkylsilanes (n-BuSiH3, C6H5CH2SiH3) function as efficient chain-transfer agents. In the case of ethylene polymerization mediated by [(Me5C5)2SmH]2, the mechanism of chain transfer is supported by the observation that M n of the capped polyethylenes formed at constant [catalyst], [PhSiH3], [ethylene] is inversely proportional to [PhSiH3]. Using silane-activated Me2Si(Me4C5)2LnCH(SiMe3)2 precatalysts, this chain-transfer process also efficiently produces silyl-endcapped ethylene + 1-hexene copolymers and ethylene + styrene copolymers.
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In the case of ethylene polymerization mediated by [(Me5C5)2SmH]2, the mechanism of chain transfer is supported by the observation that M n of the capped polyethylenes formed at constant [catalyst], [PhSiH3], [ethylene] is inversely proportional to [PhSiH3]. Using silane-activated Me2Si(Me4C5)2LnCH(SiMe3)2 precatalysts, this chain-transfer process also efficiently produces silyl-endcapped ethylene + 1-hexene copolymers and ethylene + styrene copolymers.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ma981462o</doi><tpages>8</tpages></addata></record>
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subjects Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
title Organolanthanide-Mediated Silanolytic Chain Transfer Processes. Scope and Mechanism of Single Reactor Catalytic Routes to Silapolyolefins
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