Silicon-modified Ziegler-Natta polymerization. Catalytic approaches to silyl-capped and silyl-linked polyolefins using 'single-site' cationic Ziegler-Natta catalysts

Kwangmo Koo, Tobin J Marks

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64 Citations (Scopus)

Abstract

This contribution reports-efficient and selective organotitanium- mediated silanolytic (PhSiH3, PhMeSiH2, Me2SiH2, Et2SiH2) chain transfer in the homogeneous polymerization and copolymerization of a variety of α-olefins. The result is several broad classes of silyl-capped and silyl- linked polyolefins which have been characterized by 1H/13C/29Si NMR and IR spectroscopy as well as by GPC. 'Single-site' Ziegler-Natta catalysts effect this chain transfer with significant efficiency and scope. For [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 --mediated propylene polymerization, the mechanism of chain transfer is supported by the observation that M(n) of the capped atactic polypropylenes produced at constant [catalyst], [PhSiH3], and [propylene] is inversely proportional to [PhSiH3]. Using the same catalyst, this process also efficiently produces silyl endcapped poly(1- hexene), ethylene + 1-hexene copolymers, ethylene + styrene copolymers (both with high degrees of comonomer incorporation), and (at low temperatures) polyethylene. In the case of rac-C2H4(ind)2TiMe+B-(C6F5)4 - + propylene and (Me5C5)TiMe2+B(C6F5)4 - + styrene, PhH2Si-functionalized isotatic polypropylene and syndiotactic polystyrene, respectively, are produced. Using 1,4-disilabenzene and 1,3,5-trisilabenzene as chain-transfer agents in the presence of [Me2Si(Me4C5)1BuN]TiMe+B(C6F5)4 - + propylene, linear diblock and starlike atactic polypropylene structures, respectively, are produced. In addition to primary silanes, secondary silanes (PhMeSiH2, Me2SiH2, Et2SiH2) are efficient and selective chain-transfer agents in this organotitanium-mediated polymerization. In the presence of [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 - + propylene, (Me5C5)TiMe2 +B(C6F5)4 - + propylene, and (Me5C5)TiMe2 +B(C6F5)4 - + styrene, PhMeHSi- or Me2HSi-capped atactic polypropylene and PhMeHSi-, Me2HSi-, or Et2HSi-capped syndiotactic polystyrene are produced, respectively. Using PhH2Si-capped polypropylene as a chain-transfer agent, an atactic polypropylene-syndiotactic polystyrene AB block copolymer is produced in the presence of (Me5C5)TiMe2 +B(C6F5)4 - + styrene.

Original languageEnglish
Pages (from-to)8791-8802
Number of pages12
JournalJournal of the American Chemical Society
Volume121
Issue number38
DOIs
Publication statusPublished - Sep 29 1999

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Polypropylenes
Polyolefins
Silicon
Polymerization
Propylene
Catalysts
Styrene
Polystyrenes
Silanes
Ethylene
Copolymers
Alkenes
Polyethylene
Copolymerization
Nuclear magnetic resonance spectroscopy
Olefins
Block copolymers
PL 732
propylene
Polyethylenes

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{c3757fade1a94b2c8b41fabcacc67bb5,
title = "Silicon-modified Ziegler-Natta polymerization. Catalytic approaches to silyl-capped and silyl-linked polyolefins using 'single-site' cationic Ziegler-Natta catalysts",
abstract = "This contribution reports-efficient and selective organotitanium- mediated silanolytic (PhSiH3, PhMeSiH2, Me2SiH2, Et2SiH2) chain transfer in the homogeneous polymerization and copolymerization of a variety of α-olefins. The result is several broad classes of silyl-capped and silyl- linked polyolefins which have been characterized by 1H/13C/29Si NMR and IR spectroscopy as well as by GPC. 'Single-site' Ziegler-Natta catalysts effect this chain transfer with significant efficiency and scope. For [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 --mediated propylene polymerization, the mechanism of chain transfer is supported by the observation that M(n) of the capped atactic polypropylenes produced at constant [catalyst], [PhSiH3], and [propylene] is inversely proportional to [PhSiH3]. Using the same catalyst, this process also efficiently produces silyl endcapped poly(1- hexene), ethylene + 1-hexene copolymers, ethylene + styrene copolymers (both with high degrees of comonomer incorporation), and (at low temperatures) polyethylene. In the case of rac-C2H4(ind)2TiMe+B-(C6F5)4 - + propylene and (Me5C5)TiMe2+B(C6F5)4 - + styrene, PhH2Si-functionalized isotatic polypropylene and syndiotactic polystyrene, respectively, are produced. Using 1,4-disilabenzene and 1,3,5-trisilabenzene as chain-transfer agents in the presence of [Me2Si(Me4C5)1BuN]TiMe+B(C6F5)4 - + propylene, linear diblock and starlike atactic polypropylene structures, respectively, are produced. In addition to primary silanes, secondary silanes (PhMeSiH2, Me2SiH2, Et2SiH2) are efficient and selective chain-transfer agents in this organotitanium-mediated polymerization. In the presence of [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 - + propylene, (Me5C5)TiMe2 +B(C6F5)4 - + propylene, and (Me5C5)TiMe2 +B(C6F5)4 - + styrene, PhMeHSi- or Me2HSi-capped atactic polypropylene and PhMeHSi-, Me2HSi-, or Et2HSi-capped syndiotactic polystyrene are produced, respectively. Using PhH2Si-capped polypropylene as a chain-transfer agent, an atactic polypropylene-syndiotactic polystyrene AB block copolymer is produced in the presence of (Me5C5)TiMe2 +B(C6F5)4 - + styrene.",
author = "Kwangmo Koo and Marks, {Tobin J}",
year = "1999",
month = "9",
day = "29",
doi = "10.1021/ja990617k",
language = "English",
volume = "121",
pages = "8791--8802",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "38",

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TY - JOUR

T1 - Silicon-modified Ziegler-Natta polymerization. Catalytic approaches to silyl-capped and silyl-linked polyolefins using 'single-site' cationic Ziegler-Natta catalysts

AU - Koo, Kwangmo

AU - Marks, Tobin J

PY - 1999/9/29

Y1 - 1999/9/29

N2 - This contribution reports-efficient and selective organotitanium- mediated silanolytic (PhSiH3, PhMeSiH2, Me2SiH2, Et2SiH2) chain transfer in the homogeneous polymerization and copolymerization of a variety of α-olefins. The result is several broad classes of silyl-capped and silyl- linked polyolefins which have been characterized by 1H/13C/29Si NMR and IR spectroscopy as well as by GPC. 'Single-site' Ziegler-Natta catalysts effect this chain transfer with significant efficiency and scope. For [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 --mediated propylene polymerization, the mechanism of chain transfer is supported by the observation that M(n) of the capped atactic polypropylenes produced at constant [catalyst], [PhSiH3], and [propylene] is inversely proportional to [PhSiH3]. Using the same catalyst, this process also efficiently produces silyl endcapped poly(1- hexene), ethylene + 1-hexene copolymers, ethylene + styrene copolymers (both with high degrees of comonomer incorporation), and (at low temperatures) polyethylene. In the case of rac-C2H4(ind)2TiMe+B-(C6F5)4 - + propylene and (Me5C5)TiMe2+B(C6F5)4 - + styrene, PhH2Si-functionalized isotatic polypropylene and syndiotactic polystyrene, respectively, are produced. Using 1,4-disilabenzene and 1,3,5-trisilabenzene as chain-transfer agents in the presence of [Me2Si(Me4C5)1BuN]TiMe+B(C6F5)4 - + propylene, linear diblock and starlike atactic polypropylene structures, respectively, are produced. In addition to primary silanes, secondary silanes (PhMeSiH2, Me2SiH2, Et2SiH2) are efficient and selective chain-transfer agents in this organotitanium-mediated polymerization. In the presence of [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 - + propylene, (Me5C5)TiMe2 +B(C6F5)4 - + propylene, and (Me5C5)TiMe2 +B(C6F5)4 - + styrene, PhMeHSi- or Me2HSi-capped atactic polypropylene and PhMeHSi-, Me2HSi-, or Et2HSi-capped syndiotactic polystyrene are produced, respectively. Using PhH2Si-capped polypropylene as a chain-transfer agent, an atactic polypropylene-syndiotactic polystyrene AB block copolymer is produced in the presence of (Me5C5)TiMe2 +B(C6F5)4 - + styrene.

AB - This contribution reports-efficient and selective organotitanium- mediated silanolytic (PhSiH3, PhMeSiH2, Me2SiH2, Et2SiH2) chain transfer in the homogeneous polymerization and copolymerization of a variety of α-olefins. The result is several broad classes of silyl-capped and silyl- linked polyolefins which have been characterized by 1H/13C/29Si NMR and IR spectroscopy as well as by GPC. 'Single-site' Ziegler-Natta catalysts effect this chain transfer with significant efficiency and scope. For [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 --mediated propylene polymerization, the mechanism of chain transfer is supported by the observation that M(n) of the capped atactic polypropylenes produced at constant [catalyst], [PhSiH3], and [propylene] is inversely proportional to [PhSiH3]. Using the same catalyst, this process also efficiently produces silyl endcapped poly(1- hexene), ethylene + 1-hexene copolymers, ethylene + styrene copolymers (both with high degrees of comonomer incorporation), and (at low temperatures) polyethylene. In the case of rac-C2H4(ind)2TiMe+B-(C6F5)4 - + propylene and (Me5C5)TiMe2+B(C6F5)4 - + styrene, PhH2Si-functionalized isotatic polypropylene and syndiotactic polystyrene, respectively, are produced. Using 1,4-disilabenzene and 1,3,5-trisilabenzene as chain-transfer agents in the presence of [Me2Si(Me4C5)1BuN]TiMe+B(C6F5)4 - + propylene, linear diblock and starlike atactic polypropylene structures, respectively, are produced. In addition to primary silanes, secondary silanes (PhMeSiH2, Me2SiH2, Et2SiH2) are efficient and selective chain-transfer agents in this organotitanium-mediated polymerization. In the presence of [Me2Si(Me4C5)(t)BuN]TiMe+B(C6F5)4 - + propylene, (Me5C5)TiMe2 +B(C6F5)4 - + propylene, and (Me5C5)TiMe2 +B(C6F5)4 - + styrene, PhMeHSi- or Me2HSi-capped atactic polypropylene and PhMeHSi-, Me2HSi-, or Et2HSi-capped syndiotactic polystyrene are produced, respectively. Using PhH2Si-capped polypropylene as a chain-transfer agent, an atactic polypropylene-syndiotactic polystyrene AB block copolymer is produced in the presence of (Me5C5)TiMe2 +B(C6F5)4 - + styrene.

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