d0/fn-mediated ring-opening Ziegler polymerization (ROZP) and copolymerization with mono- and disubstituted methylenecyclopropanes. Diverse mechanisms and a new chain-capping termination process

Tryg R. Jensen, James J. O'Donnell, Tobin J Marks

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23 Citations (Scopus)

Abstract

The mono- and disubstituted methylenecyclopropane derivatives 2-phenyl-1-methylene-cyclopropane (A) and 7-methylenebicyclo[4.1.0]heptane (B) have been successfully implemented in ring-opening Ziegler polymerization. Homogeneous ethylene + 2-phenyl-1-methylenecyclopropane (A) random copolymerizations are mediated efficiently by the single-site catalysts Cp*2ZrMe+B(C6F5) 4-, [Cp*2LuH]2, [Cp*2SmH]2, and [Cp*2 YH]2 (Cp* = C5Me5) to produce a copolymer (C) with A enchained in a ring-opened fashion. Single-site coordinative polymerization of 7-methylenebicyclo[4.1.0]heptane (B) proceeds via either ring-opened or ring-unopened pathways. In the presence of Cp*2ZrMe+ MeB(C6F5) 3- at 0°C, B undergoes polymerization to afford the insoluble, ring-unopened homopolymer D, which was characterized by CPMAS NMR, DSC, elemental analysis, FTIR, TGA, and XRD. The melting point of polymer D lies above its decomposition temperature (> 300°C). Random copolymerizations of B and ethylene mediated by Cp*2 ZrMe+MeB(C6F5)3- at room temperature result in polymer E, a polyethylene capped by a ring-opened B fragment. The formation of B-capped polymer E is a consequence of a new chain transfer mechanism, as evidenced by a linear relationship between Mn and [B]-1. The rate constant for insertion of ethylene is ∼25× greater than the rate constant for insertion of monomer B into the metal-alkyl bond. Random copolymers (F) of ring-opened B and ethylene are produced when the catalysts Me2Si(Me4C5)(tBuN)ZrMe2, Me2Si(Me4C5)(tBuN)TiMe2 (activated by either (C6H5)3C+ B(C6F5)4- or B(C6F5)3), and [Cp*2LuH]2 are employed.

Original languageEnglish
Pages (from-to)740-754
Number of pages15
JournalOrganometallics
Volume23
Issue number4
DOIs
Publication statusPublished - Feb 16 2004

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Ring opening polymerization
copolymerization
Copolymerization
polymerization
Heptanes
Polymers
rings
ethylene
Rate constants
Copolymers
Polymerization
Catalysts
heptanes
Polyethylene
Homopolymerization
insertion
copolymers
polymers
Melting point
Monomers

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

@article{f50b4bd3891142b98e61f300ebc50366,
title = "d0/fn-mediated ring-opening Ziegler polymerization (ROZP) and copolymerization with mono- and disubstituted methylenecyclopropanes. Diverse mechanisms and a new chain-capping termination process",
abstract = "The mono- and disubstituted methylenecyclopropane derivatives 2-phenyl-1-methylene-cyclopropane (A) and 7-methylenebicyclo[4.1.0]heptane (B) have been successfully implemented in ring-opening Ziegler polymerization. Homogeneous ethylene + 2-phenyl-1-methylenecyclopropane (A) random copolymerizations are mediated efficiently by the single-site catalysts Cp*2ZrMe+B(C6F5) 4-, [Cp*2LuH]2, [Cp*2SmH]2, and [Cp*2 YH]2 (Cp* = C5Me5) to produce a copolymer (C) with A enchained in a ring-opened fashion. Single-site coordinative polymerization of 7-methylenebicyclo[4.1.0]heptane (B) proceeds via either ring-opened or ring-unopened pathways. In the presence of Cp*2ZrMe+ MeB(C6F5) 3- at 0°C, B undergoes polymerization to afford the insoluble, ring-unopened homopolymer D, which was characterized by CPMAS NMR, DSC, elemental analysis, FTIR, TGA, and XRD. The melting point of polymer D lies above its decomposition temperature (> 300°C). Random copolymerizations of B and ethylene mediated by Cp*2 ZrMe+MeB(C6F5)3- at room temperature result in polymer E, a polyethylene capped by a ring-opened B fragment. The formation of B-capped polymer E is a consequence of a new chain transfer mechanism, as evidenced by a linear relationship between Mn and [B]-1. The rate constant for insertion of ethylene is ∼25× greater than the rate constant for insertion of monomer B into the metal-alkyl bond. Random copolymers (F) of ring-opened B and ethylene are produced when the catalysts Me2Si(Me4C5)(tBuN)ZrMe2, Me2Si(Me4C5)(tBuN)TiMe2 (activated by either (C6H5)3C+ B(C6F5)4- or B(C6F5)3), and [Cp*2LuH]2 are employed.",
author = "Jensen, {Tryg R.} and O'Donnell, {James J.} and Marks, {Tobin J}",
year = "2004",
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T1 - d0/fn-mediated ring-opening Ziegler polymerization (ROZP) and copolymerization with mono- and disubstituted methylenecyclopropanes. Diverse mechanisms and a new chain-capping termination process

AU - Jensen, Tryg R.

AU - O'Donnell, James J.

AU - Marks, Tobin J

PY - 2004/2/16

Y1 - 2004/2/16

N2 - The mono- and disubstituted methylenecyclopropane derivatives 2-phenyl-1-methylene-cyclopropane (A) and 7-methylenebicyclo[4.1.0]heptane (B) have been successfully implemented in ring-opening Ziegler polymerization. Homogeneous ethylene + 2-phenyl-1-methylenecyclopropane (A) random copolymerizations are mediated efficiently by the single-site catalysts Cp*2ZrMe+B(C6F5) 4-, [Cp*2LuH]2, [Cp*2SmH]2, and [Cp*2 YH]2 (Cp* = C5Me5) to produce a copolymer (C) with A enchained in a ring-opened fashion. Single-site coordinative polymerization of 7-methylenebicyclo[4.1.0]heptane (B) proceeds via either ring-opened or ring-unopened pathways. In the presence of Cp*2ZrMe+ MeB(C6F5) 3- at 0°C, B undergoes polymerization to afford the insoluble, ring-unopened homopolymer D, which was characterized by CPMAS NMR, DSC, elemental analysis, FTIR, TGA, and XRD. The melting point of polymer D lies above its decomposition temperature (> 300°C). Random copolymerizations of B and ethylene mediated by Cp*2 ZrMe+MeB(C6F5)3- at room temperature result in polymer E, a polyethylene capped by a ring-opened B fragment. The formation of B-capped polymer E is a consequence of a new chain transfer mechanism, as evidenced by a linear relationship between Mn and [B]-1. The rate constant for insertion of ethylene is ∼25× greater than the rate constant for insertion of monomer B into the metal-alkyl bond. Random copolymers (F) of ring-opened B and ethylene are produced when the catalysts Me2Si(Me4C5)(tBuN)ZrMe2, Me2Si(Me4C5)(tBuN)TiMe2 (activated by either (C6H5)3C+ B(C6F5)4- or B(C6F5)3), and [Cp*2LuH]2 are employed.

AB - The mono- and disubstituted methylenecyclopropane derivatives 2-phenyl-1-methylene-cyclopropane (A) and 7-methylenebicyclo[4.1.0]heptane (B) have been successfully implemented in ring-opening Ziegler polymerization. Homogeneous ethylene + 2-phenyl-1-methylenecyclopropane (A) random copolymerizations are mediated efficiently by the single-site catalysts Cp*2ZrMe+B(C6F5) 4-, [Cp*2LuH]2, [Cp*2SmH]2, and [Cp*2 YH]2 (Cp* = C5Me5) to produce a copolymer (C) with A enchained in a ring-opened fashion. Single-site coordinative polymerization of 7-methylenebicyclo[4.1.0]heptane (B) proceeds via either ring-opened or ring-unopened pathways. In the presence of Cp*2ZrMe+ MeB(C6F5) 3- at 0°C, B undergoes polymerization to afford the insoluble, ring-unopened homopolymer D, which was characterized by CPMAS NMR, DSC, elemental analysis, FTIR, TGA, and XRD. The melting point of polymer D lies above its decomposition temperature (> 300°C). Random copolymerizations of B and ethylene mediated by Cp*2 ZrMe+MeB(C6F5)3- at room temperature result in polymer E, a polyethylene capped by a ring-opened B fragment. The formation of B-capped polymer E is a consequence of a new chain transfer mechanism, as evidenced by a linear relationship between Mn and [B]-1. The rate constant for insertion of ethylene is ∼25× greater than the rate constant for insertion of monomer B into the metal-alkyl bond. Random copolymers (F) of ring-opened B and ethylene are produced when the catalysts Me2Si(Me4C5)(tBuN)ZrMe2, Me2Si(Me4C5)(tBuN)TiMe2 (activated by either (C6H5)3C+ B(C6F5)4- or B(C6F5)3), and [Cp*2LuH]2 are employed.

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