Living Vinyl Addition Polymerization of Substituted Norbornenes by a t-Bu3P-Ligated Methylpalladium Complex

Dong Gyun Kim; Andrew Bell; Richard A. Register

doi:10.1021/acsmacrolett.5b00079

Living Vinyl Addition Polymerization of Substituted Norbornenes by a t-Bu₃P-Ligated Methylpalladium Complex

Dong Gyun Kim, Andrew Bell, Richard A. Register

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Abstract

The vinyl addition polymerization of substituted norbornene (NB) monomers, via (t-Bu₃P)PdMeCl activated by [Li(OEt₂)_2.5]B(C₆F₅)₄, is investigated. NB monomers bearing alkyl, aryl, fluoroaryl, and even hexafluoroisopropanol substituents yield polymers exhibiting monomodal and narrow molecular weight distributions, with molecular weight controlled by reaction time and monomer to initiator ratio, demonstrating the living nature of these polymerizations. These polymers are soluble in common organic solvents and possess excellent thermal stability. Block copolymers are also prepared via sequential monomer addition; these are the first examples of well-defined block copolymers of substituted NB monomers enchained by vinyl addition polymerization. (Figure Presented).

Original language	English (US)
Pages (from-to)	327-330
Number of pages	4
Journal	ACS Macro Letters
Volume	4
Issue number	3
DOIs	https://doi.org/10.1021/acsmacrolett.5b00079
State	Published - Mar 17 2015

All Science Journal Classification (ASJC) codes

Materials Chemistry
Polymers and Plastics
Inorganic Chemistry
Organic Chemistry

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title = "Living Vinyl Addition Polymerization of Substituted Norbornenes by a t-Bu3P-Ligated Methylpalladium Complex",

abstract = "The vinyl addition polymerization of substituted norbornene (NB) monomers, via (t-Bu3P)PdMeCl activated by [Li(OEt2)2.5]B(C6F5)4, is investigated. NB monomers bearing alkyl, aryl, fluoroaryl, and even hexafluoroisopropanol substituents yield polymers exhibiting monomodal and narrow molecular weight distributions, with molecular weight controlled by reaction time and monomer to initiator ratio, demonstrating the living nature of these polymerizations. These polymers are soluble in common organic solvents and possess excellent thermal stability. Block copolymers are also prepared via sequential monomer addition; these are the first examples of well-defined block copolymers of substituted NB monomers enchained by vinyl addition polymerization. (Figure Presented).",

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T1 - Living Vinyl Addition Polymerization of Substituted Norbornenes by a t-Bu3P-Ligated Methylpalladium Complex

AU - Kim, Dong Gyun

AU - Bell, Andrew

AU - Register, Richard A.

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N2 - The vinyl addition polymerization of substituted norbornene (NB) monomers, via (t-Bu3P)PdMeCl activated by [Li(OEt2)2.5]B(C6F5)4, is investigated. NB monomers bearing alkyl, aryl, fluoroaryl, and even hexafluoroisopropanol substituents yield polymers exhibiting monomodal and narrow molecular weight distributions, with molecular weight controlled by reaction time and monomer to initiator ratio, demonstrating the living nature of these polymerizations. These polymers are soluble in common organic solvents and possess excellent thermal stability. Block copolymers are also prepared via sequential monomer addition; these are the first examples of well-defined block copolymers of substituted NB monomers enchained by vinyl addition polymerization. (Figure Presented).

AB - The vinyl addition polymerization of substituted norbornene (NB) monomers, via (t-Bu3P)PdMeCl activated by [Li(OEt2)2.5]B(C6F5)4, is investigated. NB monomers bearing alkyl, aryl, fluoroaryl, and even hexafluoroisopropanol substituents yield polymers exhibiting monomodal and narrow molecular weight distributions, with molecular weight controlled by reaction time and monomer to initiator ratio, demonstrating the living nature of these polymerizations. These polymers are soluble in common organic solvents and possess excellent thermal stability. Block copolymers are also prepared via sequential monomer addition; these are the first examples of well-defined block copolymers of substituted NB monomers enchained by vinyl addition polymerization. (Figure Presented).

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Living Vinyl Addition Polymerization of Substituted Norbornenes by a t-Bu₃P-Ligated Methylpalladium Complex

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