Nitroxide-Mediated Polymerization of Vinyl Chloride at Low Temperature: Kinetic and Computational Studies

Carlos M.R. Abreu; Patrícia V. Mendonça; Arménio C. Serra; Benjamin B. Noble; Tamaz Guliashvili; Julien Nicolas; Michelle L. Coote; Jorge F.J. Coelho

doi:10.1021/acs.macromol.5b02017

Nitroxide-Mediated Polymerization of Vinyl Chloride at Low Temperature: Kinetic and Computational Studies

Carlos M.R. Abreu, Patrícia V. Mendonça, Arménio C. Serra, Benjamin B. Noble, Tamaz Guliashvili^*, Julien Nicolas, Michelle L. Coote, Jorge F.J. Coelho

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

The synthesis of poly(vinyl chloride) (PVC) by nitroxide-mediated polymerization (NMP) using the SG1-based BlocBuilder alkoxyamine at low temperature (30 and 42 °C) is reported. The reaction system was studied regarding the nature of the solvent, the monomer-to-solvent ratio, the polymerization temperature, and the target molecular weight. First-order kinetics and linear evolutions of the molecular weight with vinyl chloride (VC) conversion were obtained in dichloromethane (DCM) and dimethyl sulfoxide (DMSO) together with decreasing dispersities (Ä?) down to 1.59-1.47. The resulting PVC was fully characterized by ¹H nuclear magnetic resonance spectroscopy (¹H NMR), ³¹P NMR, and size exclusion chromatography (SEC). The ¹H NMR and ³¹P NMR revealed the existence of very small content of structural defects and the presence of chain-end functional groups (∼91% SG1 chain-end functionality). Chain extension experiments were performed with VC, methyl methacrylate (MMA), and a mixture of monomers (90% of MMA and 10% of styrene (S)) and confirmed the "livingness" of the PVC-SG1 macroinitiators, giving access to different PVC-based block copolymers. High level ab initio molecular orbital calculations suggested that the C-O bond in the PVC-SG1 alkoxyamine is too strong to mediate the NMP of VC by simple "classic" activation-deactivation equilibrium and is possibly being mediated by a SG1-mediated dehydrochlorination mechanism. The results presented in this study established a new route to afford a wide range of new complex macrostructures based on PVC segments.

Original language	English
Pages (from-to)	490-498
Number of pages	9
Journal	Macromolecules
Volume	49
Issue number	2
DOIs	https://doi.org/10.1021/acs.macromol.5b02017
Publication status	Published - 26 Jan 2016

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@article{53181285042a474e9642f6be6158ff4f,

title = "Nitroxide-Mediated Polymerization of Vinyl Chloride at Low Temperature: Kinetic and Computational Studies",

abstract = "The synthesis of poly(vinyl chloride) (PVC) by nitroxide-mediated polymerization (NMP) using the SG1-based BlocBuilder alkoxyamine at low temperature (30 and 42 °C) is reported. The reaction system was studied regarding the nature of the solvent, the monomer-to-solvent ratio, the polymerization temperature, and the target molecular weight. First-order kinetics and linear evolutions of the molecular weight with vinyl chloride (VC) conversion were obtained in dichloromethane (DCM) and dimethyl sulfoxide (DMSO) together with decreasing dispersities ({\"A}?) down to 1.59-1.47. The resulting PVC was fully characterized by 1H nuclear magnetic resonance spectroscopy (1H NMR), 31P NMR, and size exclusion chromatography (SEC). The 1H NMR and 31P NMR revealed the existence of very small content of structural defects and the presence of chain-end functional groups (∼91% SG1 chain-end functionality). Chain extension experiments were performed with VC, methyl methacrylate (MMA), and a mixture of monomers (90% of MMA and 10% of styrene (S)) and confirmed the {"}livingness{"} of the PVC-SG1 macroinitiators, giving access to different PVC-based block copolymers. High level ab initio molecular orbital calculations suggested that the C-O bond in the PVC-SG1 alkoxyamine is too strong to mediate the NMP of VC by simple {"}classic{"} activation-deactivation equilibrium and is possibly being mediated by a SG1-mediated dehydrochlorination mechanism. The results presented in this study established a new route to afford a wide range of new complex macrostructures based on PVC segments.",

author = "Abreu, {Carlos M.R.} and Mendon{\c c}a, {Patr{\'i}cia V.} and Serra, {Arm{\'e}nio C.} and Noble, {Benjamin B.} and Tamaz Guliashvili and Julien Nicolas and Coote, {Michelle L.} and Coelho, {Jorge F.J.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = jan,

day = "26",

doi = "10.1021/acs.macromol.5b02017",

language = "English",

volume = "49",

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journal = "Macromolecules",

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publisher = "American Chemical Society",

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T1 - Nitroxide-Mediated Polymerization of Vinyl Chloride at Low Temperature

T2 - Kinetic and Computational Studies

AU - Abreu, Carlos M.R.

AU - Mendonça, Patrícia V.

AU - Serra, Arménio C.

AU - Noble, Benjamin B.

AU - Guliashvili, Tamaz

AU - Nicolas, Julien

AU - Coote, Michelle L.

AU - Coelho, Jorge F.J.

PY - 2016/1/26

Y1 - 2016/1/26

N2 - The synthesis of poly(vinyl chloride) (PVC) by nitroxide-mediated polymerization (NMP) using the SG1-based BlocBuilder alkoxyamine at low temperature (30 and 42 °C) is reported. The reaction system was studied regarding the nature of the solvent, the monomer-to-solvent ratio, the polymerization temperature, and the target molecular weight. First-order kinetics and linear evolutions of the molecular weight with vinyl chloride (VC) conversion were obtained in dichloromethane (DCM) and dimethyl sulfoxide (DMSO) together with decreasing dispersities (Ä?) down to 1.59-1.47. The resulting PVC was fully characterized by 1H nuclear magnetic resonance spectroscopy (1H NMR), 31P NMR, and size exclusion chromatography (SEC). The 1H NMR and 31P NMR revealed the existence of very small content of structural defects and the presence of chain-end functional groups (∼91% SG1 chain-end functionality). Chain extension experiments were performed with VC, methyl methacrylate (MMA), and a mixture of monomers (90% of MMA and 10% of styrene (S)) and confirmed the "livingness" of the PVC-SG1 macroinitiators, giving access to different PVC-based block copolymers. High level ab initio molecular orbital calculations suggested that the C-O bond in the PVC-SG1 alkoxyamine is too strong to mediate the NMP of VC by simple "classic" activation-deactivation equilibrium and is possibly being mediated by a SG1-mediated dehydrochlorination mechanism. The results presented in this study established a new route to afford a wide range of new complex macrostructures based on PVC segments.

AB - The synthesis of poly(vinyl chloride) (PVC) by nitroxide-mediated polymerization (NMP) using the SG1-based BlocBuilder alkoxyamine at low temperature (30 and 42 °C) is reported. The reaction system was studied regarding the nature of the solvent, the monomer-to-solvent ratio, the polymerization temperature, and the target molecular weight. First-order kinetics and linear evolutions of the molecular weight with vinyl chloride (VC) conversion were obtained in dichloromethane (DCM) and dimethyl sulfoxide (DMSO) together with decreasing dispersities (Ä?) down to 1.59-1.47. The resulting PVC was fully characterized by 1H nuclear magnetic resonance spectroscopy (1H NMR), 31P NMR, and size exclusion chromatography (SEC). The 1H NMR and 31P NMR revealed the existence of very small content of structural defects and the presence of chain-end functional groups (∼91% SG1 chain-end functionality). Chain extension experiments were performed with VC, methyl methacrylate (MMA), and a mixture of monomers (90% of MMA and 10% of styrene (S)) and confirmed the "livingness" of the PVC-SG1 macroinitiators, giving access to different PVC-based block copolymers. High level ab initio molecular orbital calculations suggested that the C-O bond in the PVC-SG1 alkoxyamine is too strong to mediate the NMP of VC by simple "classic" activation-deactivation equilibrium and is possibly being mediated by a SG1-mediated dehydrochlorination mechanism. The results presented in this study established a new route to afford a wide range of new complex macrostructures based on PVC segments.

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U2 - 10.1021/acs.macromol.5b02017

DO - 10.1021/acs.macromol.5b02017

M3 - Article

SN - 0024-9297

VL - 49

SP - 490

EP - 498

JO - Macromolecules

JF - Macromolecules

IS - 2

ER -

Nitroxide-Mediated Polymerization of Vinyl Chloride at Low Temperature: Kinetic and Computational Studies

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