Accessible microstructures of polybutadiene by anionic polymerization

Forens, Antoine; Roos, Kévin; Dire, Charlotte; Gadenne, Benoit; Carlotti, Stéphane

doi:10.1016/j.polymer.2018.07.071

Cited by 28 publications

(30 citation statements)

References 49 publications

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“…These reticulated chains are a signature of the PB manufacturing process. 18 . Similarly for PI, the major family of oligomers with the highest intensity [(C8H12)O4 + (C5H8)n + 7 Li + ] expands from one monomer of PI at m/z 247.1516 (C13H20O4 + 7 Li + ) up to 20 monomers at m/z 1540.3410 (C108H172O4 + 7 Li + ).…”

Section: Resultsmentioning

confidence: 99%

Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Comparison with Pyrolysis-Comprehensive Two-Dimensional Gas Chromatography/Mass Spectrometry, Atmospheric Solid Analysis Probe, Direct Inlet Probe-Atmospheric Pressure Chemical Ionization Mass Spectrometry, and Ion Mobility Spectrometry-Mass Spectrometry

et al. 2020

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Polybutadiene (PB) and Polyisoprene (PI) the two most common polydienes (PD), are involved in a large number of materials and used in a wide variety of applications. The characterization of these polymers by mass spectrometry (MS) continues to be very challenging due to their high insolubility and the difficulty to ionize them. In this work, cross-metathesis reaction was used to generate end-functionalized acetoxy ionizable oligomers for the structural deciphering of different commercial PB and PI samples. A cross-metathesis reaction was carried out between polymers and the Z-1,4-diacetoxy-2-butene as chain transfer agent in dichloromethane using Hoveyda-Grubbs second-generation catalyst. Well-defined acetoxy telechelic structures were obtained and analysed by Fourier-Transform ion cyclotron resonance (FTICR) high resolution MS. However, after depolymerization, low molar mass polyolefins contained some units with different configurations, suggesting an olefin isomerization reaction due to the decomposition of the catalyst. The addition of an electron-deficient reagent such as 2,6-dichloro-1,4-benzoquinone suppressed this isomerization in the case of both Z-and E-PB and PI. Ion-mobility spectrometry-mass spectrometry (IMS-MS) and energy resolved tandem mass spectrometry (ERMS) analyses confirmed a successful isomerization suppression. For comparing the results obtained by depolymerisation with classical methods for polymer analysis, pyrolysis-comprehensive two-dimensional gas chromatography/mass spectrometry (Py-GC×GC-MS), atmospheric solid analysis probe (ASAP) and DIP-APCI analyses were performed on the same polymers. This strategy can be applied on a variety of synthetic and natural not yet characterized polymers. File list (2) download file view on ChemRxiv Ziad Mahmoud.pdf (883.65 KiB) download file view on ChemRxiv Ziad_Mahmoud_SI.pdf (1.04 MiB)

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Section: Resultsmentioning

confidence: 99%

Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Comparison with Pyrolysis-Comprehensive Two-Dimensional Gas Chromatography/Mass Spectrometry, Atmospheric Solid Analysis Probe, Direct Inlet Probe-Atmospheric Pressure Chemical Ionization Mass Spectrometry, and Ion Mobility Spectrometry-Mass Spectrometry

et al. 2020

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show abstract

Section: Resultsmentioning

confidence: 99%

Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High Resolution FTICR Mass Spectrometry. Comparison with Py-GCxGC-MS, ASAP&DIP-APCI MS and IMS-MS

Rolando

Afonso²,

Hubert‐Roux³

et al. 2020

Preprint

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Polybutadiene (PB) and Polyisoprene (PI) the two most common polydienes (PD), are involved in a large number of materials and used in a wide variety of applications. The characterization of these polymers by mass spectrometry (MS) continues to be very challenging due to their high insolubility and the difficulty to ionize them. In this work, cross-metathesis reaction was used to generate end-functionalized acetoxy ionizable oligomers for the structural deciphering of different commercial PB and PI samples. A cross-metathesis reaction was carried out between polymers and the Z-1,4-diacetoxy-2-butene as chain transfer agent in dichloromethane using Hoveyda-Grubbs second-generation catalyst. Well-defined acetoxy telechelic structures were obtained and analysed by Fourier-Transform ion cyclotron resonance (FTICR) high resolution MS. However, after depolymerization, low molar mass polyolefins contained some units with different configurations, suggesting an olefin isomerization reaction due to the decomposition of the catalyst. The addition of an electron-deficient reagent such as 2,6-dichloro-1,4-benzoquinone suppressed this isomerization in the case of both Z- and E- PB and PI. Ion-mobility spectrometry-mass spectrometry (IMS-MS) and energy resolved tandem mass spectrometry (ERMS) analyses confirmed a successful isomerization suppression. For comparing the results obtained by depolymerisation with classical methods for polymer analysis, pyrolysis-comprehensive two-dimensional gas chromatography/mass spectrometry (Py-GC×GC-MS), atmospheric solid analysis probe (ASAP) and DIP-APCI analyses were performed on the same polymers. This strategy can be applied on a variety of synthetic and natural not yet characterized polymers.

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“…Like for other polydienes the anionic polymerization of myrcene produces different microstructures depending on the polarity of the solvent or the presence of additives, often called "modifiers". For instance, polar modifiers and retarders have been investigated for the polybutadiene system [35] and for polyisoprene. [36][37][38][39][40][41] In brief, previous studies revealed an increase of the 1,2 addition instead of the 1,4 diene addition mode with increasing content of polar modifier.…”

Section: Doi: 101002/marc202000513mentioning

confidence: 99%

Temperature Variation Enables the Design of Biobased Block Copolymers via One‐Step Anionic Copolymerization

Bareuther

Plank

Kuttich

et al. 2020

Macromol. Rapid Commun.

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A one‐pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature‐induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at −78 °C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (−38 °C to room temperature) leads to poly(styrene‐block‐myrcene) formation due to polymerization of myrcene. Well‐defined BCPs featuring molar masses in the range of 44–117.2 kg mol−1 with dispersities, Ð, of 1.09–1.21, and polymyrcene volume fractions of 30–64% are accessible. Matrix assisted laser desorption ionization‐time of flight mass spectrometry measurements reveal the temperature‐controlled polymyrcene block formation, while both transmission electron microscopy and small‐angle X‐ray scattering measurements prove the presence of clearly microphase‐separated, long range‐ordered domains in the block copolymers. The temperature‐controlled one‐pot anionic block copolymerization approach may be general for other terpene‐diene monomers.

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Accessible microstructures of polybutadiene by anionic polymerization

Cited by 28 publications

References 49 publications

Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High Resolution FTICR Mass Spectrometry. Comparison with Py-GCxGC-MS, ASAP&DIP-APCI MS and IMS-MS

Temperature Variation Enables the Design of Biobased Block Copolymers via One‐Step Anionic Copolymerization

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Accessible microstructures of polybutadiene by anionic polymerization

Cited by 28 publications

References 49 publications

Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High Resolution FTICR Mass Spectrometry. Comparison with Py-GCxGC-MS, ASAP&amp;DIP-APCI MS and IMS-MS

Temperature Variation Enables the Design of Biobased Block Copolymers via One‐Step Anionic Copolymerization

Contact Info

Product

Resources

About

Regio- and Stereo-Specific Chemical Depolymerization of High Molecular Weight Polybutadiene and Polyisoprene for Their Analysis by High Resolution FTICR Mass Spectrometry. Comparison with Py-GCxGC-MS, ASAP&DIP-APCI MS and IMS-MS