Understanding the Microstructure of Poly(p-phenylenevinylene)s Prepared by Ring Opening Metathesis Polymerization Using 13C-Labeled Paracyclophanediene Monomers

Dharam Kumar; Benjamin Lidster; Ralph Adams; Michael Turner

doi:10.1021/acs.macromol.8b00705

Understanding the Microstructure of Poly(p-phenylenevinylene)s Prepared by Ring Opening Metathesis Polymerization Using ¹³C-Labeled Paracyclophanediene Monomers

Dharam Kumar, Benjamin Lidster, Ralph Adams, Michael Turner

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

Abstract

Selectively main chain ¹³C-labeled poly(p-phenylenevinylene)s (PPVs) were synthesized by ring-opening metathesis polymerization (ROMP) of ¹³C-labeled dialkoxy-substituted [2,2] paracyclophane-1,9-dienes (M) using the Grubbs second generation ruthenium carbene complex (G2). Analysis of the natural abundance and ¹³C-labeled PPVs by NMR spectroscopy showed no main chain structural defects for these polymers. Comparison of the in situ ¹H and ¹³C NMR spectroscopy during the ROMP of labeled and unlabeled monomer enabled the active ruthenium carbene chain ends present during the initiation and propagation reaction to be definitively characterized. Using ¹³C NMR spectroscopy, the regiochemistry of the propagation of the asymmetric monomer M with G2 was found to be essentially regiorandom.

Original language	English
Journal	Macromolecules
Early online date	8 Jun 2018
DOIs	https://doi.org/10.1021/acs.macromol.8b00705
Publication status	Published - 2018

Keywords

Poly(p-phenylenevinylene)s
ring opening metathesis polymerization
mechanism
polymer microstructure
13C-labeling

Access to Document

10.1021/acs.macromol.8b00705

Cite this

@article{8278989898104502810025bd8a3725bd,

title = "Understanding the Microstructure of Poly(p-phenylenevinylene)s Prepared by Ring Opening Metathesis Polymerization Using 13C-Labeled Paracyclophanediene Monomers",

abstract = "Selectively main chain 13C-labeled poly(p-phenylenevinylene)s (PPVs) were synthesized by ring-opening metathesis polymerization (ROMP) of 13C-labeled dialkoxy-substituted [2,2] paracyclophane-1,9-dienes (M) using the Grubbs second generation ruthenium carbene complex (G2). Analysis of the natural abundance and 13C-labeled PPVs by NMR spectroscopy showed no main chain structural defects for these polymers. Comparison of the in situ 1H and 13C NMR spectroscopy during the ROMP of labeled and unlabeled monomer enabled the active ruthenium carbene chain ends present during the initiation and propagation reaction to be definitively characterized. Using 13C NMR spectroscopy, the regiochemistry of the propagation of the asymmetric monomer M with G2 was found to be essentially regiorandom.",

keywords = "Poly(p-phenylenevinylene)s, ring opening metathesis polymerization, mechanism, polymer microstructure , 13C-labeling ",

author = "Dharam Kumar and Benjamin Lidster and Ralph Adams and Michael Turner",

year = "2018",

doi = "10.1021/acs.macromol.8b00705",

language = "English",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Understanding the Microstructure of Poly(p-phenylenevinylene)s Prepared by Ring Opening Metathesis Polymerization Using 13C-Labeled Paracyclophanediene Monomers

AU - Kumar, Dharam

AU - Lidster, Benjamin

AU - Adams, Ralph

AU - Turner, Michael

PY - 2018

Y1 - 2018

N2 - Selectively main chain 13C-labeled poly(p-phenylenevinylene)s (PPVs) were synthesized by ring-opening metathesis polymerization (ROMP) of 13C-labeled dialkoxy-substituted [2,2] paracyclophane-1,9-dienes (M) using the Grubbs second generation ruthenium carbene complex (G2). Analysis of the natural abundance and 13C-labeled PPVs by NMR spectroscopy showed no main chain structural defects for these polymers. Comparison of the in situ 1H and 13C NMR spectroscopy during the ROMP of labeled and unlabeled monomer enabled the active ruthenium carbene chain ends present during the initiation and propagation reaction to be definitively characterized. Using 13C NMR spectroscopy, the regiochemistry of the propagation of the asymmetric monomer M with G2 was found to be essentially regiorandom.

AB - Selectively main chain 13C-labeled poly(p-phenylenevinylene)s (PPVs) were synthesized by ring-opening metathesis polymerization (ROMP) of 13C-labeled dialkoxy-substituted [2,2] paracyclophane-1,9-dienes (M) using the Grubbs second generation ruthenium carbene complex (G2). Analysis of the natural abundance and 13C-labeled PPVs by NMR spectroscopy showed no main chain structural defects for these polymers. Comparison of the in situ 1H and 13C NMR spectroscopy during the ROMP of labeled and unlabeled monomer enabled the active ruthenium carbene chain ends present during the initiation and propagation reaction to be definitively characterized. Using 13C NMR spectroscopy, the regiochemistry of the propagation of the asymmetric monomer M with G2 was found to be essentially regiorandom.

KW - Poly(p-phenylenevinylene)s

KW - ring opening metathesis polymerization

KW - mechanism

KW - polymer microstructure

KW - 13C-labeling

U2 - 10.1021/acs.macromol.8b00705

DO - 10.1021/acs.macromol.8b00705

M3 - Article

SN - 0024-9297

JO - Macromolecules

JF - Macromolecules