Transforming Polybutadiene with Tetrazine Click Chemistry into Antioxidant Foams That Fluoresce with Oxidation

Robb E. Bagge, Timothy C. Mauldin, Dylan J. Boday, Brandon M. Kobilka, Douglas A Loy

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The extent to which oxidative degradation of macromolecules can be delayed is generally limited by the low solubility of antioxidants in most polymers. This can be surmounted by synthesizing macromolecules with covalently attached antioxidant functionalities, but these are frequently expensive. Here, we demonstrate a simple click modification of polybutadienes (PDB) with 3,6-dichloro-1,2,4,5-tetrazine (DCT) that, in addition to modifying and stiffening the polymer chains, releases nitrogen gas to foam the solidifying polymers and generates dihydropyridazine groups that transform them into macromolecular antioxidants. Tetrazines react by a cycloaddition/cycloreversion reaction (Carboni-Lindsey reaction) with the C=C bonds to install 1,4-dihydropyridazine groups that increase the mass and rigidity of the butadiene macromolecules. The 1,4-dihydropyridazine group is an effective antioxidant that donates two hydrogen atoms per ring to combine with radicals and forms an aromatic pyridazine ring whose white fluorescence under UV permits visual monitoring of oxidation. Foams made by reacting liquid hydroxyl-terminated polybutadienes with DCT stabilize with thermoset formation through substitution reactions between the hydroxyl and dichlorodihydropyridazine groups.

Original languageEnglish (US)
Pages (from-to)7953-7960
Number of pages8
JournalChemistry of Materials
Volume29
Issue number18
DOIs
StatePublished - Sep 26 2017

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Polybutadienes
Antioxidants
Foams
Macromolecules
Oxidation
Polymers
Hydroxyl Radical
Cycloaddition
Thermosets
Butadiene
Rigidity
Hydrogen
Substitution reactions
Nitrogen
Solubility
Gases
Fluorescence
Degradation
Atoms
polybutadiene

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Transforming Polybutadiene with Tetrazine Click Chemistry into Antioxidant Foams That Fluoresce with Oxidation. / Bagge, Robb E.; Mauldin, Timothy C.; Boday, Dylan J.; Kobilka, Brandon M.; Loy, Douglas A.

In: Chemistry of Materials, Vol. 29, No. 18, 26.09.2017, p. 7953-7960.

Research output: Contribution to journalArticle

Bagge, Robb E. ; Mauldin, Timothy C. ; Boday, Dylan J. ; Kobilka, Brandon M. ; Loy, Douglas A. / Transforming Polybutadiene with Tetrazine Click Chemistry into Antioxidant Foams That Fluoresce with Oxidation. In: Chemistry of Materials. 2017 ; Vol. 29, No. 18. pp. 7953-7960.
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