Metal-Catalyzed Alkynylation of Brominated Polyphenylenes. Thermoset Precursors of High Density Monolithic Glassy Carbon

Abstract

The functionalization of brominated polyphenylenes with several alkynes is described. The bromide groups on the polymer were replaced with terminal alkynes using a Pd/Cu catalyst system. Substitution of nearly all the original bromide locations was achieved. The functionalized polymers, freely soluble in THF, exhibited high char yields of up to 89% on thermolysis to 900 deg C under a nitrogen atmosphere. Several of the functionalized polymers, derived from brominated polyphenylenes with approximately equal amounts of meta- and para-linkages, flowed on heating. The polymer that was functionalized with phenylacetylene exhibited a well-defined melting point at approximately 200 deg C and flowed to produce a monolithic disk of glassy carbon. The amount of acetylenic crosslinking units in the polymers functionalized with phenylacetylene appears to be directly related to the char yields of the functionalized polymers. Predominantly meta-linked brominated polyphenylenes were also functionalized with a number of terminal alkynes and though high char yields of up to 86% were observed, these materials offered no improvements in flow properties. The structure/property relationships and material applications are discussed.

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Document Details

Document Type
Technical Report
Publication Date
Nov 22, 1993
Accession Number
ADA273232

Entities

People

  • Eric B. Stephens
  • James Tour

Organizations

  • University of South Carolina

Tags

Communities of Interest

  • Biomedical

DTIC Thesaurus Topics

  • Acetylenes
  • Alkynes
  • Atmospheres
  • Body Weight
  • Chemical Synthesis
  • Chemistry
  • Chlorides
  • Controlled Atmospheres
  • Gunpowder
  • High Density
  • Materials
  • Organic Chemistry
  • Polymers
  • Resins
  • South Carolina
  • Thermal Properties
  • Thermosetting Plastics

Readers

  • Organic Chemistry
  • Polymer Science and Engineering.
  • Reinforced Composite Materials