Synthesis, Characterization and Properties of Chain Terminated Polyhedral Oligomeric Silsesquioxane-Functionalized Perfluorocyclobutyl Aryl Ether Copolymers (Postprint)

Abstract

A new class of perfluorocyclobutyl (PFCB) polymers covalently functionalized with polyhedral oligomeric silsesquioxnes (POSS) is presented. Three discreetly functionalized POSS monomers possessing thermally reactive trifluorovinyl aryl ethers (TFVE) were prepared in good yields. The POSS TFVE monomers were prepared by initial corner capping of cyclopentyl (-C5H9), iso-butyl (-CH2CH(CH3)2), or trifluoropropyl (-CH2CH2CF3) functionalized POSS trisilanols with acetoxyethyltrichlorsilane followed by sequential acid-catalyzed deprotection and coupling with 4-(trifluorovinyloxy)benzoic acid. TFVE functionalized POSS monomers were thermally polymerized with 4,4'-bis(4-trifluorovinyloxy)biphenyl or 2,2-bis(4-trifluorovinyloxybiphenyl)-1,1,1,3,3,3-hexafluoropropane monomers via a condensate-free, [2+2] step-growth polymerization. The polymerization afforded solution processable PFCB polymers with POSS macromers installed on the polymer chain ends. POSS monomers and their corresponding copolymers were characterized by 1H, 13C, 19F, and 29Si NMR, GPC, ATR-FTIR, and elemental combustion analysis. GPC trace analysis showed agreeable number-average molecular weight for various weight percent of iso-butyl and trifluoropropyl chain terminated POSS PFCB copolymers. DSC analysis showed the introduction of increasing POSS weight percent in the endcapped PFCB copolymers lowers glass transition temperatures as high as 31 deg C. On the other hand, the trifluoropropyl POSS endcapped PFCB polymer glass transition temperature was unaffected when copolymerized with the more fluorinated 2,2-bis(4-trifluorovinyloxybiphenyl)-1,1,1,3,3,3-hexafluoropropane monomer.

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Document Details

Document Type
Technical Report
Publication Date
Jan 01, 2007
Accession Number
ADA497781

Entities

People

  • Dennis W. Smith Jr.
  • Joseph M Mabry
  • Scott T Iacono
  • Stephen M. Budy

Organizations

  • Clemson University

Tags

Communities of Interest

  • Advanced Electronics
  • Energy and Power Technologies

DTIC Thesaurus Topics

  • Air Force Research Laboratories
  • Aryl Ethers
  • Biomedical And Dental Materials
  • Chemical Synthesis
  • Chemistry
  • Composite Materials
  • Copolymers
  • Decomposition
  • Glass
  • Glass Transition Temperature
  • Materials
  • Materials Laboratories
  • Materials Science
  • Molecular Weight
  • Polymers
  • Thermal Stability
  • Transition Temperature

Fields of Study

  • Chemistry

Readers

  • Polymer Science and Technology

Technology Areas

  • Microelectronics