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Synthesis of Fluorinated Homopolymers by ATRP and the Determination of Their Extent Solubility in CO 2 by Light Scatter

Synthesis of Fluorinated Homopolymers by ATRP and the Determination of Their Extent Solubility in CO 2 by Light Scattering. Tiffani Nicole Bailey i sarah l. folk ii , joseph m. desimone ii,iii. I. Hampton University School of Science Hampton, VA 23668

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Synthesis of Fluorinated Homopolymers by ATRP and the Determination of Their Extent Solubility in CO 2 by Light Scatter

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  1. Synthesis of Fluorinated Homopolymers by ATRP andthe Determination of Their Extent Solubility in CO2 by Light Scattering Tiffani Nicole Baileyi sarah l. folkii, joseph m. desimoneii,iii I.Hampton University School of Science Hampton, VA 23668 II.University of North Carolina at Chapel Hill Dept of Chemistry, Venable Hall CB 3290 Chapel Hill, NC 27599 III. North Carolina State University Dept of Chemical Engineering Raleigh, NC 27695 NSF Science and Technology Center for Environmentally Responsible Solvents and Processes

  2. Objective • To determine the relative solubilities of • a collection of fluorinated Methacrylates • and Acrylates in CO2 as a function of • molecular weight and structure.

  3. Atom Transfer Radical Polymerization A CLASSICAL ATRP REACTION SCHEME

  4. Polymerization of MMA

  5. PMMA – GPC results OO Mn, targeted = 22,000g/mol GPC of PMMA synthesized in toluene (33 v/v% monomer) Eluent = THF

  6. Polymerization of FOMA

  7. PFOMA – Monitoring of Conversion monomer monomer polymer polymer polymer monomer 7 6 5 4 3 2 1 0 7 6 5 4 3 2 1 0 7 6 5 4 3 2 1 0 4hr 5min 74.2% 1hr 15min 12.8% 22hr 30min 93.3%

  8. PFOMA – Molecular Weight Determination 7 6 5 4 3 2 1 ppm

  9. Cloud Point Curve of PFOMA one phase two phase 1.2 w/w% in CO2

  10. Light Scattering • Conventional solvents • isorefractive • too little contrast • In CO2 we can determine • Molecular Weight • Size • A2 (second virial coefficient) Comparison of fluorinated homopolymer solubilities by A2

  11. Future Works 25% Branching of Fluorinated Chains 25% Branching of Fluorinated Chains Perfectly Linear Perfectly Linear

  12. Acknowledgments • North Carolina at Chapel Hill SPGRE Program/ • National Science Foundation • Dr. Mireille Adam, Dr. Darlene Taylor, • Dr. Jason Keiper, and Karen Erford • This material is based upon work supported in part • by the STC Program of the National Science • Foundation under Agreement No. CHE-9876674.

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