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REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES COVERED (From - To) January 2012 Viewgraph January 2012-March 2012 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER FUNCTIONALIZED FLUORINATED POLYHEDRAL OLIGOMERIC In-House SILSESQUIOXANE (F-POSS) 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER Sean M. Ramirez, Yvonne J. Diaz, Timothy S. Haddad, Joseph M. Mabry 5e. TASK NUMBER 5f. WORK UNIT NUMBER 23030521 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NO. Air Force Research Laboratory (AFMC) AFRL/RQRP 10 E. Saturn Blvd. Edwards AFB CA 93524-7680 9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S ACRONYM(S) Air Force Research Laboratory (AFMC) AFRL/RQR 5 Pollux Drive 11. SPONSOR/MONITOR’S REPORT Edwards AFB CA 93524-7048 NUMBER(S) AFRL-RZ-ED-VG-2012-058 12. DISTRIBUTION / AVAILABILITY STATEMENT Distribution A: Approved for Public Release; Distribution Unlimited. PA#12551 13. SUPPLEMENTARY NOTES Conference paper for the American Chemical Society National Conference, San Diego, California in 25-29 March 2012. 14. ABSTRACT Incompletely-condensed fluoroalkyl-functional Polyhedral Oligomeric SilSesquioxanes (F-POSS) have been synthesized via a scaleable three-step synthetic process with an overall yield of 52%. The primary byproduct of each step in the synthesis is the completely-condensed F-POSS starting material, which enables the recycling of the starting materials. The incompletely condensed structures were readily reacted with a variety of functional dichlorosilanes to introduce reactive or unreactive functionality and produce unsymmetrical F-POSS structures. Chemical structures were confirmed by elemental analysis, multinuclear NMR (1H, 13C, 19F, and 29Si), and FT-IR methods. Single crystal X-ray diffraction was used to elucidate the crystal structure of the precursor F-POSS disilanol. The functionalized F-POSS structures were found to possess variable solubility properties, generally superior to those of the closed- cage F-POSS starting material. Dynamic contact angle measurements of these compounds were examined using water and hexadecane as the wetting liquids. Copolymers of poly(methyl methacrylate) containing F-POSS were synthesized from methacrylate F-POSS macromers. These novel structures can be used as building blocks for the development of low surface energy materials. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION 18. NUMBER 19a. NAME OF OF ABSTRACT OF PAGES RESPONSIBLE PERSON Joseph Mabry a. REPORT b. ABSTRACT c. THIS PAGE 19b. TELEPHONE NO SAR 31 (include area code) Unclassified Unclassified Unclassified 661-525-5857 Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std. 239.18 FUNCTIONALIZED FLUORINATED POLYHEDRAL OLIGOMERIC SILSESQUIOXANE (F-POSS) Sean M. Ramirez,1 Yvonne J. Diaz,2 Timothy S. Haddad,1 and Joseph M. Mabry2 ERC Inc.1, Air Force Research Laboratory2 Propulsion Directorate Edwards Air Force Base, CA San Diego, CA ACS Meeting 2012 Distribution A: Approved for public release; distribution unlimited PA ClearanceNumber 11111 Polymer Working Group The Polymer Working Group at Edwards Air Force Base: Dr. Joseph Mabry Mr. Brian Moore Mr. Pat Ruth Mr. Kevin Lamison Ms. Vandana Vij Dr. Tim Haddad Dr. Greg Yandek Dr. Andy Guenthner Dr. Josiah Reams Dana Pinson Financial Support: Air Force Office of Scientific Research Air Force Research Laboratory, Propulsion Directorate Distribution A: Approved for public release; distribution unlimited 22 Hybrid Inorganic/Organic Polymers Ceramics R R' O Si Si O O R O Si Si O O R HYBRID O O PROPERTIES R Si Si O O R O Si Si O R R Polymers Toughness, Lightweight & Ease of Processing Distribution A: Approved for public release; distribution unlimited 33 POSS (RSiO ) 1.5 n • Organic-inorganic framework R R O Inorganic Si-O core • Well-defined, 3-D nanostructure Si Si O R O O Si Si Organic peripheral O O • R Can carry functional groups O R O Si Si • O O R Thermally and chemically robust O Si Si O R R • Used in thermoset and thermoplastic polymers, temperature nanocomposites, coatings, surface ~0.5 nm Si to Si modifiers, and many other applications 0.5-1.5 nm particles Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chem. Rev. 2010, 110, 2081. Phillips, S. H.; Haddad, T. S.; Tomczak, S. J. Current Opinion in Solid State and Materials Science 2004, 8, 21. Distribution A: Approved for public release; distribution unlimited 44 Introduction F-POSS • Fluorinated polyhedral oligomeric silsesquioxane (F-POSS) possesses oone of the lowest surface energies leading to the creation of ssuperhydrophobic and oleophobic surfaces • Close-caged structures are accessible and have proven versatile in polymer composites – Limitations • Solubility, mechanical robustness (surface abrasion), no sites for functionality PMMA + 44 wt% POSS electrospun • Open-caged structures would allow for functionalization of F-POSS coating (beads on a string) morphology (water, methanol, – Open door for use a building block material for low surface energy diiodomethane, octane) materials R R f O f • Applications Si Si O O – Mechanical robust superhydrophobic/oleophobic/omniphobic surfaces Rf Si Si O O O R f • Via covalently attached F-POSS to substrate (surface, nanoparticle, O R O polymer matrix) f Si Si O O R f O – Effects on polymer composite properties Si Si O R f R • Wetting, phase behavior, solubility, etc…. f FluorodecylPOSS Rf =CH2CH2(CF2)7CF3 (a)Mabry,J.M.;Vij,A.;Iacono,S.T.;Viers,b.D.,Angew.Chem.,Int.Ed.2008,47,4137-4140;(b)Iacono,S.T.;Budy,S.M.;Mabry,J.M.;Smith,D.W.,Jr.,Macromolecules2007,40,9517-9522;(c)Iacono,S.T.;Vij,A.;Grabow,W.;Smith,D.W.,Jr.;Mabry,J.M., Chem.Commun.2007,4992-4994.(d)Choi,W.;Tuteja,A.;Chhatre,S.;Mabry,J.M.;Cohen,R.E.;McKinley,G.H.,Adv.Mater.2009,21,2190-2195;(e)Tuteja,A.;Choi,W.;Mabry,J.M.;McKinely,G.H.;Cohen,R.E.,Proc.Natl.Acad.Sci.U.S.A.2008,105, 18200-18205,;(c)Tuteja,A.;Choi,W.;Ma,M.;Mabry,J.M.;Mazzella,S.A.;Rutledge,G.C.;McKinley,G.H.;Cohen,R.E.,Science2007,318,1618-1622;(f)Chhatre,S.S.;Guardado,J.O.;Moore,B.M.;Haddad,T.S.;Mabry,J.M.;McKinley,G.H.;Cohen,R. E.,ACSAppl.Mater.Interfaces2010,2,3544-3554. Distribution A: Approved for public release; distribution unlimited 5 Fluorinated polyhedral oligomeric silsesquioxane (F-POSS) F-POSS, a subclass of POSS which consists of a silicon-oxide core [SiO ] with a 1.5 periphery of long-chain fluorinated alkyl groups. F-POSS possesses one of the lowest surface energies leading to the creation of superhydrophobic and oleophobic surfaces. F F F F F F F F F F FF FF F F F F F F F F F F F F F F FF F F FF F F FF F F F FF O F F F F FF F FF F F SiOOSOi Si OSOi FFF F F F F F F F FF F F FF F FF F FF F OSiOSOi OSOi OSi FFFFFF FF F F F F F F F FF FF F F FF F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F (a)Mabry,J.M.;Vij,A.;Iacono,S.T.;Viers,b.D.,Angew.Chem.,Int.Ed.2008,47,4137-4140;(b)Iacono,S.T.;Budy,S.M.;Mabry,J.M.;Smith,D.W.,Jr.,Macromolecules2007,40,9517-9522; (c)Iacono, S. T.;Vij, A.; Grabow,W.; Smith, D.W.,Jr.; Mabry, J.M., Chem. Commun. 2007, 4992-4994. (d)Choi,W.;Tuteja, A.; Chhatre, S.; Mabry, J.M.;Cohen, R. E.; McKinley, G.H.,Adv. Mater.2009,21,2190-2195;(e)Tuteja,A.;Choi,W.;Mabry,J.M.;McKinely,G.H.;Cohen,R.E.,Proc.Natl.Acad.Sci.U.S.A.2008,105,18200-18205,;(c)Tuteja,A.;Choi,W.;Ma,M.;Mabry,J. M.;Mazzella,S.A.;Rutledge,G.C.;McKinley,G.H.;Cohen,R.E.,Science2007,318,1618-1622;(f)Chhatre,S.S.;Guardado,J.O.;Moore,B.M.;Haddad,T.S.;Mabry,J.M.;McKinley,G.H.; Cohen,R.E.,ACSAppl.Mater.Interfaces2010,2,3544-3554. Distribution A: Approved for public release; distribution unlimited 6 Fluorinated Polyhedral Oligomeric Silsesquioxane (F-POSS) Methylene Iodide Water Octane FFlluuoorroohheexxyyll TT FFlluuoorrooddeeccyyll TT 88 88 88 88 Methanol Mabry, J. M.; Vij, A.; Iacono, S. T.; Viers, b. D. Angew. Chem., Int. Ed. 2008, 47, 4137.(left) Tuteja, A.; Choi, W.; Ma, M.; Mabry, J. M.; Mazzella, S. A.; Rutledge, G. C.; McKinley, G. H.; Cohen, R. E. Science 2007, 318, 1618.(right) Distribution A: Approved for public release; distribution unlimited 7 Functional F-POSS • Close-caged structures are accessible and have proven versatile in polymer composites – Limitations • Solubility, mechanical robustness (surface abrasion), no sites for functionality • Open-caged structures would allow for functionalization of F-POSS – Open door for use a building block material for low surface energy materials • Applications – Mechanical robust superhydrophobic/oleophobic/omniphobic surfaces • Via covalently attached F-POSS to substrate (surface, nanoparticle, polymer matrix) – Effects on polymer composite properties • Wetting, phase behavior, solubility, etc…. Distribution A: Approved for public release; distribution unlimited 8 Methods to Produce Incompletely Condensed Silsesquioxanes • Bottom-up approach • Top-down Approach – Acid or base mediated from – Strong acid or base mediated RSiCl or RSi(OR) – Starting from a POSS cage 3 3 – Condensation reaction – Conversion of Si-O-Si bonds – Balance of stoichiometry, to Si-O (-) C(+) or Si-OH bonds temperature, reaction time, – Opening up POSS cage patience, and luck – Stopping POSS synthesis early, before cage fully condenses – More common approach Which method can be applied to F-POSS? Feher, F. J.; Terroba, R.; Ziller, J. W. Chemical Communications 1999,2309.Feher, F. J.; Newman D.A;. Walzer, J.M., J. Am. Chem. Soc., 1989, 111, 1741. Feher, F. J.; Soulivong, D.; Nguyen, F.; Ziller, J. W. Angew.Chem. Inter. Ed.1998, 37, 2663.Feher, F. J.; Soulivong, D.; Nguyen, F. Chem. Commun. 1998, 1279. Distribution A: Approved for public release; distribution unlimited 9