A perfluorocycloalkene (PFCA) fluorocarbon structure with a cycloalkene core. PFCAs have shown reactivity with a wide variety of nucleophiles including phenoxides, alkoxides, organometallic, amines, thiols, and azoles.[1] They or their derivatives are reported to have nonlinear optical activity,[2] and be useful as lubricants,[3] etching agents,[4] components of fuel cells,[5] low dielectric materials, and super hydrophobic and oleophobic coatings.[6]
Examples of perfluorocycloalkenes
Tetrafluorocyclopropene
Hexafluorocyclobutene
Octafluorocyclopentene
Decafluorocyclohexene
Reactivityedit
Derivatization of these PFCA rings via displacement of fluorine atoms with nucleophiles occurs through an addition-elimination reaction in the presence of a base. Attack of the nucleophile on the PFCA ring generates a carbanion which can eliminate a fluoride ion, resulting in vinyl substituted and allyl substituted products (Scheme 1). The ratio of vinylic to allylic products depends on the ring size, reaction conditions and nucleophile.[1][7]
PFCAs have a huge potential to be used as a monomer to produce a variety of polymers. The first time, Smith et al. showed the polycondensation of bisphenols with PFCAs. A unique class of aromatic ether polymers containing perfluorocyclopentenyl (PFCP) enchainment was prepared from the simple step growth polycondensation of commercial available bisphenols and octafluorocyclopentene (OFCP) in the presence of triethylamine (Scheme 3 and 4).[6][9]
Smith et al. further extended his recently published work on perfluorocyclopentenyl (PFCP) aryl ether polymers and perfuorocycloalkenyl (PFCA) aryl ether monomers, and reported the synthesis of a new class of fluoropolymers, namely, perfluorocyclohexenyl (PFCH) aryl ether polymers, via step-growth polycondensation of commercial bisphenols and decafluorocycloalkene (DFCH) in the presence of triethylamine (Scheme 5).[7][10]
^ abcdWigglesworth, Tony J.; Sud, David; Norsten, Tyler B.; Lekhi, Vikram S.; Branda, Neil R. (2005). "Chiral Discrimination in Photochromic Helicenes". Journal of the American Chemical Society. 127 (20): 7272–3. doi:10.1021/ja050190j. PMID 15898750.
^Matsui, Masaki; Tsuge, Michinori; Funabiki, Kazumasa; Shibata, Katsuyoshi; Muramatsu, Hiroshige; Hirota, Kazuo; Hosoda, Masahiro; Tai, Kazuo; Shiozaki, Hisayoshi; Kim, Misa; Nakatsu, Kazumi (1999). "Synthesis of azo chromophores containing a perfluorocyclo-alkenyl moiety and their second-order optical nonlinearity". Journal of Fluorine Chemistry. 97 (1–2): 207–12. doi:10.1016/S0022-1139(99)00050-0.
^Takahashi, Kazuo; Itoh, Atsushi; Nakamura, Toshihiro; Tachibana, Kunihide (2000). "Radical kinetics for polymer film deposition in fluorocarbon (C4F8, C3F6 and C5F8) plasmas". Thin Solid Films. 374 (2): 303–10. Bibcode:2000TSF...374..303T. doi:10.1016/S0040-6090(00)01160-3.
^"Patent US20140162173 - Sulfonated perfluorocyclopentenyl polymers and uses thereof - Google Patents". Google.com. 2013-10-09. Retrieved 2017-01-05.
^ abSharma, Babloo; Verma, Rajneesh; Baur, Cary; Bykova, Julia; Mabry, Joseph M.; Smith, Dennis W. (2013). "Ultra low dielectric, self-cleansing and highly oleophobic POSS-PFCP aryl ether polymer composites". Journal of Materials Chemistry C. 1 (43): 7222–7. doi:10.1039/C3TC31161A.
^ abcSharma, Babloo; Faisal, Mohammad; Liff, Shawna M.; Smith, Dennis W. (2014). "Triarylamine-enchained semifluorinated perfluorocycloalkenyl (PFCA) aryl ether polymers". Applied Petrochemical Research. 5: 35. doi:10.1007/s13203-014-0063-0.
^ abGarg, Sonali; Twamley, Brendan; Zeng, Zhuo; Shreeve, Jean'neM. (2009). "Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes". Chemistry: A European Journal. 15 (40): 10554–62. doi:10.1002/chem.200901508. PMID 19746368.
^ abcCracowski, Jean-Marc; Sharma, Babloo; Brown, Dakarai K.; Christensen, Kenneth; Lund, Benjamin R.; Smith, Dennis W. (2012). "Perfluorocyclopentenyl (PFCP) Aryl Ether Polymers via Polycondensation of Octafluorocyclopentene with Bisphenols". Macromolecules. 45 (2): 766–71. Bibcode:2012MaMol..45..766C. doi:10.1021/ma2024599.
^ abSharma, Babloo; Hill, Sarah C.; Liff, Shawna M.; Pennington, William T.; Smith, Dennis W. (2014). "Perfluorocyclohexenyl aryl ether polymers via polycondensation of decafluorocyclohexene with bisphenols". Journal of Polymer Science Part A: Polymer Chemistry. 52 (2): 232–8. Bibcode:2014JPoSA..52..232S. doi:10.1002/pola.26995.
April 27, 2024
perfluorocycloalkene, this, article, relies, excessively, references, primary, sources, please, improve, this, article, adding, secondary, tertiary, sources, find, sources, news, newspapers, books, scholar, jstor, january, 2024, learn, when, remove, this, temp. This article relies excessively on references to primary sources Please improve this article by adding secondary or tertiary sources Find sources Perfluorocycloalkene news newspapers books scholar JSTOR January 2024 Learn how and when to remove this template message A perfluorocycloalkene PFCA fluorocarbon structure with a cycloalkene core PFCAs have shown reactivity with a wide variety of nucleophiles including phenoxides alkoxides organometallic amines thiols and azoles 1 They or their derivatives are reported to have nonlinear optical activity 2 and be useful as lubricants 3 etching agents 4 components of fuel cells 5 low dielectric materials and super hydrophobic and oleophobic coatings 6 Examples of perfluorocycloalkenes Tetrafluorocyclopropene Hexafluorocyclobutene Octafluorocyclopentene DecafluorocyclohexeneReactivity editDerivatization of these PFCA rings via displacement of fluorine atoms with nucleophiles occurs through an addition elimination reaction in the presence of a base Attack of the nucleophile on the PFCA ring generates a carbanion which can eliminate a fluoride ion resulting in vinyl substituted and allyl substituted products Scheme 1 The ratio of vinylic to allylic products depends on the ring size reaction conditions and nucleophile 1 7 nbsp Scheme 1 Derivatization of the PFCA ring 1 Under favorable conditions a good nucleophile can replace all the fluorine atoms on PFCA ring Scheme 2 8 nbsp Scheme 2 Multi substitution on PFCA ring 1 8 PFCAs have a huge potential to be used as a monomer to produce a variety of polymers The first time Smith et al showed the polycondensation of bisphenols with PFCAs A unique class of aromatic ether polymers containing perfluorocyclopentenyl PFCP enchainment was prepared from the simple step growth polycondensation of commercial available bisphenols and octafluorocyclopentene OFCP in the presence of triethylamine Scheme 3 and 4 6 9 nbsp Scheme 3 Perfluorocyclopentenyl PFCP aryl ether polymer synthesis 9 nbsp Scheme 4 Bis heptafluorocyclopentenyl aryl ether monomers synthesis and polymerization 9 Smith et al further extended his recently published work on perfluorocyclopentenyl PFCP aryl ether polymers and perfuorocycloalkenyl PFCA aryl ether monomers and reported the synthesis of a new class of fluoropolymers namely perfluorocyclohexenyl PFCH aryl ether polymers via step growth polycondensation of commercial bisphenols and decafluorocycloalkene DFCH in the presence of triethylamine Scheme 5 7 10 nbsp Scheme 5 Perfluorocycloalkenyl PFCA aryl ether polymer synthesis 7 10 References edit a b c d Wigglesworth Tony J Sud David Norsten Tyler B Lekhi Vikram S Branda Neil R 2005 Chiral Discrimination in Photochromic Helicenes Journal of the American Chemical Society 127 20 7272 3 doi 10 1021 ja050190j PMID 15898750 Matsui Masaki Tsuge Michinori Funabiki Kazumasa Shibata Katsuyoshi Muramatsu Hiroshige Hirota Kazuo Hosoda Masahiro Tai Kazuo Shiozaki Hisayoshi Kim Misa Nakatsu Kazumi 1999 Synthesis of azo chromophores containing a perfluorocyclo alkenyl moiety and their second order optical nonlinearity Journal of Fluorine Chemistry 97 1 2 207 12 doi 10 1016 S0022 1139 99 00050 0 Organometallic Derivatives Of Perfluorocycloalkenes Minnesota Mining Mfg Co Us Freepatentsonline com 1971 08 25 Retrieved 2017 01 05 Takahashi Kazuo Itoh Atsushi Nakamura Toshihiro Tachibana Kunihide 2000 Radical kinetics for polymer film deposition in fluorocarbon C4F8 C3F6 and C5F8 plasmas Thin Solid Films 374 2 303 10 Bibcode 2000TSF 374 303T doi 10 1016 S0040 6090 00 01160 3 Patent US20140162173 Sulfonated perfluorocyclopentenyl polymers and uses thereof Google Patents Google com 2013 10 09 Retrieved 2017 01 05 a b Sharma Babloo Verma Rajneesh Baur Cary Bykova Julia Mabry Joseph M Smith Dennis W 2013 Ultra low dielectric self cleansing and highly oleophobic POSS PFCP aryl ether polymer composites Journal of Materials Chemistry C 1 43 7222 7 doi 10 1039 C3TC31161A a b c Sharma Babloo Faisal Mohammad Liff Shawna M Smith Dennis W 2014 Triarylamine enchained semifluorinated perfluorocycloalkenyl PFCA aryl ether polymers Applied Petrochemical Research 5 35 doi 10 1007 s13203 014 0063 0 a b Garg Sonali Twamley Brendan Zeng Zhuo Shreeve Jean neM 2009 Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes Chemistry A European Journal 15 40 10554 62 doi 10 1002 chem 200901508 PMID 19746368 a b c Cracowski Jean Marc Sharma Babloo Brown Dakarai K Christensen Kenneth Lund Benjamin R Smith Dennis W 2012 Perfluorocyclopentenyl PFCP Aryl Ether Polymers via Polycondensation of Octafluorocyclopentene with Bisphenols Macromolecules 45 2 766 71 Bibcode 2012MaMol 45 766C doi 10 1021 ma2024599 a b Sharma Babloo Hill Sarah C Liff Shawna M Pennington William T Smith Dennis W 2014 Perfluorocyclohexenyl aryl ether polymers via polycondensation of decafluorocyclohexene with bisphenols Journal of Polymer Science Part A Polymer Chemistry 52 2 232 8 Bibcode 2014JPoSA 52 232S doi 10 1002 pola 26995 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