Skip to main content
SpringerLink
Log in

Electrophilic Routes to 6F Polymers and Attempted Synthesis of Semi-fluorinated Group IVB Metallocene Polymers

  • Research
  • Published:
Journal of Inorganic and Organometallic Polymers and Materials Aims and scope Submit manuscript

Abstract

Since the seminal work presented by Olah in 1966 on fluorinated carbocations, several strategies have been presented to introduce fluorinated moieties in polymer backbones via carbocation chemistry. The hexafluoroisopropylidene (6F) group is well known for its ability to enhance thermal properties and processability of polymers. However, its direct electrophilic incorporation into polymers has been largely ignored due to the challenges posed by activating hexafluoroacetone monomer for electrophilic aromatic substitution (EAS). In this article, we review the role of fluorinated carbocations from 1966 up to our recent versatile fluoroalkylation strategy to directly enchain the 6F group in polymers. Via EAS interfacial polymerization we reacted hexafluoroacetone trihydrate (HFAH) with aromatic monomers in triflic anhydride (Tf2O) and 1,2-dichloroethane (DCE) with Aliquat® 336. In addition, the polymerization of dibenzo-1,4-dioxin with HFAH is presented. A semi-fluorinated diol, 4,4′-bis(2-hydroxyhexafluoroisopropyl)diphenyl ether, was synthesized by this method and used to prepare the first reported polycarbonate with hexafluoroisopropoxy groups –C(CF3)2O– incorporated in the main chain via polycondensation. Polysilyl ethers were also prepared from this diol. Additionally, we briefly mention Carraher’s legacy in the synthesis of metal-containing polymers via reactions of group IVB metallocene dichloride with dinucleophiles (diamines, diol, dicarboxylic acids, and dithiols) in solution and interfacial conditions in terms of electrophilic vs nucleophilic polycondensation. The new acidic, sterically hindered semi-fluorinated diol and bisphenol AF were reacted with group IVB metallocene dichloride in attempts to form metallocene condensation polymers with improved solubility.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14
Fig. 15
Fig. 16
Fig. 17
Fig. 18
Fig. 19
Fig. 20
Fig. 21
Fig. 22
Fig. 23
Fig. 24
Fig. 25

Similar content being viewed by others

Data Availability

No datasets were generated or analysed during the current study.

References

  1. G.A. Olah, C.A. Cupas, M.B. Comisarow, J. Am. Chem. Soc. 88, 362 (1966)

    Article  CAS  Google Scholar 

  2. G.A. Olah, C.U. Jr. Pittman, J. Am. Chem. Soc. 88, 3310 (1966)

    Article  CAS  Google Scholar 

  3. P.G. Gassman, T.T. Tidwell, Acc. Chem. Res. 16, 279 (1983)

    Article  CAS  Google Scholar 

  4. C.G. Krespan, V.A. Petrov, Chem. Rev. 96, 3269 (1996)

    Article  CAS  PubMed  Google Scholar 

  5. K. Mikami, Y. Itoh, M. Yamanaka, Chem. Rev. 104, 1 (2004)

    Article  CAS  PubMed  Google Scholar 

  6. G.A. Olah, Angewandte Chemie Int. Ed. Engl. 32, 767 (1993)

    Article  Google Scholar 

  7. G.A. Olah, A. Germain, H.C. Lin, D.A. Forsyth, J. Am. Chem. Soc. 97, 2928 (1975)

    Article  CAS  Google Scholar 

  8. N. Hartz, G. Rasul, G.A. Olah, J. Am. Chem. Soc. 115, 1277 (1993)

    Article  CAS  Google Scholar 

  9. Xavier, Creary, Chem. Rev. 91, 1625 (1991)

    Article  Google Scholar 

  10. D.A. Klumpp, in Recent Developments in Carbocation and Onium Ion Chemistry, ed. by K. Laali. ACS Symposium Series (2007), p. 144

  11. W.D. Kray, R.W. Rosser, J. Org. Chem. 42, 1186 (1977)

    Article  CAS  Google Scholar 

  12. M. Zolotukhin, S. Fomine, R. Salcedo, L. Khalilov, Chem. Commun. 1030 (2004)

  13. A.M. Diaz, M.G. Zolotukhin, S. Fomine, R. Salcedo, O. Manero, G. Cedillo, V.M. Velasco, M.T. Guzman, D. Fritsch, A.F. Khalizov, Macromol. Rapid Commun. 28, 183 (2007)

    Article  CAS  Google Scholar 

  14. A.R. Cruz, M.C.G. Hernandez, M.T. Guzmán-Gutiérrez, M.G. Zolotukhin, S. Fomine, S.L. Morales, H. Kricheldorf, E.S. Wilks, J. Cárdenas, M. Salmón, Macromolecules. 45, 6774 (2012)

    Article  CAS  Google Scholar 

  15. L.I. Olvera, M.T. Guzmán-Gutiérrez, M.G. Zolotukhin, S. Fomine, J. Cárdenas, F.A. Ruiz-Trevino, D. Villers, T.A. Ezquerra, E. Prokhorov, Macromolecules. 46, 7245 (2013)

    Article  CAS  Google Scholar 

  16. G.L. Tullos, P.E. Cassidy, K St Clair Macromol. 24, 6059 (1991)

    Article  CAS  Google Scholar 

  17. K.S.Y. Lau, T.K. Dougherty, U.S. Patent 4,827,054 (1989)

  18. P.E. Cassidy, T.M. Aminabhavi, J.M. Farley, J. Macromolecular Sci. Part. C: Polym. Reviews. 29, 365 (1989)

    Article  Google Scholar 

  19. C.-C. Kuo, Y.-C. Lin, Y.-C. Chen, P.-H. Wu, S. Ando, M. Ueda, W.-C. Chen, ACS Appl. Polym. Mater. 3, 362 (2021)

    Article  CAS  Google Scholar 

  20. M. Bruma, J.W. Fitch, P.E. Cassidy, J. Macromolecular Sci. Part. C: Polym. Reviews. 36, 119 (1996)

    Article  Google Scholar 

  21. P.A. Havelka-Rivard, K. Nagai, B.D. Freeman, V.V. Sheares, Macromolecules. 32, 6418 (1999)

    Article  CAS  Google Scholar 

  22. S.V. Kostjuk, E. Ortega, F. Ganachaud, B. Améduri, B. Boutevin, Macromolecules. 42, 612 (2009)

    Article  CAS  Google Scholar 

  23. U.J. Castillo, M.G. Zolotukhin, L. Fomina, D.R. Nieto, L.O. Garza, S. Fomine, J. Mol. Model. 19, 793 (2013)

    Article  CAS  PubMed  Google Scholar 

  24. N.P. Gambaryan, E.M. Rokhlin, Y.V. Zeifman, C. Ching-yun, I.L. Knunyants, Angewandte Chemie Int. Ed. Engl. 5, 947 (1966)

    Article  CAS  Google Scholar 

  25. A.D. Allen, V.M. Kanagasabapathy, T.T. Tidwell, J. Am. Chem. Soc. 108, 3470 (1986)

    Article  CAS  Google Scholar 

  26. L. Tao, H. Yang, J. Liu, L. Fan, S. Yang, Synth. Commun. 43, 2319 (2013)

    Article  CAS  Google Scholar 

  27. G.S. Stamatoff, J.W. Wittmann, U.S. Patent 3,291,777 (1966)

  28. G. Muñoz, K.M. Chamberlain, S. Athukorale, G. Ma, X. Gu, C.U. Jr. Pittman, D.W. Jr Smith, Macromol. Rapid Commun. 44 (2023)

  29. G. Muñoz, K.M. Chamberlain, S. Athukorale, C.U. Pittman Jr., D.W. Smith Jr., Polym. (Guildf). 293, 126642 (2024)

    Article  Google Scholar 

  30. S.A. Reines, J.R. Griffith, J.G. O’Rear, J. Org. Chem. 35, 2772 (1970)

    Article  CAS  Google Scholar 

  31. S.A. Reines, J.R. Griffith, J.G. O’Rear, J. Org. Chem. 36, 1209 (1971)

    Article  CAS  Google Scholar 

  32. D.E. Field, J.R. Griffith, U.S. Patent 3,872,045 (1975)

  33. T.M. Keller, J. Polym. Science: Polym. Chem. Ed. 23, 2557 (1985)

    CAS  Google Scholar 

  34. P.E. Cassidy, J. Macromolecular Sci. Part. C: Polym. Reviews. 34, 1 (1994)

    Article  Google Scholar 

  35. V. Sreenivasulu Reddy, P.E. Cassidy, J.W. Fitch, B.D. Lunceford, D. Person, Polym. (Guildf). 37, 4873 (1996)

    Article  Google Scholar 

  36. M. Chen, J. Li, L. Chen, Y. Qin, M. Xiao, Y. Wang, Polym. (Guildf). 253, 125012 (2022)

    Article  CAS  Google Scholar 

  37. D.S. Gupta, V.S. Reddy, P.E. Cassidy, J.W. Fitch, Polym. (Guildf). 34, 4173 (1993)

    Article  CAS  Google Scholar 

  38. T. Doi, Y. Yada, K. Nishino, M. Sugiura, T. Shimokawa, J. Polym. Sci. 58, 1062 (2020)

    Article  CAS  Google Scholar 

  39. C.E. Jr. Carraher, J. Inorg. Organomet. Polym. Mater. 15, 121 (2005)

    Article  CAS  Google Scholar 

  40. C.E. Jr. Carraher, S.T. Bajah, Polym. (Guildf). 14, 42 (1973)

    Article  CAS  Google Scholar 

  41. C.E. Jr. Carraher, L.M. Jambaya, Die Angewandte Makromolekulare Chemie. 39, 69 (1974)

    Article  CAS  Google Scholar 

  42. C.E. Jr. Carraher, L.M. Jambaya, Die Angewandte Makromolekulare Chemie. 52, 111 (1976)

    Article  CAS  Google Scholar 

  43. C.E. Jr. Carraher, Eur. Polym. J. 8, 215 (1972)

    Article  CAS  Google Scholar 

  44. C.E. Jr Carraher, R.L. Dammeier, J. Polym. Sci. A 1(10), 413 (1972)

    Article  Google Scholar 

  45. C.E. Jr. Carraher, Die Makromolekulare Chemie. 166, 31 (1973)

    Article  CAS  Google Scholar 

  46. C.E. Jr. Carraher, J.L. Lee, J. Macromolecular Science: Part. - Chem. 9, 191 (1975)

    Article  Google Scholar 

  47. C.E. Jr Carraher, R.J. Nordin, J. Polym. Sci. A 1(10), 521 (1972)

    Article  Google Scholar 

  48. C.E. Jr. Carraher, R.J. Nordin, J. Appl. Polym. Sci. 18, 53 (1974)

    Article  CAS  Google Scholar 

  49. C.E. Jr Carraher, Polym. (Guildf). 17, 231 (1976)

    Article  CAS  Google Scholar 

  50. C. Jr Carraher, P. Lessek, Eur. Polym. J. 8, 1339 (1972)

    Article  CAS  Google Scholar 

  51. C.E. Jr Carraher, S. Jorgensen, J. Polym. Science: Polym. Chem. Ed. 16, 2965 (1978)

    CAS  Google Scholar 

Download references

Acknowledgements

The authors would like to acknowledge the Department of Chemistry, Mississippi State University for supporting this project.

Author information

Authors and Affiliations

  1. Department of Chemistry, Mississippi State University, Starkville, MS, 39762, USA

    Gustavo Muñoz, Kari M. Chamberlain, Maxim E. Solovyev, Dennis W. Smith Jr. & Charles U. Pittman Jr.

Authors
  1. Gustavo Muñoz
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kari M. Chamberlain
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Maxim E. Solovyev
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Dennis W. Smith Jr.
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Charles U. Pittman Jr.
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

GM: Conceptualization, experimental work, data interpretation, data curation, writing—reviewing, and editing original draft. KMC: Experimental work and writing—reviewing. MES: Experimental work and writing—reviewing. DWS: Conceptualization, funding acquisition, data interpretation, supervision, and writing—reviewing. CUP: Conceptualization, data interpretation, administration, and writing—reviewing.

Corresponding author

Correspondence to Charles U. Pittman Jr..

Ethics declarations

Competing Interests

The authors declare no competing interests.

Additional information

Memorial tribute to Professor Charles Carraher

The senior authors of this paper, CUP and DWS, honor Professor Charles Carraher’s life, legacy and his personal interactions with each of us. CUP and Charles were organometallic and inorganic polymer research contemporaries beginning in the 1970s and continuing into the 2020s. Together they edited 16 books on these topics, the first appearing in 1978 and the last in 2010. Other contributors to some of these books included the Editors of JIOPM. CUP remembers Charles’ dry humor and personal kindness. On one occasion in the late 1970s at a National Meeting of the ACS in Washington, Charles offered to share a hotel room with CUP when none were available at the last minute. The next few days brought pouring rain, which led to miles of running in suit jackets and leather shoes between several distant meeting hotels, jumping curbs and knifing through traffic, neither of us willing to slow to a walk or appear out of breath. Charles wrote a nice tribute in JIOPM after CUP’s retirement. DWS fondly remembers Charles’ passion, encouragement, and tireless support for the POLYED program of the ACS. During DWS’s service as the POLY Chair (2009), Charles was the go-to-senior leader behind POLYED’s success and its ancillary outreach activities, including the International Polymer Education Council and the Polymer Ambassadors program designed to teach K-12 teachers how to use polymers present in everyday life to covey physical science concepts. Charles was a highly driven advocate for macromolecular teaching and development. With professionalism and wit, he demonstrated the ability to recruit and enlist generations of others in this cause. Like the Energizer Bunny, he just kept going and going (and he may still be at it).

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 8014.3 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Muñoz, G., Chamberlain, K.M., Solovyev, M.E. et al. Electrophilic Routes to 6F Polymers and Attempted Synthesis of Semi-fluorinated Group IVB Metallocene Polymers. J Inorg Organomet Polym (2024). https://doi.org/10.1007/s10904-024-03031-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10904-024-03031-5

Keywords

Search

Navigation