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Advances in Fluoropolymers
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Advances in Fluoropolymers

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (1 September 2023) | Viewed by 7822

Special Issue Editors

Prof. Dr. Scott T. Iacono

E-Mail Website
Guest Editor
Department of Chemistry & Chemistry Research Center, United States Air Force Academy, Colorado Springs, CO, USA
Interests: fluoropolymers; composites; polymers; surfaces & interfaces; coatings; conjugated polymers; monomer synthesis
Dr. Abby R. Jennings

E-Mail Website
Guest Editor
Department of Chemistry & Chemistry Research Center, United States Air Force Academy, Colorado Springs, CO, USA
Interests: fluoropolymers; composites; polymers; surfaces & interfaces; coatings; conjugated polymers; monomer synthesis

Special Issue Information

Dear Colleagues,

Fluoropolymers are enabling materials that find applications in critical technologies from energy conversion to microelectronics and photonics, extreme environment applications, and biomaterials.

Traditional fluoropolymer technology is nearly 70 years old, and it still maintains a growth rate above the US GNP. In addition to perfluoropolymers, partially fluorinated polymers will continue to impact a wide range of technologies as better control of their unique optical, electronic, processing, extreme environment stability, and surface properties is achieved.

This Special Issue on “Advances in Fluoropolymers” will include invited contributions to the biennial Fluoropolymer 2023 Workshop sponsored by the ACS Division of Polymer Chemistry.

Prof. Dr. Scott T. Iacono
Dr. Abby R. Jennings
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • fluoropolymers
  • monomer synthesis
  • composites
  • surfaces & interfaces
  • coatings
  • aerospace materials

Published Papers (4 papers)

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Research

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12 pages, 5434 KiB  
Article
Efficient Mineralization of Fluoroelastomers Using Superheated Water in the Presence of Potassium Hydroxide
by Jin Hamaura, Hisao Hori, Ayane Fujishima and Hirofumi Mukae
Molecules 2023, 28(20), 7057; https://doi.org/10.3390/molecules28207057 - 12 Oct 2023
Viewed by 1032
Abstract
The mineralization of fluoroelastomers (FKMs) in superheated water in the presence of potassium hydroxide (KOH) was investigated with the aim of developing a methodology for recycling the fluorine element. Two FKMs—an “uncrosslinked FKM”, representing a poly(vinylidene fluoride-co-hexafluoropropylene) (poly(VDF-co-HFP)) copolymer [...] Read more.
The mineralization of fluoroelastomers (FKMs) in superheated water in the presence of potassium hydroxide (KOH) was investigated with the aim of developing a methodology for recycling the fluorine element. Two FKMs—an “uncrosslinked FKM”, representing a poly(vinylidene fluoride-co-hexafluoropropylene) (poly(VDF-co-HFP)) copolymer with a VDF/HFP molar ratio of 78/22 and a “crosslinked FKM” consisting of this copolymer (cured by peroxide) and carbon black—were treated. The fluorine content of these FKMs was efficiently transformed into F− ions in the reaction solution using low KOH concentrations (0.10–0.50 M) at 200–250 °C. When the uncrosslinked or crosslinked FKMs reacted with aqueous KOH (0.20 M) at a rather low temperature (200 °C) for 18 h, the fluorine content of these FKMs was completely mineralized (both F− yields were 100%). Although the crosslinked FKM contained carbon black, the fluorine mineralization of the FKM was not inhibited. The addition of Ca(OH)2 to the reaction solutions after the superheated water treatment at 250 °C for 6 h with aqueous KOH (0.50 M) led to the production of pure CaF2, identified using X-ray spectroscopy, with 100% and 93% yields for the uncrosslinked and crosslinked FKMs, respectively. Full article
(This article belongs to the Special Issue Advances in Fluoropolymers)
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15 pages, 1405 KiB  
Article
New Fluorine-Containing Diamine Monomers for Potentially Improved Polyimides
by Cassandra J. Hager, Colin D. McMillen, Rakesh Sachdeva, Arthur W. Martin and Joseph S. Thrasher
Molecules 2023, 28(19), 6855; https://doi.org/10.3390/molecules28196855 - 28 Sep 2023
Viewed by 1371
Abstract
Two new fluorine-containing diamine monomers were designed with the goal of reducing charge transfer complex (CTC) interactions between neighboring chains in polyimides (i.e., high transparency/low color) while hopefully maintaining the well-known thermal stability and flexibility generally associated with polyimides. The proposed diamines have [...] Read more.
Two new fluorine-containing diamine monomers were designed with the goal of reducing charge transfer complex (CTC) interactions between neighboring chains in polyimides (i.e., high transparency/low color) while hopefully maintaining the well-known thermal stability and flexibility generally associated with polyimides. The proposed diamines have been prepared through (1) the functionalization of 1,3-bis[(pentafluorobenzyl)oxy]benzene with 4-aminophenol and (2) the addition of 2-chloro-5-nitrobenzotrifluoride to 4,4′-bicyclohexanol followed by reduction of the resulting dinitro compound. The new compounds have been characterized by multinuclear NMR and IR spectroscopy and high-resolution liquid chromatography-mass spectrometry as well as single-crystal X-ray diffraction on the new diamine prepared from 4,4′-bicyclohexanol. Not only was the structure of the proposed new diamine confirmed, but another interesting example of hydrogen bonding between an N-H proton and the π-system of an aromatic ring was observed and documented. Initial polymerizations have been carried out via the two-step imidization process. Full article
(This article belongs to the Special Issue Advances in Fluoropolymers)
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6 pages, 1212 KiB  
Article
Influencing the Crystalline Domains of Poly(vinylidenedifluoride) Composites Using Fluorinated Silica Nanoparticles as Drop-In Modifiers
by Nathan J. Weeks, Cole R. Phelps, Enrique T. Gazmin and Scott T. Iacono
Molecules 2022, 27(23), 8398; https://doi.org/10.3390/molecules27238398 - 1 Dec 2022
Viewed by 1350
Abstract
Improvements to fluoropolymer processing techniques by way of utilizing nanoparticles as drop-in processing aids have pronounced effects on bulk composite properties. In this work, we prepared fluoroalkyl-silanized silica nanoparticles (F-SiNPs, ca. 200 nm) that were solvent-blended with polyvinylenedifluoride (PVDF) in order to prepare [...] Read more.
Improvements to fluoropolymer processing techniques by way of utilizing nanoparticles as drop-in processing aids have pronounced effects on bulk composite properties. In this work, we prepared fluoroalkyl-silanized silica nanoparticles (F-SiNPs, ca. 200 nm) that were solvent-blended with polyvinylenedifluoride (PVDF) in order to prepare composites with varying weight fractions. We demonstrated that the ability to functionalize SiNPs with long fluoroalkylchains that induced co-crystallization with the PVDF matrix, resulting in uniform particle dispersion and improved interlaminate adhesion. This was quantitatively investigated using calorimetry and thermogravimetric analysis, which showed a decrease in the bulk crystallinity of the virgin PVDF from 37% to 10% with minimal 10 wt % F-SiNP loading, rendering a nearly amorphous PVDF. Additional discussions in this work include the effects of various bare and fluoroalkyl-functionalized SiNP loadings on the amorphous and crystalline domains of the PVDF matrix, as well as thermal decomposition. Full article
(This article belongs to the Special Issue Advances in Fluoropolymers)
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Review

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33 pages, 7062 KiB  
Review
Fluoropolymers as Unique and Irreplaceable Materials: Challenges and Future Trends in These Specific Per or Poly-Fluoroalkyl Substances
by Bruno Améduri
Molecules 2023, 28(22), 7564; https://doi.org/10.3390/molecules28227564 - 13 Nov 2023
Cited by 7 | Viewed by 3195
Abstract
In contrast to some low-molar-mass per- and polyfluoroalkyl substances (PFASs), which are well established to be toxic, persistent, bioaccumulative, and mobile, fluoropolymers (FPs) are water-insoluble, safe, bioinert, and durable. These niche high-performance polymers fulfil the 13 polymer-of-low-concern (PLC) criteria in their recommended conditions [...] Read more.
In contrast to some low-molar-mass per- and polyfluoroalkyl substances (PFASs), which are well established to be toxic, persistent, bioaccumulative, and mobile, fluoropolymers (FPs) are water-insoluble, safe, bioinert, and durable. These niche high-performance polymers fulfil the 13 polymer-of-low-concern (PLC) criteria in their recommended conditions of use. In addition, more recent innovations (e.g., the use of non-fluorinated surfactants in aqueous radical (co)polymerization of fluoroalkenes) from industrial manufacturers of FPs are highlighted. This review also aims to show how these specialty polymers endowed with outstanding properties are essential (even irreplaceable, since hydrocarbon polymer alternatives used in similar conditions fail) for our daily life (electronics, energy, optics, internet of things, transportation, etc.) and constitute a special family separate from other “conventional” C1–C10 PFASs found everywhere on Earth and its oceans. Furthermore, some information reports on their recycling (e.g., the unzipping depolymerization of polytetrafluoroethylene, PTFE, into TFE), end-of-life FPs, and their risk assessment, circular economy, and regulations. Various studies are devoted to environments involving FPs, though they present a niche volume (with a yearly production of 330,300 t) compared to all plastics (with 460 million t). Complementary to other reviews on PFASs, which lack of such above data, this review presents both fundamental and applied strategies as evidenced by major FP producers. Full article
(This article belongs to the Special Issue Advances in Fluoropolymers)
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