Fluorinated Polymers Research Articles

Multiphoton-Driven Photocatalytic Defluorination of Persistent Perfluoroalkyl Substances and Polymers by Visible Light.

Perfluoroalkyl substances (PFASs) and fluorinated polymers (FPs) have been extensively utilized in various industries, whereas their extremely high stability poses environmental persistence and difficulty in waste treatment. Current decomposition approaches of PFASs and FPs typically require harsh conditions such as heating over 400 °C. Thus, there is a pressing need to develop a new technique capable of decomposing them under mild conditions. Here, we demonstrated that perfluorooctanesulfonate (PFOS), known as a "persistent chemical," and Nafion, a widely utilized sulfonated FP for ion-exchange membranes, can be efficiently decomposed into fluorine ions under ambient conditions via the irradiation of visible LED light onto semiconductor nanocrystals (NCs). PFOS was completely defluorinated within 8-h irradiation of 405-nm LED light, and the turnover number of the C-F bond dissociation per NC was 17200. Furthermore, 81 % defluorination of Nafion was achieved for 24-h light irradiation, demonstrating the efficient photocatalytic properties under visible light. We revealed that this decomposition is driven by cooperative mechanisms involving light-induced ligand displacements and Auger-induced electron injections via hydrated electrons and higher excited states. This study not only demonstrates the feasibility of efficiently breaking down various PFASs and FPs under mild conditions but also paves the way for advancing toward a sustainable fluorine-recycling society.

Multiphoton‐Driven Photocatalytic Defluorination of Persistent Perfluoroalkyl Substances and Polymers by Visible Light

AbstractPerfluoroalkyl substances (PFASs) and fluorinated polymers (FPs) have been extensively utilized in various industries, whereas their extremely high stability poses environmental persistence and difficulty in waste treatment. Current decomposition approaches of PFASs and FPs typically require harsh conditions such as heating over 400 °C. Thus, there is a pressing need to develop a new technique capable of decomposing them under mild conditions. Here, we demonstrated that perfluorooctanesulfonate (PFOS), known as a “persistent chemical,” and Nafion, a widely utilized sulfonated FP for ion‐exchange membranes, can be efficiently decomposed into fluorine ions under ambient conditions via the irradiation of visible LED light onto semiconductor nanocrystals (NCs). PFOS was completely defluorinated within 8‐h irradiation of 405‐nm LED light, and the turnover number of the C−F bond dissociation per NC was 17200. Furthermore, 81 % defluorination of Nafion was achieved for 24‐h light irradiation, demonstrating the efficient photocatalytic properties under visible light. We revealed that this decomposition is driven by cooperative mechanisms involving light‐induced ligand displacements and Auger‐induced electron injections via hydrated electrons and higher excited states. This study not only demonstrates the feasibility of efficiently breaking down various PFASs and FPs under mild conditions but also paves the way for advancing toward a sustainable fluorine‐recycling society.

High Glass Transition Temperature Fluorinated Polymers Based on Transfer Learning with Small Experimental Data

High Glass Transition Temperature Fluorinated Polymers Based on Transfer Learning with Small Experimental Data

High Glass Transition Temperature Fluorinated Polymers Based on Transfer Learning with Small Experimental Data.

Machine learning can be used to predict the properties of polymers and explore vast chemical spaces. However, the limited number of available experimental datasets hinders the enhancement of the predictive performance of a model. This study proposes a machine learning approach that leverages transfer learning and ensemble modeling to efficiently predict the glass transition temperature (Tg) of fluorinated polymers and guide the design of high Tg copolymers. Initially, the quantum machine 9 (QM9) dataset is employed for model pretraining, thus providing robust molecular representations for the subsequent fine-tuning of a specialized copolymer dataset. Ensemble modeling is used to further enhance prediction robustness and reliability, effectively addressing the problems owing to the limited and unevenly distributed nature of the copolymer dataset. Finally, a fine-tuned ensemble model is used to navigate a vast chemical space comprising 61 monomers and identify promising candidates for high Tg fluorinated polymers. The model predicts 247 entries capable of achieving a Tg over 390 K, of which 14 are experimentally validated. This study demonstrates the potential of machine learning in material design and discovery, highlighting the effectiveness of transfer learning and ensemble modeling strategies for overcoming the challenges posed by small datasets in complex copolymer systems.

Introducing Photo-Cross-Linkable Functionalities on P(VDF-co-TrFE) Ferroelectric Copolymer.

Ferroelectric polymers have emerged as crucial materials for the development of advanced organic electronic devices. Their recent high-end commercial applications as fingerprint sensors have only increased the amount of scientific interest around them. Despite an ever-larger body of studies focusing on optimizing the properties of ferroelectric polymers by physical means (e. g., annealing, stretching, blending or nano-structuring), post-polymerization chemical modification of such polymers has only recently become a field of active study with great promise in expanding the scope of those polymers. In this work, a solution-based post-polymerization modification method was developed for the safe and facile grafting of a plethora of functional groups to the backbone of commercially available Poly(vinylidene fluoride-co-trifluoroethylene P(VDF-co-TrFE) ferroelectric polymers. To showcase the versatility of this approach, photosensitive groups were grafted onto the polymeric backbone, enabling them to undergo photo-cross-linking. Finally, these modified polymers were used as functional negative photoresists in a photolithographic process, highlighting the potential of this method to integrate ferroelectric fluorinated electroactive polymers into standard electronic microfabrication production lines.

Defect Passivation Toward Designing High‐Performance Fluorinated Polymers for Liquid–Solid Contact‐Electrification and Contact‐Electro‐Catalysis

AbstractContact‐electrification at solid–liquid interfaces (SL‐CE) and contact‐electro‐catalysis (CEC) are two blooming research areas with promising applications in sustainable energy, sensing, and chemical processes. However, prior research has neglected the impact of electronic defects on the ability of high‐performance tribo‐materials, like fluorinated polymers, to perform SL‐CE/CEC. Here, through first‐principle calculations, the addition of surface functional groups to fluorinated ethylene propylene (FEP) enables the tuning of its molecular orbitals' positions, and displacing deep‐level defect states from the HOMO‐LUMO gap is shown. Thereafter, FEP films are modified accordingly by plasma etching; resulting in a significant performance improvement of up to 202% (charge) in SL‐CE experiments, and up to 398% (kinetic rate) in CEC dye degradation. This study provides a theoretical and experimental framework to design high‐performance materials for SL‐CE and CEC, and insights into their physical mechanisms and defect passivation, which are all fundamental for the advancement of these fields.

Highly Damping and Self-Healable Ionic Elastomer from Dynamic Phase Separation of Sticky Fluorinated Polymers.

Shock-induced low-frequency vibration damage is extremely harmful to bionic soft robots and machines that may incur the malfunction of fragile electronic elements. However, current skin-like self-healable ionic elastomers as the artificial sensing and protecting layer still lack the ability to dampen vibrations, due to their almost opposite design for molecular frictions to material's elasticity. Inspired by the two-phase structure of adipose tissue (the natural damping skin layer), here, a highly damping ionic elastomer with energy-dissipating nanophases embedded in an elastic matrix is introduced, which is formed by polymerization-induced dynamic phase separation of sticky fluorinated copolymers in the presence of lithium salts. Such a supramolecular design decouples the elastic and damping functions into two distinct phases, and thus reconciles a few intriguing properties including ionic conductivity, high stretchability, softness, strain-stiffening, elastic recovery, room-temperature self-healability, recyclability, and most importantly, record-high damping capacity at the human motion frequency range (loss factor tan δ>1 at 0.1-50Hz). This study opens the door for the artificial syntheses of high-performance damping ionic skins with robust sensing and protective applications in soft electronics and robotics.

Bioinspired Durable Antibacterial and Antifouling Coatings Based on Borneol Fluorinated Polymers: Demonstrating Direct Evidence of Antiadhesion.

Substituting natural products for traditional poison-killing antifouling agents is an efficient and promising method to alleviate the increasingly serious ecological crisis and aggravate the loss due to marine biofouling. Herein, the successful synthesis of poly(methyl methacrylate-co-ethyl acrylate-co-hexafluorobutyl methacrylate-co-isobornyl methacrylate) copolymer (PBAF) with borneol monomers and fluorine by a free radical polymerization method is reported. The PBA0.09F coating exhibits outstanding antibacterial and antifouling activity, achieving 98.2% and 92.3% resistance to Escherichia coli and Staphylococcus aureus, respectively, and the number of Halamphora sp. adhesion is only 26 (0.1645 mm2) in 24 h. This remarkable antibacterial and antifouling performance is attributed to the incorporation of fluorine components into the copolymer, which induces a low surface energy and hydrophobicity and the complex molecular structure of the natural nontoxic antifouling agent borneol. In addition, the results showed that the contents of the adhesion-related proteins mfp-3, mfp-5, and mfp-6 were significantly reduced, which proved that natural substances affect the secretion of biological proteins. Importantly, the PBAF coating exhibits excellent environmental friendliness and long-term stability. The antifouling mechanism is clarified, and an effective guide for an environmentally friendly antifouling coating design is proposed.

Optimized synthesis of fluorinated dithienyl-diketopyrrolopyrroles and new copolymers obtained via direct heteroarylation polymerization

Optimized synthesis of fDT-DPP and related 3-fluorothiophene comonomers and application in highly fluorinated polymers obtained via direct heteroarylation polymerization.

Study of Biofilm Growth on Slippery Liquid-Infused Porous Surfaces Made from Fluoropor.

Undesired growth of biofilms represents a fundamental problem for all surfaces in long-term contact with aqueous media. Mature biofilms resist most biocide treatments and often are a pathogenic threat. One way to prevent biofilm growth on surfaces is by using slippery liquid-infused porous surfaces (SLIPS). SLIPS consist of a porous substrate which is infused with a lubricant immiscible with the aqueous medium in which the bacteria are suspended. Because of the lubricant, bacteria cannot attach to the substrate surface and thus formation of the biofilm is prevented. For this purpose, we manufactured substrates with different porosity and surface roughness values via UV-initiated free-radical polymerization in Fluoropor. Fluoropor is a class of highly fluorinated bulk-porous polymers with tunable porosity, which we recently introduced. We investigated the growth of the biofilm on the substrates, showing that a reduced surface roughness is beneficial for the reduction of biofilm growth. Samples of low roughness effectively reduced Pseudomonas aeruginosa biofilm growth for 7 days in a flow chamber experiment. The low-roughness samples also become transparent when infused with the lubricant, making such surfaces ideal for real-time observation of biofilm growth by optical examination.

Electroactive behavior on demand in Poly(vinylidene fluoride-co-vinyl alcohol) copolymers

Ferroelectric polymers, such as poly(vinylidene fluoride) (PVDF), are attractive electroactive materials that can be integrated in advanced electronic devices. Unfortunately, to obtain the ferroelectric phase in PVDF, additional processing methods or expensive copolymerizations with trifluoroethylene have to be employed. Moreover, the highly fluorinated polymers lack functionalities to gain improved properties, such as wettability and possibilities for crosslinking and nanoobject dispersion. In this work, the synthesis and electroactive behavior of poly(vinylidene fluoride-co-vinyl alcohol) (P(VDF-co-VA)) copolymers are demonstrated using a cheap vinyl acetate-based precursor. We show that the switching properties can be tuned by varying the vinyl alcohol content in the copolymers. Linear dielectric behavior is observed for copolymers with 10 mol % VA due to a mixture of α- and β-crystals. Intriguingly, the incorporation of 15 mol % VA results in the direct crystallization into the ferroelectric β-phase from the melt. Consequently, this P(VDF-co-VA) copolymer with hydroxyl functional groups in the polymer backbone is ferroelectric without additional processing and demonstrates a coercive field and a remnant polarization of 80 MV m−1 and 2.8 μC cm−2 at 200 MV m−1, respectively, showing its high potential for advanced electronic applications.

Highly Fluorinated Methacrylates for Optical 3D Printing of Microfluidic Devices.

Highly fluorinated perfluoropolyether (PFPE) methacrylates are of great interest for transparent and chemically resistant microfluidic chips. However, so far only a few examples of material formulations for three-dimensional (3D) printing of these polymers have been demonstrated. In this paper we show that microfluidic chips can be printed using these highly fluorinated polymers by 3D stereolithography printing. We developed photocurable resin formulations that can be printed in commercial benchtop stereolithography printers. We demonstrate that the developed formulations can be printed with minimal cross-sectional area of 600 µm for monolithic embedded microfluidic channels and 200 µm for open structures. The printed and polymerized PFPE methacrylates show a good transmittance above 70% at wavelengths between 520–900 nm and a high chemical resistance when being exposed to organic solvents. Microfluidic mixers were printed to demonstrate the great variability of different designs that can be printed using stereolithography.

Durably Antibacterial and Bacterially Antiadhesive Cotton Fabrics Coated by Cationic Fluorinated Polymers.

Considerable attention has been devoted to producing antibacterial fabrics due to their very wide applications in medicine, hygiene, hospital, etc. However, the poor antibacterial durability and bad bacterial antiadhesion capacity of most existing antibacterial fabrics limit their applications. In this work, a series of antibacterial and polymeric quaternary ammonium monomers with different alkyl chain length were successfully synthesized to copolymerize with fluorine-containing and other acrylic monomers to generate cationic fluorinated polymer emulsions and durably antibacterial and bacterially antiadhesive cotton fabrics. The relation between antibacterial constituent and its antibacterial activity was investigated. The study indicated that the alkyl chain length and contents of the antibacterial monomers, as well as the add-on percentage of polymer greatly influenced the antibacterial activities of the fabrics. In addition, it was found that incorporation of fluorine component into the polymer greatly enhanced the antibacterial activity and bacterial antiadhesion of the treated fabrics due to the low surface energy induced hydrophobicity. Finally, antibacterial and antiadhesive models of action of the obtained fabrics were illustrated.

Highly fluorinated polymers with sulfonate, sulfamide and N,N-diethylamino groups for the capillary electromigration separation of proteins and steroid hormones.

Highly fluorinated polymers are promising materials in separation methods due to their combination of high chemical and thermally stability, hydro- and oleophobicity, and weak intermolecular forces. However, application of these polymers in chromatography is limited because of their low solubility in aqueous-organic solvents. In our research, the highly fluorinated water soluble polymers with -SO3- N(Et)4+ , -SO2 NH2 , and -N(Et)2 terminal groups were synthesized and applied as additives to the background electrolyte for the separation of steroid hormones and proteins by capillary electromigration methods. It is shown that highly fluorinated polymers can be used both as pseudo-stationary phases in electrokinetic chromatography for high separation efficiency (N∼200×103 ) and selectivity (α∼1.1) of uncharged analytes (e.g., steroid hormones), and as dynamic modifiers of fused silica capillary walls. The highest separation efficiency (N∼1×106 ) and selectivity (α∼1.3) of steroid hormones was achieved by combination of sodium dodecyl sulfate and fluoropolymer with sulfonate groups in background electrolyte with pH 2. Dynamic wall coatings based on fluoropolymer with -SO2 NH2 (which are easier and faster to create and wash off) exhibit significantly higher separation efficiency and selectivity compared to capillary electrochromatography on capillary columns based on polymethacrylate polymers.

Combined soft lithographic transfer‐printing and patterning method of highly fluorinated polymers as a facile surface treatment protocol

ABSTRACTA combined soft lithographic transfer‐printing and patterning method of highly fluorinated polymers was investigated aiming to establish a facile surface treatment protocol for various substrates. Spin‐coated layers of poly(1H,1H,2H,2H‐perfluorodecyl methacrylate) (PFDMA) on patterned polydimethylsiloxane (PDMS) molds were transfer‐printed successfully on silicon, glass, aluminum substrates, resulting in the well‐controlled production of nano to micrometer‐scale periodic structures. With careful optimization of the dimension and density of the PFDMA patterns, it was possible to achieve a water contact angle as high as 175° on the transfer‐printed highly fluorinated polymer film. One of the advantages of the transfer‐patterning method is that highly fluorinated polymer films can be printed on curved surfaces while retaining their superhydrophobic and corrosion‐prevention character. In addition, the transfer‐printed PFDMA layers on the glass plates showed enhanced light transmission, which led to the extraction of 10% more light when they were applied to the emitting side of green organic light‐emitting devices. The micro‐patterned PFDMA surfaces also exhibited a significantly reduced level of bacterial adhesion when they were incubated in human bile juice. These results strongly suggest that the proposed facile transfer‐patterning protocol of highly fluorinated polymer films can be a suitable surface‐treatment technique for implantable electronic devices that exhibit improved device performance and anti‐biofouling nature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45184.

New highly fluorinated polymers: Modifiers of chromatographic and electrophoretic systems

A set of four highly fluorinated copolymers that differ from each other in the length of perfluorinated pendants to the fluorine-containing polymer backbone chain, charge, and acid–base functions of terminal groups (sulfonate, carboxylate, sulfamide, and N,N-diethylcarbamide) is obtained for the first time. Packed columns for gas–liquid chromatography (GLC) are prepared on the basis of synthesized fluoropolymers as stationary phases. Evaluation of main types of interactions between fluoropolymers and analytes of different nature and relative polarity of phases obtained is performed using McReynolds constants and Kovats retention indices. It is found that, under the conditions of capillary electrophoresis (CE) and micellar electrokinetic chromatography (MEKC), the influence of fluoropolymer as a component of supporting electrolyte on the increase in the efficiency (by two to three times) and separation selectivity of neutral analytes (steroid hormones) is due to two reasons: modification of walls of quartz capillary by the polymer and formation of a pseudostationary phase. Under the conditions of high-performance thin-layer chromatography (HPTLC) the introduction of highly fluorinated polymers into eluent composition results in the increase in the efficiency by two to four times in the determination of amino acids and water-soluble vitamins.

Influence of fluorination on the characterization of fluorotelomer-based acrylate polymers by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The relative degree of fluorotelomer-based acrylate polymers (FTACPs) fluorination was demonstrated to influence the sample preparation protocol for matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry. A homologous series of FTACPs were synthesized from fluorotelomer and hydrocarbon acrylates of different chain lengths, which varied the ratio of perfluorinated to hydrogenated carbons (RF/RH). The solubility of FTACPs in tetrahydrofuran (THF) and chloroform was observed to decrease for highly fluorinated FTACPs (RF/RH>0.5) promoting FTACP aggregation. No dependence on the degree of fluorination was observed for the solubility of FTACPs in the fluorinated solvents α,α,α-trifluorotoluene (TFT) or dichloropentafluoropropanes (HCFC-225). For FTACPs with a low degree of fluorination such as poly(8:2 FTAC-co-HDA) (RF/RH=0.375), MALDI-ToF analysis was successful using a conventional sample preparation protocol with THF, and dithranol (Dith) matrix. Conversely, the poor solubility of the highly fluorinated poly(8:2 FTAC-co-BA) (RF/RH=1.5) in THF resulted in mass discrimination. Several fluorinated sample preparation protocols were evaluated for poly(8:2 FTAC-co-BA) using TFT and HCFC-225, and decafluoroazobenzene (DFAB) or 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB) matrices. The high volatility of HCFC-225 decreased FTACP pooling during solvent evaporation in comparison to the less volatile TFT, and improved the quantity of detectable signals. MALDI-ToF analysis of poly(8:2 FTAC-co-BA) in a 95:5 HCFC-225:methanol with DCTB being the best sample preparation protocol for highly fluorinated FTACPs in this study producing the highest number of observable signals. Employing a fluorinated sample preparation offers the capability of analyzing other highly fluorinated polymers that are not compatible with conventional sample preparations.

Addressable Carbene Anchors for Gold Surfaces

New strategies to access functional monolayers could augment current surface modification methods. Here we present addressable N-heterocyclic carbene (ANHC) anchors for gold surfaces. A suite of experimental and theoretical methods was used to characterize ANHC monolayers. We demonstrate grafting of highly fluorinated polymers from surface-bound ANHCs. This work establishes ANHCs as viable anchors for gold surfaces.

Fluorinated monomers and polymers with specific properties for integrated optics and photonics

Nowadays, fluorinated polymeric materials are increasingly used in integrated optics owing to their high functionality and manufacturability [1–4]. As distinct from hydrocarbon polymers, fluorinated poly� mers have lower absorption in all three telecom wave� length ranges near 0.85, 1.3, and 1.55 µm. This is caused by the fact that the stretching vibra� tion overtones of the C–F bonds are shifted toward longer wavelengths as compared with the C–H over� tones responsible for the absorption in the given spec� tral ranges [5]. Yet another specific feature of fluori� nated monomers is the low refractive index ( nD). The

P1—Nomenclature and acronyms for highly fluorinated substances—Polymers and chemicals

P1—Nomenclature and acronyms for highly fluorinated substances—Polymers and chemicals