Fluoropolymer Nanoparticles Synthesized via Reversible-Deactivation Radical Polymerizations and Their Applications.

Fluorinated polymeric nanoparticles (FPNPs) combine unique properties of fluorocarbon and polymeric nanoparticles, which has stimulated massive interest for decades. However, fluoropolymers are not readily available from nature, resulting in synthetic developments to obtain FPNPs via free radical polymerizations. Recently, while increasing cutting-edge directions demand tailored FPNPs, such materials have been difficult to access via conventional approaches. Reversible-deactivation radical polymerizations (RDRPs) are powerful methods to afford well-defined polymers. Researchers have applied RDRPs to the fabrication of FPNPs, enabling the construction of particles with improved complexity in terms of structure, composition, morphology, and functionality. Related examples can be classified into three categories. First, well-defined fluoropolymers synthesized via RDRPs have been utilized as precursors to form FPNPs through self-folding and solution self-assembly. Second, thermally and photoinitiated RDRPs have been explored to realize in situ preparations of FPNPs with varied morphologies via polymerization-induced self-assembly and cross-linking copolymerization. Third, grafting from inorganic nanoparticles has been investigated based on RDRPs. Importantly, those advancements have promoted studies toward promising applications, including magnetic resonance imaging, biomedical delivery, energy storage, adsorption of perfluorinated alkyl substances, photosensitizers, and so on. This Review should present useful knowledge to researchers in polymer science and nanomaterials and inspire innovative ideas for the synthesis and applications of FPNPs.

TFE Terpolymers: Once Promising - Are There Still Perspectives in the 21st Century? Part II: Processing, Properties, Applications.

Tetrafluoroethylene (TFE) terpolymers have emerged as advantageous substitutes for polytetrafluoroethylene (PTFE). Therefore, they are being considered as alternatives to PTFE in many application areas. The advantages of TFE terpolymers include their facile processability at elevated temperatures, their solubility in some polar organic solvents, their inertness against aqueous acids, aqueous bases and a large number of mostly nonpolar organic solvents, their low dielectric constant, their low refractive index as well as useful electro- and thermochemical properties. This review on TFE terpolymers focuses on their processing including shaping and surface modification as well as on selected properties including wettability, dielectric properties, mechanical response behavior, chemical stability, and degradability. Applications including their use as elastomeric sealing material, liner and cladding layer as well as their use as material for membranes, microfluidic devices, photonics, photovoltaics, energy storage, energy harvesting, sensors, and nanothermitic composites will be discussed. The review concludes with a discussion of the future potential of TFE terpolymers and scientific challenges to be addressed by future research on TFE terpolymers.

TFE Terpolymers: Once Promising - Are There Still Perspectives in the 21st Century: Synthesis, Characterization, and Properties-Part I.

Polytetrafluoroethylene (PTFE) exhibits outstanding properties such as high-temperature stability, low surface tension, and chemical resistance against most solvents, strong acids, and bases. However, these traits make it challenging to subject PTFE to standard polymer processing procedures, such as thermoforming and hot incremental forming. While polymer processing at temperatures above the melting point of PTFE is already demanding, the typically large molar mass of PTFE results in extremely high melt viscosities, complicating the processing of PTFE. Also, PTFE tends to decompose at temperatures close to its melting point. Therefore, fluoropolymers obtained by copolymerizing tetrafluoroethylene (TFE) with various co-monomers are studied as alternatives to PTFE (e.g., fluorinated ethylene-propylene (FEP)), combining its advantages with better processability. TFE terpolymers have emerged as desirable PTFE alternatives. This review provides an overview of the synthesis with various comonomers and microstructural analysis of PTFE terpolymers and the relationships between the microstructures of TFE terpolymers and their properties.

Plant-environment microscopy tracks interactions of Bacillus subtilis with plant roots across the entire rhizosphere.

Our understanding of plant-microbe interactions in soil is limited by the difficulty of observing processes at the microscopic scale throughout plants' large volume of influence. Here, we present the development of three-dimensional live microscopy for resolving plant-microbe interactions across the environment of an entire seedling growing in a transparent soil in tailor-made mesocosms, maintaining physical conditions for the culture of both plants and microorganisms. A tailor-made, dual-illumination light sheet system acquired photons scattered from the plant while fluorescence emissions were simultaneously captured from transparent soil particles and labeled microorganisms, allowing the generation of quantitative data on samples ∼3,600 mm3 in size, with as good as 5 µm resolution at a rate of up to one scan every 30 min. The system tracked the movement of Bacillus subtilis populations in the rhizosphere of lettuce plants in real time, revealing previously unseen patterns of activity. Motile bacteria favored small pore spaces over the surface of soil particles, colonizing the root in a pulsatile manner. Migrations appeared to be directed toward the root cap, the point of "first contact," before the subsequent colonization of mature epidermis cells. Our findings show that microscopes dedicated to live environmental studies present an invaluable tool to understand plant-microbe interactions.

Recycling and the end of life assessment of fluoropolymers: recent developments, challenges and future trends.

Herein, we present the state of the art technology on the recycling, reuse, thermal decomposition (by thermolysis, thermal processing, flash pyrolysis, smoldering, open burning, open-air detonation, and incineration), and the life cycle assessment of fluoropolymers (FPs, ranging from poly(tetrafluoroethylene), PTFE, and poly(vinylidene fluoride), PVDF, to various fluorinated copolymers based on VDF and TFE). FPs are niche specialty polymers endowed with exceptional properties and have found many applications in high-tech industries. However, compared to other polymers, the reuse of FPs is still not well-established and is in its infancy. Accordingly, their recycling has attracted increasing interest, even reaching the pilot stage. In addition, recently, several studies have been reported on vitrimers, which are regarded as polymers ranking between thermosets and thermoplastics. In this case, although many articles have reported to date on the thermal degradation of these technical polymers, intensive efforts have been devoted to avoiding the release of low molar mass oligomers and per- and poly-fluoroalkyl substances (PFAS, and especially polymerisation aids such as perfluorooctanoic acid (PFOA) and its alternatives), while various reports demonstrated the complete decomposition of PTFE, leading to the formation of TFE (and hexafluoropropylene or octafluorocyclobutane to a lesser extent). Incineration is one of only a few technologies that can potentially degrade FPs and completely degrade PTFE and other PFAS from 850 °C. Recent studies on the mineralisation of FPs under subcritical water represent an interesting approach to close the loop of the fluorine chemistry cycle. Because of the high molar masses (several million for PTFE) and thermal, chemical, photochemical, and hydrolytic inertness and biological stability of FPs, it has been clearly evidenced that they satisfy the 13 accepted regulatory assessment criteria to be considered as polymers of low concern.

Structural Characterization and Physicochemical Properties of Functionally Porous Proton-Exchange Membrane Based on PVDF-SPA Graft Copolymers.

Fluorinated proton-exchange membranes (PEMs) based on graft copolymers of dehydrofluorinated polyvinylidene fluoride (D-PVDF), 3-sulfopropyl acrylate (SPA), and 1H, 1H, 2H-perfluoro-1-hexene (PFH) were prepared via free radical copolymerization and characterized for fuel cell application. The membrane morphology and physical properties were studied via small-(SAXS) and wide-angle X-ray scattering (WAXS), SEM, and DSC. It was found that the crystallinity degree is 17% for PEM-RCF (co-polymer with SPA) and 16% for PEM-RCF-2 (copolymer with SPA and PFH). The designed membranes possess crystallite grains of 5-6 nm in diameter. SEM images reveal a structure with open pores on the surface of diameters from 20 to 140 nm. Their transport and electrochemical characterization shows that the lowest membrane area resistance (0.9 Ωcm2) is comparable to perfluorosulfonic acid PEMs (such as Nafion®) and polyvinylidene fluoride (PVDF) based CJMC cation-exchange membranes (ChemJoy Polymer Materials, China). Key transport and physicochemical properties of new and commercial membranes were compared. The PEM-RCF permeability to NaCl diffusion is rather high, which is due to a relatively low concentration of fixed sulfonate groups. Voltammetry confers that the electrochemical behavior of new PEM correlates to that of commercial cation-exchange membranes, while the ionic conductivity reveals an impact of the extended pores, as in track-etched membranes.

Fluoropolymers as Unique and Irreplaceable Materials: Challenges and Future Trends in These Specific Per or Poly-Fluoroalkyl Substances.

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.

Are (Co)Polymers of 1,1,3,3,3-Pentafluoropropene Possible?

The copolymerization and terpolymerization of 1,1,3,3,3-pentafluoropropene (PFP) with various combinations of fluorinated and hydrogenated comonomers were investigated. The chosen fluoromonomers were vinylidene fluoride (VDF), 3,3,3-trifluoropropene (TFP), hexafluoropropene (HFP), perfluoromethylvinyl ether (PMVE), chlorotrifluoroethylene (CTFE) and tert-butyl-2-trifluoromethacrylate (MAF-TBE), while the hydrocarbon comonomers were vinylene carbonate (VCA), ethyl vinyl ether (EVE) and 3-isopropenyl-α,α-dimethylbenzyl isocyanate (m-TMI). Copolymers of PFP with non-homopolymerizable monomers (HFP, PMVE and MAF-TBE) led to quite low yields, while the introduction of VDF enabled the synthesis of poly(PFP-ter-VDF-ter-M3) terpolymers with improved yields. PFP does not homopolymerize and delays the copolymerizations. All polymers were either amorphous fluoroelastomers or fluorothermoplastics with glass transition temperatures ranging from -56 °C to +59 °C, and they exhibited good thermal stability in air.

Original Fluorinated Non-Isocyanate Polyhydroxyurethanes.

New fluorinated polyhydroxyurethanes (FPHUs) with various molar weights were synthesized via the polyaddition reaction of a fluorinated telechelic bis(cyclocarbonate) (bis-CC) with a diamine. The fluorinated bis-CC was initially synthesized by carbonylation of a fluorinated diepoxide, 1,4-bis(2',3'-epoxypropyl)perfluorobutane, in the presence of LiBr catalyst, in high yield. Then, several reaction conditions were optimized through the model reactions of the fluorinated bis-CC with hexylamine. Subsequently, fluorinated polymers bearing hydroxyurethane moieties (FPHUs) were prepared by reacting the bis-CC with different hexamethylenediamine amounts in bulk at 80 °C and the presence of a catalyst. The chemoselective polymerization reaction yielded three isomers bearing primary and secondary hydroxyl groups in 61-82% yield. The synthesized fluorinated CCs and the corresponding FPHUs were characterized by 1H, 19F, and 13C NMR spectroscopy. They were compared to their hydrogenated homologues synthesized in similar conditions. The gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) data of the FPHUs revealed a higher molar mass and a slight increase in glass transition and decomposition temperatures compared to those of the PHUs.

Synthesis of Calamitic Fluorinated Mesogens with Complex Crystallization Behavior.

This work presents the synthesis and self-organization of the calamitic fluorinated mesogen, 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-4-iodobutoxy)ethanesulfonic acid, a potential model for perfluorosulfonic acid membranes (PFSA). The compound is derived in three steps from 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride, achieving a 78% overall yield. The resulting compound exhibits intricate thermal behavior. At 150 °C, a crystal-to-crystal transition is observed due to the partial disordering of calamitic molecules, which is followed by isotropization at 218 °C. Upon cooling, sample ordering occurs through the formation of large smectic liquid crystalline phase domains. This thermotropic state transforms into a layered crystal phase at lower temperatures, characterized by alternating hydrophilic and hydrophobic layers. Using X-ray diffraction, crystalline unit cell models at both room temperature and 170 °C were proposed. Computer simulations of the molecule across varying temperatures support the idea that thermal transitions correlate with a loss of molecular orientation. Importantly, the study underscores the pivotal role of precursor self-organization in aligning channels during membrane fabrication, ensuring controlled and oriented positioning.

Growth-Induced Wrinkles and Dotlike Patterns of a Swollen Fluoroalkylated Thin Film by the Reaction of Surface-Attached Polymethylhydrosiloxane.

The design of hydrophobic surfaces requires a material which has a low solid surface tension and a simple fabrication process for anchoring and controlling the surface morphology. A generic method for the spontaneous formation of robust instability patterns is proposed through the hydrosilylation of a fluoroalkene bearing dangling chains, Rf = C6F13(CH2)3-, with a soft polymethylhydrosiloxane (PMHS) spin-coated gel polymer (0.8 µm thick) using Karstedt catalyst. These patterns were easily formed by an irreversible swelling reaction due to the attachment of a layer to various substrates. The buckling instability was created by two different approaches for a gel layer bound to a rigid silicon wafer substrate (A) and to a soft nonswelling silicone elastomer foundation (B). The observations of grafted Rf-PMHS films in the swollen state by microscopy revealed two distinct permanent patterns on various substrates: dotlike of wavelength λ = 0.4-0.7 µm (A) or wrinkle of wavelength λ = 4-7 µm (B). The elastic moduli ratios of film/substrate were determined using PeakForce quantitative nanomechanical mapping. The characteristic wavelengths (λ) of the patterns for systems A and B were quantitatively estimated in relation to the thickness of the top layer. A diversity of wrinkle morphologies can be achieved by grafting different side chains on pristine PMHS films. The water contact angle (WCA) hysteresis of fluorinated chain (Rf) was enhanced upon roughening the surfaces, giving highly hydrophobic surface properties for water with static/hysteresis WCAs of 136°/74° in the resulting wrinkle (B) and 119°/41° in the dotlike of lower roughness (A). The hydrophobic properties of grafted films on A with various mixtures of hexyl/fluoroalkyl chains were characterized by static CA: WCA 104-119°, ethylene glycol CA 80-96°, and n-hexadecane CA 17-61°. A very low surface energy of 15 mN/m for Rf-PMHS was found on the smoother dotlike pattern.

Trends in the Diels-Alder reaction in polymer chemistry.

The Diels-Alder (DA) reaction is regarded as quite a useful strategy in organic and macromolecular syntheses. The reversibility of this reaction and the advent of self-repair technology, as well as other applications in controlled macromolecular architectures and crosslinking, have strongly boosted the research activity, which is still attracting a huge interest in both academic and industrial research. The DA reaction is a simple and scalable toolbox. Though it is well-established that furan/maleimide is the most studied diene/dienophile couple, this perspective article reports strategies using other reversible systems with deeper features on other types of diene/dienophile pairs being either petro-sourced (cyclopentadiene, anthracene) or bio-sourced (muconic and sorbic acids, myrcene and farnesene derivatives, eugenol, cardanol). This review is composed of four sections. The first one briefly recalls the background on the DA reactions involving cyclodimerizations, dienes, and dienophiles, parameters affecting the reaction, while the second part deals with the furan/maleimide reaction. The third one deals with petro-sourced and bio-sourced (or products becoming bio-sourced) reactants involved in DA reactions are also listed and discussed. Finally, the authors' opinion is given on the potential future of the crosslinking-decrosslinking reaction, especially regarding the process (e.g., key temperatures of decrosslinking) or possibly monocomponents. It presents both fundamental and applied research on the DA reaction and its applications.

Polytetrafluoroethylene: Synthesis and Characterization of the Original Extreme Polymer.

This Review aims to be a comprehensive, authoritative, and critical review of general interest to the chemistry community (both academia and industry) as it contains an extensive overview of all published data on the homopolymerization of tetrafluoroethylene (TFE), detailing the TFE homopolymerization process and the resulting chemical and physical properties. Several reviews and encyclopedia chapters on the properties and applications of fluoropolymers in general have been published, including various reviews that extensively report copolymers of TFE (listed below). Despite this, a thorough review of the specific methods of synthesis of the homopolymer, and the relationships between synthesis conditions and the physicochemical properties of the material prepared, has not been available. This Review intends to fill that gap. As known, PTFE and its marginally modified derivatives comprise some 60-65% of the total international fluoropolymer market with a global increase of ca. 7% per annum of its production. Numerous companies, such as Asahi Glass, Solvay Specialty Polymers, Daikin, DuPont/Chemours, Juhua, 3F, 3M/Dyneon, etc., produce TFE homopolymers. Such polymers, both high-molecular-mass materials and waxes, are chemically inert and hydrophobic and exhibit an excellent thermal stability as well as an exceptionally low coefficient of friction. These polymers find use in applications ranging from coatings and lubrication to pyrotechnics, and an extensive industry (electronic, aerospace, wires and cables, and textiles) has been built around them. South Africa, being the third largest producer of fluorspar (CaF2), the precursor to hydrogen fluoride and fluorine, has embarked on an industrial initiative to locally beneficiate its fluorspar reserves, with the local production of fluoropolymers being one projected outcome. As our manuscript focuses specifically on the homopolymerization of TFE (the starting point for all fluoropolymer industries), it will be of considerable use to start-up companies and other commercial entities looking to enter the fluoropolymer market, as well as to end-user companies. The manuscript commences with a short discussion on the synthesis and production of TFE (both at industrial and laboratory scales), including the safety aspects surrounding handling (because that monomer is regarded as explosive if brought into contact with oxygen due to the formation of peroxides), transport, and storage, and then expands into detailed discussions dealing with aspects such as the various additives used (buffers, chain transfer agents, surfactants, etc.), the solvent environment, and the reaction conditions. A further section reports the properties of PTFE with respect to the polymerization conditions as well as an overview on the specialized techniques used to characterize PTFE. Finally, the applications of PTFE in various fields, ranging from electrical insulation to tribological to medical applications, as well as chemically resistant coatings and pyrotechnics, are discussed.

Unexpected Radical Telomerisation of Vinylidene Fluoride with 2-Mercaptoethanol.

The radical telomerisation of vinylidene fluoride (VDF) with 2-mercaptoethanol as chain transfer agent (CTA) was studied to synthesise fluorinated telomers which bear a hydroxy end-group, such as H(VDF)nS(CH2)2OH, under thermal (di-tert-butyl peroxide as the initiator) or photochemical initiations. A careful structural study of a typical H-VDF-S(CH2)2OH telomer was performed by 1H and 19F NMR spectroscopy. These analytical methods allowed us to explore the selective addition of the thiyl radical onto the hydrogenated side of VDF, and the telomer containing one VDF unit was obtained selectively. Surprisingly, for higher [VDF]o initial concentrations, a monoadduct telomer was produced as well as PVDF homopolymer. This feature was related to the fast consumption of the CTA. The kinetics of radical telomerisation led to a quite high transfer constant of the CTA (40 at 140 °C) that evidences the formation of a monoadduct as the only telomer formed.

May Trifluoromethylation and Polymerization of Styrene Occur from a Perfluorinated Persistent Radical (PPFR)?

The radical polymerization of styrene (St) initiated by a trifluoromethyl radical generated from a perfluorinated highly branched persistent radical (PPFR) is presented with an isolated yield above 70 %. The release of . CF3 radical occurred from a temperature above 85 °C. Deeper 1 H and 19 F NMR spectroscopies of the resulting fluorinated polystyrenes (CF3 -PSts) evidenced the presence of both CF3 end-group of the PSt chain and the trifluoromethylation of the phenyl ring (in meta-position mainly). [PPFR]0 /[St]0 initial molar ratios of 3:1, 3:10 and 3:100 led to various molar masses ranging from 1750 to 5400 g mol-1 in 70-86 % yields. MALDI-TOF spectrometry of such CF3 -PSts highlighted polymeric distributions which evidenced differences between m/z fragments of 104 and 172 corresponding to styrene and trifluoromethyl styrene units, respectively. Such CF3 -PSt polymers were also compared to conventional PSts produced from the radical polymerization of St initiated by a peroxydicarbonate initiator. A mechanism of the polymerization is presented showing the formation of a trifluoromethyl styrene first, followed by its radical (co)polymerization with styrene. The thermal properties (thermal stability and glass transition temperature, Tg ) of these polymers were also compared and revealed a much better thermal stability of the CF3 -PSt (10 % weight loss at 356-376 °C) and a Tg of around 70 °C.

Fluoropolymer Nanoparticles Prepared Using Trifluoropropene Telomer Based Fluorosurfactants.

A fluorosurfactant based on 3,3,3-trifluoropropene (TFP) telomer was synthesized as an environmentally friendly alternative to perfluorooctanoic acid (PFOA) using TFP and 2-iodoperfluoropropane ((CF3)2CF-I) as starting materials. TFP telomerization was initiated by addition of di-tert-butylperoxide in the presence of (CF3)2CF-I as a chain transfer agent. The surfactant was obtained by modification of the iodine end-group on the TFP telomer to form an allylic functionality followed by the addition of thioglycolic acid via a thiol-ene reaction. The resulting fluorosurfactant exhibited a lower critical micellar concentration (CMC = 0.87 g·L-1) than that of PFOA (CMC = 3.0 g·L-1). This surfactant was used to prepare fluoropolymer nanoparticles by solvent evaporation from a solution composed of the surfacant and poly[2-(perfluorobutyl)ethyl methacrylate]. The oil-in-water emulsion was initially formed due to the adsorption of the surfactant molecules at the oil/water interface and subsequently converted into a nanoparticle suspension after solvent evaporation. Because of the strong hydrophobic interactions between the fluorinated surfactant tail and fluoropolymer, the obtained nanoparticle suspension was quite stable against water dialysis.

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives.

Thermal decarbonylation of the acyl compounds [Mn(CO)5 (CORF )] (RF =CF3 , CHF2 , CH2 CF3 , CF2 CH3 ) yielded the corresponding alkyl derivatives [Mn(CO)5 (RF )], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12 CO)4 (eq-13 CO)(RF )] and [Mn(12 CO)4 (ax-13 CO)(RF )] isotopomers and a ranking of the RF donor power in the order CF3

Fluoropolymers: The Right Material for the Right Applications.

An overview on the synthesis, properties, and applications of fluoropolymers (PFs) is presented. First, a non-exhaustive summary on the homopolymers from conventional radical polymerization of fluoromonomers is proposed. FPs are interesting materials thanks to their outstanding properties such as thermal, oxidative and chemical resistances, low dissipation factor, refractive index, permittivity, and water absorptivity, as well as excellent durability and weatherability. Various strategies of synthesis are proposed, especially on recent studies on radical (co)polymerization of fluoroalkenes, just like their properties and applications ranging from coatings and energy-related materials (e.g. fuel cell membranes, components for lithium ion batteries, electroactive devices, and photovoltaics) to original fluorinated elastomers, surfactants, thermoplastic elastomers, thermostables, and optical devices.

Organometallic-Mediated Radical Polymerization of Vinylidene Fluoride.

An unprecedented level of control for the radical polymerization of vinylidene fluoride (VDF), yielding well-defined PVDF (at least up to 14 500 g mol-1 ) with low dispersity (≤1.32), was achieved using organometallic-mediated radical polymerization (OMRP) with an organocobalt compound as initiator. The high chain-end fidelity was demonstrated by the synthesis of PVDF- and PVAc-containing di-and triblock copolymers. DFT calculations rationalize the efficient reactivation of both head and tail chain end dormant species.

Organometallic-Mediated Alternating Radical Copolymerization of tert-Butyl-2-Trifluoromethacrylate with Vinyl Acetate and Synthesis of Block Copolymers Thereof.

Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly(VAc-alt-MAF-TBE) copolymers composed of two electronically distinct monomers: vinyl acetate (VAc, donor, D) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, acceptor, A), with low dispersity (≤1.24) and molar masses up to 57 000 g mol-1 . These copolymers have a precise 1:1 alternating structure over a wide range of comonomer feed compositions. The reactivity ratios are determined as rVAc = 0.01 ± 0.01 and rMAF-TBE = 0 at 40 °C. Remarkably, from a feed containing >50% molar VAc content, poly(VAc-alt-MAF-TBE)-b-PVAc block copolymers are produced via a one-pot synthesis. Such diblock copolymers exhibit two glass transition temperatures attributed to the alternating and homopolymer sequences. The OMRP of this fluorine-containing alternating monomer system may provide access to a wide range of new polymer materials.