微反应技术在氟化反应中的应用

有机含氟化合物因其独特的理化性质被广泛应用于精细化工领域,但传统釜式氟化仍存在在线量大、易产生热点等问题,而微反应技术作为一种高效传质传热的新型技术,有望解决以上问题。因此,该文根据底物类型,综述了近二十年微反应技术的研究进展,以及微反应技术在氟化反应中的应用。微反应技术的应用可以极大地提高氟化效率,相信微反应技术的出现将推动氟化反应向着更为高效、安全、环保、可控及连续化的方向发展,但仍需突破釜式思考模式,并对微反应技术的连续后处理过程进行进一步研究。     

Enhanced anti-graffiti or adhesion properties of polymers using versatile combination of fluorination and polymer grafting

Commonly used polymers and polymer articles have some advantages, e.g. low. But very often they have not very good adhesion, barrier properties, low conductivity, etc. Specialty polymers possessing necessary properties, e.g. fluoropolymers, can be used to fabricate polymer articles. However, practical use of specially synthesized polymers is restricted due to their high cost and complexity of synthesis. It is possible to coat a polymer with another polymer layer with necessary properties but this co-extrusion method is difficult to apply due to a complexity of applied equipment. Also the problems of adhesion between two polymers and polymers compatibility are to be solved. Very often application properties of polymer goods (adhesion, barrier properties, conductivity, etc.) are defined mainly by their surface properties. Hence, it is not necessary to fabricate articles from specialty polymers but simpler, cheaper, and more convenient to apply a surface treatment of articles made from commonly used relatively cheap polymers. In this case, only thin surface layer several nm to several μm in thickness is to be modified and direct fluorination (treatment with mixture of F₂ and other gases) can be effectively used. For our research we have chosen common widely used polymers. We targeted to improve hydrophobicity/hydrophylicity, adhesion properties and surface conductivity of polymers. For the first time modification of the surface of high density (HDPE), low density (LDPE) and ultrahigh molecular weight polyethylene (UHMWPE), polypropylene (PP), polyethylene terephthalate (PET) and polyvinylchloride (PVC) was performed by direct fluorination followed by a grafting of acrylic acid, styrene, acrylonitrile, vinylidene chloride, aniline and thiophene from the gas phase. Aniline grafting was studied to improve surface conductivity of polymers. Grafting of polymers was confirmed by ATR and MATR FTIR spectroscopy and energy-dispersive X-ray microprobe spectroscopy (cartography). AFM was used to study polymers surface. Influence of the nature of grafted monomers on the surface energy was studied. It was shown that depending on the nature of a grafted monomer hydrophobicity or hydrophilicity can be markedly improved. The hydrophobicity of modified polymers is not changed and is even improved with time contrary to virgin polymers. For the case of PP and UHMWPE grafting of styrene and acrylonitrile improved anti-graffiti properties (graffiti and pollutions from the polymer surface can be easier removed). For the case of HDPE and LDPE grafting of styrene and acrylonitrile improved printability. Grafting of aniline did not improved electrical conductivity. The uniformity of grafted polymers distribution was investigated by energy-dispersive X-ray microprobe spectroscopy (cartography) for the first time.     

氟气在直接氟化反应中的应用

介绍了氟气的性质及其应用,同时介绍了氟气在无机氟化反应和有机氟化反应中的应用。     

Ligand‐Assisted Palladium(II)/(IV) Oxidation for sp3 C?H Fluorination

The direct functionalization of inert sp³ C H bonds is limited to a few bond types. Although the activation of sp³ C H bonds can be accomplished under mild conditions using palladium catalysts, the subsequent functionalization is not trivial due to the high energy required to convert palladium(II) to palladium(IV). We have systematically studied the palladium oxidation using computation‐guided experiments for reactions involving strong chelation control. We find that a mild external ligand could significantly accelerate the oxidation of palladium(II) to palladium(IV) for strong bidentate directing groups. The acceleration is believed to be a result of ligand stabilization of both the palladium(II) and palladium(IV) intermediates.

     

Fluorine in Drug Design: A Case Study with Fluoroanisoles

Anisole and fluoroanisoles display distinct conformational preferences, as evident from a survey of their crystal structures. In addition to altering the free ligand conformation, various degrees of fluorination have a strong impact on physicochemical and pharmacokinetic properties. Analysis of anisole and fluoroanisole matched molecular pairs in the Pfizer corporate database reveals interesting trends: 1) PhOCF₃ increases log D by ～1 log unit over PhOCH₃ compounds; 2) PhOCF₃ shows lower passive permeability despite its higher lipophilicity; and 3) PhOCF₃ does not appreciably improve metabolic stability over PhOCH₃. Emerging from the investigation, difluoroanisole (PhOCF₂H) strikes a better balance of properties with noticeable advantages of log D and transcellular permeability over PhOCF₃. Synthetic assessment illustrates that the routes to access difluoroanisoles are often more straightforward than those for trifluoroanisoles. Whereas replacing PhOCH₃ with PhOCF₃ is a common tactic to optimize ADME properties, our analysis suggests PhOCF₂H may be a more attractive alternative, and greater exploitation of this motif is recommended.     

The Effect of Gradual Fluorination on the Properties of FnZnPc Thin Films and FnZnPc/C60 Bilayer Photovoltaic Cells

Motivated by the possibility of modifying energy levels of a molecule without substantially changing its band gap, the impact of gradual fluorination on the optical and structural properties of zinc phthalocyanine (F_nZnPc) thin films and the electronic characteristics of F_nZnPc/C₆₀ (n = 0, 4, 8, 16) bilayer cells is investigated. UV–vis measurements reveal similar Q‐ and B‐band absorption of F_nZnPc thin films with n = 0, 4, 8, whereas for F₁₆ZnPc a different absorption pattern is detected. A correlation between structure and electronic transport is deduced. For F₄ZnPc/C₆₀ cells, the enhanced long range order supports fill factors of 55% and an increase of the short circuit current density by 18%, compared to ZnPc/C₆₀. As a parameter being sensitive to the organic/organic interface energetics, the open circuit voltage is analyzed. An enhancement of this quantity by 27% and 50% is detected for F₄ZnPc‐ and F₈ZnPc‐based devices, respectively, and is attributed to an increase of the quasi‐Fermi level splitting at the donor/acceptor interface. In contrast, for F₁₆ZnPc/C₆₀ a decrease of the open circuit voltage is observed. Complementary photoelectron spectroscopy, external quantum efficiency, and photoluminescence measurements reveal a different working principle, which is ascribed to the particular energy level alignment at the interface of the photoactive materials.     

Behavior of Ruthenium in Fluoride-Volatility Processes, (VI)

Hydrogen gas evolution from water dispersing nanoparticles induced by ⁶⁰Co γ-ray irradiation was studied. Nanoparticles of TiO₂ and Al_2O3 with average sizes of 7–33 nm supplied from several suppliers were examined. It was indicated that reactions enhancing the hydrogen evolution proceed on particle's surface. It was implied that the yield depends on size of agglomerated particle regardless of their primary particle size and chemical species. Reactions that enhance the hydrogen yields were discussed, and radiolysis process was concluded dominant in the total enhancement mechanism.     

Fluorinated graphene: Fluorographene: A Two‐Dimensional Counterpart of Teflon (Small 24/2010)

A stoichiometric derivative of graphene with a fluorine atom attached to each carbon is reported. Raman, optical, structural, micromechanical, and transport studies show that the material is qualitatively different from the known graphene‐based nonstoichiometric derivatives. Fluorographene is a high‐quality insulator (resistivity >10¹² Ω) with an optical gap of 3 eV. It inherits the mechanical strength of graphene, exhibiting a Young’s modulus of 100 N m^?1 and sustaining strains of 15%. Fluorographene is inert and stable up to 400 °C even in air, similar to Teflon.