Synthesis,structure, and thermal properties of fluorinated cesium beta-diketonates

Four fluorinated cesium beta-diketonates, Cs(CF₃COCHCOCF₃) (Cs(hfac)), Cs(CF₃COCHCOCH₃) (Cs(tfac)), Cs(OH₂)((Me)₃CCOCHCOCF₃) (Cs(OH₂)(ptac)), and Cs(OH₂)(PhCOCHCOCF₃) (Cs(OH₂)(btfac)), were synthesized by interaction of the corresponding beta-diketone and Cs₂CO₃ in Et₂O. The formation of Сs(CF₃C(OH)₂CH₂C(OH)₂CF₃)(CF₃COO) or Cs(CF₃C(OH)₂CH₂COCH₃)(tfac) was shown to be dependent on the reaction conditions. The compounds were characterized by elemental analysis, single crystal X-ray diffraction, and TG/DTA analysis. All compounds have ionic structures organized into pseudo chains (in the case of Cs(hfac) and Cs(CF₃C(OH)₂CH₂COCH₃)(tfac)) or pseudo layers (in other cases). According to the TG data Cs(hfac), Cs(tfac), Cs(OH₂)(ptac,) and Cs(OH₂)(btfac) decompose in inert atmosphere within the temperature range 30–550?°C.     

Synthesis,properties, and structure of intercalated graphite fluosulfonate fluorides

Graphite fluosulfonate fluorides of the composition C₂F_x−y(SO₃F)_y (x+y≈1) have been synthesized. The new compounds can be treated as derivatives of graphite fluorides C₂F_x(x≈1) in which approximately 1/50 of the F atoms have been replaced by SO₃F groups. The intercalates based on the new matrices have been studied by X-ray phase analysis, IR spectroscopy, mass spectrometry, and thermography. The ability of the intercalates to absorb various substances is investigated. It is shown that the introduction of a few SO₃F groups into the C₂F_x matrices significantly changes the physicochemical properties and the structure of intercalates; in particular, for intercalates of stage II structure this expands the scope of substances that can penetrate into interlayer spacings. The dependence of the penetration ability of the substances on the van der Waals sizes of their molecules makes intercalates resemble zeolites in properties. Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, Novosibirsk. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No, 1, pp. 144–151, January–February, 1995 Translated by I. Izvekova     

Composition and structure of fluorinated graphite compounds with camphor

Intercalation compounds of fluorinated graphite (ICFG) with camphor are investigated by IR spectroscopy, chromatography, and X-ray phase and element analyses. It is shown that camphor ICFG of first-degree filling (identity period ～11.6 Å) can exist at room temperature.     

The relationship between properties of fluorinated graphite intercalates and matrix composition

Inclusion compounds: intercalates of fluorinated graphite matrix with acetonitrile (C₂F_xBr_z·yCH₃CN, x=0.92, 0.87, 0.69 and 0.49, z≈0.01) were synthesized. The kinetics of the thermal decomposition (the 1^st stage of filling→the 2^nd stage of filling) was studied under isothermal conditions. The relationship between intercalates properties and composition and structure of the matrix is discussed. The online version of the original article can be found at     

The relationship between properties of fluorinated graphite intercalates and matrix composition

Inclusion compounds (intercalates) of fluorinated graphite matrix with acetone (C₂F _x Br _z ·y(CH₃)₂CO, x = 0.49, 0.69, 0.87, 0.92, z ≈ 0.01) were prepared by guest substitution from acetonitrile to acetone. The kinetics of the thermal decomposition (the first stage of filling → the second stage of filling) was studied under isothermal conditions at 292–313 K. The relationship of the host matrices structure with inclusion compounds thermal properties and kinetic parameters is discussed.     

The relationship between properties of fluorinated graphite intercalates and matrix composition

Inclusion compounds (intercalates) of fluorinated graphite matrix with methylene dichloride (C₂F _x Br _z ·yCH₂Cl₂, x = 0.49, 0.69, 0.87, 0.92, z ≈ 0.01) were synthesized by guest substitution from acetonitrile to methylene dichloride. The kinetics of the thermal decomposition (the first stage of filling → the second stage of filling) was studied under isothermal conditions at 291–303 K. The relationship between the structure of host matrices with thermal properties and kinetic parameters of inclusion compounds is discussed.     

Synthesis, characterization and properties of a novel fluorinated polyurethane

A novel fluorinated polyurethane (FPU) was prepared by fluorinated polyether glycol (PTMG-g-HFP) as a soft segment, 1,6-hexamethylene diisocyanate (HDI) or toluene diisocyanate (TDI) as a hard segment and 1,4-butanodiol (BDO) as a chain extender. Fourier transform infrared spectroscopy (FTIR), ¹H NMR, ¹³C NMR and gel permeation chromatography (GPC) were used to characterize the structure of the fluorinated polyurethane. The thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by thermogravimetric analysis (TGA). X-ray photoelectron spectroscopy (XPS) analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. And the mechanical properties of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were also measured. Chemical resistance of polyurethane films was estimated through spot tests with different solvents. The results showed that FPU had high thermal stability, strain-hardening property and good chemical resistance. The XPS measurements showed the fluorine enrichment on the surface of FPU.     

The relationship between properties of fluorinated graphite intercalates and matrix composition

Inclusion compounds (intercalates) of fluorinated graphite matrix with butanone (C₂F_xBr_z·yCH₃COC₂H₅, x = 0.49, 0.69, 0.87, 0.92, z ≈ 0.01) were prepared by guest substitution from acetonitrile to butanone. The kinetics of the thermal decomposition (the 1st stage of filling → the 2nd stage of filling) was studied under isothermal conditions at 294–313 K. The relationship of the host matrices structure with inclusion compounds’ thermal properties and kinetic parameters is discussed.     

Synthesis and properties of novel fluorinated polyurethane based on fluorinated gemini diol

In the current study, the novel fluorinated polyurethanes (FPUs) that contained the gemini branched fluoroether side groups on the hard segments were developed. In brief, to obtain these FPUs, a new class of fluorinated gemini diol with double‐branched fluoroether side groups was first synthesized and characterized by using Fourier transform infrared spectroscopy, nuclear magnetic resonance, and mass spectrometry. Subsequently, a series of FPUs were designed and prepared by using hexamethylene diisocyanate, poly (tetramethylene oxide glycol), 1,4‐butanediol, and fluorinated gemini diol. Analysis of the FPUs' surface properties from contact angle analysis indicated that the water contact angle increased from 81° to more than 120° when the content of fluorinated gemini diol was increased. Differential scanning calorimetry results revealed that introduction of fluorinated gemini dio decreased the T_g of FPUs, causing a better phase separation. Results from thermogravimetric analysis studies indicated the thermal stability of FPUs was improved. Scanning electron microscopy and energy dispersive X‐ray spectroscopy revealed that fluoroether groups migrate to and enrich on the outmost surface of FPUs.     

The relationship between properties of fluorinated graphite intercalates and matrix composition 7

Inclusion compounds (intercalates) of fluorinated graphite matrix with ethyl acetate (C₂F_xBr_z·yCH₃COOC₂H₅, x = 0.49, 0.69, 0.87, 0.92, z = 0.01) were prepared by guest substitution from acetonitrile to ethyl acetate. The kinetics of the thermal decomposition (the first stage of filling → the second stage of filling) was studied under isothermal conditions at 291–307 K. The relationship of the host matrices’ structure with inclusion compounds’ thermal properties and kinetic parameters is discussed.     

Synthesis, characterization and properties of a novel fluorinated methacrylate polymer

A fluorinated monomer of 2-(2,2,2-trifluoroethoxy)ethyl methacrylate (FEMA) was prepared by a “one pot” process and then a novel fluorinated methacrylate polymer, poly[2-(2,2,2-trifluoroethoxy)ethyl methacrylate] (PFEMA), was successfully synthesized via miniemulsion polymerization using cetyltrimethyl ammonium bromide (CTAB) as emulsifier, hexadecane (HD) as co-stabilizer and 2,2′-azobisisobutyronitrile (AIBN) as initiator. The chemical structure of PFEMA was characterized by FT-IR, ¹H NMR and ¹⁹F NMR. GPC results show that the number average molecular weight (M_n) of PFEMA was as high as 8.5 × 10⁵ g/mol and the polydispersity index (PDI) was only 1.3. SEM and DLS characterizations showed that the morphology of PFEMA latex was uniform spheres with the diameter of about 110–125 nm. It was also found that PFEMA has high thermo-stability (T_d > 200 °C), low glass transition temperature (T_g = 13.0 °C), and nice hydrophobicity (θ_water = 99.9°). Comparison studies on PFEMA and poly(2,2,2-trifluoroethyl methacrylate) show that an introduced functional group (–CH₂CH₂O–) has a significant effect on lowering T_g and improving hydrolysis resistance without impairing surface properties.     

Synthesis of fluorinated anti-fluorenacenedione and the structural, electronic, and field-effect properties

Fluorinated anti-fluorenacenedione 6 was newly synthesized by oxidation of a dehydro[12]annulene fused with tetrafluorobenzene 4. X-Ray crystallography of 6 demonstrated a totally planar structure and shorter intramolecular distances for F ... I, F ... O, and I ... O than the corresponding sums of van der Waals (vdW) radii. In the packing structure, molecules are arranged in a pi-stacked motif, and the intermolecular distances between heavy atoms (C ... I, C ... F, C ... O, F ... I, and F ... O) of the adjacent columns are also shorter than the corresponding sums of vdW radii, indicating highly dense packing for the crystal structure of 6. In the 19F NMR spectrum of 6, a signal for the fluorine atom adjacent to iodine exhibited downfield shift by 29-40 ppm as compared with the other three signals. This is attributed to the intramolecular short contact between F and I atoms, which is supposed to cause a donor-acceptor interaction. Cyclic voltammetry of 6 exhibited two reversible reduction waves at E1/2 = -0.91 and -1.45 V vs. Fc/Fc+. A thin film of 6 was prepared by vacuum deposition and was applied to a field-effect transistor (FET) device, which exhibited n-type transistor responses although the mobility was not very high.     

Synthesis and properties of fluorinated thermoplastic polyurethane elastomer

A series of fluorinated thermoplastic polyurethane elastomers (FTPU) based on self-synthesized fluorinate polyether diol (PFGE) were prepared by two-step polymerization. For the purpose of improving the molecular weight and mechanical property of FTPU, polybutylene adipate (PBA) was used to be compounded with PFGE as the soft-segment of FTPU. Effects of the mass ratio of PFGE/PBA and the mass fraction of hard-segment on the mechanical property of FTPU were investigated. The structure and morphology of FTPU were characterized by FTIR, GPC, DMA, surface tension and AFM analysis.     

Synthesis and surface properties of a fluorinated polyether

A new polyether consisting of alternate fluorinated/non-fluorinated phenylene units in the backbone has been synthesized via polycondensation of an AB monomer. At room temperature, the polymer film exhibits a low surface energy that is comparable to poly(tetrafluoroethylene) (PTFE). However, as the temperature is raised above a particular level, the surface energy of the polymer films starts to increase. Morphological measurements suggest that a smooth thin polymer film can be formed by solvent casting, but it spontaneously dewets the substrate surface when thermally annealed.     

Synthesis and mesomorphic properties of chiral fluorinated liquid crystals

Some fluorinated chiral liquid crystals were synthesized and the compounds characterized by IR, ¹H NMR, ¹⁹F NMR and mass spectroscopy and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry and polarizing optical microscopy. Nearly all of the compounds synthesized are liquid crystals with an enantiotropic cholesteric phase. Some of them exhibit a blue phase. Lateral tetrafluoro substitution decreases the clearing point and molecular polarity affects the formation of liquid crystalline phases.     

Synthesis and properties of luminophores derived from fluorinated biphenyls

A procedure was developed for the synthesis of dimethyl 2-fluoro-and 2,2′-difluorobiphenyl-4,4′-dicarboxylates. The latter were converted into fluorinated 4,4′-bis[(E)-2-(1,3-benzoxazol-2-yl)ethenyl]-and 4,4′-bis[5-(4-octyloxyphenyl)-1,3,4-oxadiazol-2-yl]biphenyls which showed strong luminescence in the crystalline state and in solution; their spectral properties were examined.     

Synthesis and mesomorphic properties of chiral fluorinated liquid crystals

Some fluorinated chiral liquid crystals were synthesized and the compounds characterized by IR, ¹H NMR, ¹⁹F NMR and mass spectroscopy and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry and polarizing optical microscopy. Nearly all of the compounds synthesized are liquid crystals with an enantiotropic cholesteric phase. Some of them exhibit a blue phase. Lateral tetrafluoro substitution decreases the clearing point and molecular polarity affects the formation of liquid crystalline phases.     

Synthesis and properties of fluorinated 2-benzoylcyclohexane-1,3-diones

Fluorinated 2-benzoylcyclohexane-1,3-diones were obtained by the O-C isomerization of the corresponding 3-benzoyloxycyclohex-2-en-1-ones under the action of acetone cyanohydrin in the presence of triethylamine in the medium of absolute acetonitrile. The structure of the target compounds was investigated by the means of IR and NMR spectroscopy, and X-ray diffraction analysis.