Polymerization of 2,2,2-trifluoroethyl vinyl ether

The polymerization of 2,2,2-trifluoroethyl vinyl ether by six different catalyst systems was examined. Low-temperature studies (?78°C) with boron trifluoride etherate catalyst in hydrocarbon and chlorinated solvents slowly yielded low molecular weight polymers which were amorphous and noncrystallizable upon cold drawing. Under similar conditions, polymerizations with boron trifluoride gas were spontaneous, quantitative, and gave relatively high molecular weight, form-stable, amorphous polymer. Heterogeneous polymerizations with chromium trioxide crystals in toluene at 68°C and bulk reactions with ethylmagnesium bromide–carbon tetrachloride catalyst at 40°C failed to produce polymer. Room temperature runs with triisobutylaluminum–titanium tetrachloride catalyst gave amorphous, tacky material. Aluminum hexahydrosulfate heptahydrate (AHS) initiated polymerizations conducted at 25 and 60°C gave low yields of mixtures of amorphous and crystalline polymers, the ratio depending upon the polymerization solvent employed. The infrared spectra and x-ray diffraction intensity curves of crystalline and amorphous poly(trifluoroethyl vinyl ether) are reported and compared herein for the first time.     

Two-dimensional chirped-pulse Fourier transform microwave spectroscopy

Two-dimensional (2D) correlation techniques are developed for chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. The broadband nature of the spectrometer coupled with fast digital electronics permits the generation of arbitrary pulse sequences and simultaneous detection of the 8-18 GHz region of the microwave spectrum. This significantly increases the number of rotation transitions that can be simultaneously probed, as well as the bandwidth in both frequency dimensions. We theoretically and experimentally evaluate coherence transfer of three- and four-level systems to relate the method with previous studies. We then extend the principles of single-quantum and autocorrelation to incorporate broadband excitation and detection. Global connectivity of the rotational energy level structure is demonstrated through the transfer of multiple coherences in a single 2D experiment. Additionally, open-system effects are observed from irradiating many-level systems. Quadrature detection in the indirectly measured frequency dimension and phase cycling are also adapted for 2D CP-FTMW spectroscopy.     

Fourier transform microwave spectrum of CO-dimethyl ether

Two sets of 32 rotational transitions were observed for the carbon monoxide-dimethyl ether (CO-DME) complex and two sets of 30 transitions for both (13)CO-DME and C(18)O-DME, in the frequency region from 3.5 to 25.2 GHz, with J ranging from 1<--0 up to 7<--6, by using a Fourier transform microwave spectrometer. The splittings between the two sets of the same transition varied from 2 to 15 MHz, and the two components were assigned to the two lowest states of the internal rotation of CO with respect to DME governed by a twofold potential. A preliminary analysis carried out separately for the two sets of the observed transition frequencies by using an ordinary asymmetric-rotor Hamiltonian indicated that the heavy-atom skeleton of the complex was essentially planar, as evidenced by the "pseudoinertial defects," i.e., the inertial defects, which involve the contributions of the out-of-plane hydrogens of the two methyl groups, I(cc)-I(aa)-I(bb) of -5.764(23) and -5.753(16) uA(2) for the symmetric and antisymmetric states, respectively. All of the observed transition frequencies were subsequently analyzed simultaneously, by using a phenomenological Hamiltonian which was described in a previous paper on Ar-DME and Ne-DME [Morita et al., J. Chem. Phys. 124, 094301 (2006)]. The rotational constants thus derived were analyzed to give the distance between the centers of gravity of the two component molecules, DME and CO, to be 3.682 A and the angle between the CO and the a-inertial axes to be 75.7 degrees ; the C end of the CO being closer to the DME. Most a-type transitions were observed as closely spaced triplets, which were ascribed to the internal rotation of the two methyl tops of DME. The V(3) potential barrier was obtained to be 772(2) cm(-1) from the first-order Coriolis coupling term between the internal rotation and overall rotation, which is about 82% of V(3) for the DME monomer, whereas the second-order contribution of the coupling to the B rotational constant led to V(3) of 705(3) cm(-1). By assuming a Lennard-Jones-type potential, the dissociation energy was estimated to be E(B)=1.6 kJ mol(-1), to be compared with 1.0 and 2.5 kJ mol(-1) for Ne-DME and Ar-DME, respectively.     

Conformational study of 2-phenylethylamine by molecular-beam Fourier transform microwave spectroscopy

The conformational preferences of the simplest amine neurotransmitter 2-phenylethylamine have been investigated using molecular beam Fourier transform microwave (MB-FTMW) spectroscopy. Two new conformers have been observed together with the two previously reported by Godfrey et al. [J. Am. Chem. Soc., 1995, 117, 8204]. The (14)N nuclear quadrupole hyperfine structure has been resolved for all four conformers. Comparison of the experimental rotational and quadrupole coupling constants with those calculated theoretically provides a conclusive test for the identification of all conformers. The two most stable conformers present a gauche (folded) disposition of the alkyl-amine chain and are stabilised by a weak NH...pi interaction between the amino group and the aromatic ring. The other two conformers show an anti (extended) arrangement of the alkyl-amine chain. Tunnelling splittings have been observed in the spectrum of one of the anti conformers. The post expansion relative abundances in the supersonic jet have been also investigated and related to the conformer energies.     

Chirped-pulse Fourier transform microwave spectroscopy of perfluoroiodoethane

The pure rotational spectrum of perfluoroiodoethane between 8.0 and 11.9 GHz has been measured on a search accelerated, correct intensity Fourier transform microwave (SACI-FTMW) spectrometer. The spectra is dense with 247 measured transitions in the given region. Only the anti conformer was observed for which rotational constants are reported. Nuclear electric quadrupole coupling constants due to the iodine-127 were determined and are reported. Also, two dipole forbidden/quadrupole allowed ΔJ=2 transitions were observed in the spectra. The observation of these transitions has been rationalized on the basis of near degeneracies between energy levels connected by χ_ab.     

Amidomethylation of Tris(2,2,2-trifluoroethyl) Phosphite

Russian Journal of General Chemistry -     

Fourier transform microwave spectroscopy and Fourier transform microwave-millimeter wave double resonance spectroscopy of the ClOO radical

Pure rotational spectra of the ClOO radical for the (35)Cl and (37)Cl isotopomers have been observed using Fourier transform microwave and Fourier transform microwave-millimeter wave double resonance spectroscopy. The rotational, centrifugal, spin-rotation coupling, and hyperfine coupling constants have been determined by least-squares fits of the observed transition frequencies. The molecular constants indicate that the electronic ground state is 2A". The r(0) structure is determined to be r(0)(ClO)=2.075 A, r(0)(OO)=1.227 A, and theta;(0)(ClOO)=116.4 degrees . Several highly accurate ab initio calculations have also been performed. Some of them turned out to be inaccurate because it is necessary to take into account both static and dynamic electronic correlations. Only multireference (single and double) configuration interaction calculations with large basis sets reproduce the present experimental results. The anharmonic force constants obtained by the ab initio calculations are used to determine the r(e) structure, r(e)(ClO)=2.084(1) A, r(e)(OO)=1.206(2) A, and theta;(e)(ClOO)=115.4(1) degrees . Unique features of the ClOO radical have become clear by the present experiment and the ab initio calculations.     

The trans-isomer of formanilide studied by microwave Fourier transform spectroscopy

The rotational spectra of the trans-isomer of formanilide was recorded by microwave Fourier transform spectroscopy. The rotational and centrifugal distorsion constants as well as the quadrupole coupling constants have been accurately determined. It is shown that the stable conformation corresponds to a planar structure. The energy barrier between this conformation and the less stable one (the amino group lies in a plane perpendicular to the phenyl ring) has been evaluated by ab initio calculations.     

Tacticity control in the radical polymerization of 2,2,2-trifluoroethyl methacrylate with fluoroalcohol

The free-radical polymerization of 2,2,2-trifluoroethyl methacrylate (TEMA) was carried out in fluoroalcohols to achieve stereoregulation. The polymerization reactivity at low temperature and syndiotactic specificity were enhanced by the use of fluoroalcohol as a solvent. The polymer having triad syndiotacticity (rr) of 70% was obtained in perfluoro-t-butyl alcohol. It was noted that the stereochemistry was nearly independent of reaction temperature. The stereoeffect of fluoroalcohols seemed to be due to the hydrogen-bonding interaction between the alcohol and the monomer or growing species. The hydrogen-bonding formation was determined by FTIR. The copolymerization of TEMA with methyl methacrylate (MMA) in hexafluoroisopropanol afforded a copolymer with syndiotactic specificity. By this method, a cladding material for an optical fiber based on poly(methyl methacrylate) (PMMA) with high mechanical strength and low refractive index could be obtained.     

Dielectric behaviour of copolymers based on 2,2,2-trifluoroethyl methacrylate and cyano co-monomers

In the frame of a research aiming at developing new dielectric polymers containing CCN and CF substituents with strong dipole moment, statistical copolymers based on cyano monomers such as acrylonitrile (AN), methacrylonitrile (MAN), methylvinylidene cyanide (MVCN) and 2,2,2-trifluoroethylmethacrylate (MATRIF), were synthesized and characterized. Elemental analysis has shown that the molar percentages of AN and MAN in the copolymers were 45 mol.%, while only 5 mol.% of MVCN was incorporated in the poly(MVCN-co-MATRIF) copolymer. These copolymers exhibit glass transition temperatures, T_g, in the range of 70-90 °C. The dynamic dielectric analyses and their complex permittivities of these copolymers were studied versus the temperature and the frequency. Evidence of an α-relaxation phenomenon in the glass transition region, which is confirmed by the Vogel-Fulcher-Tammann (VFT) temperature dependence of the relaxation times, was assigned to the cooperative reorientation motions of the cyano groups. The values of dielectric strength (Δε) for the copolymers based on MATRIF were determined by Havriliak-Negami (HN) fitting from the dispersion curves, and can be related to the polarity of the monomer unit and to the packing of the macromolecular chains. These relaxations are sometimes overlapped by conduction phenomena due to ionic impurities at low frequencies and high temperatures dipolar losses. In the glassy state, the permittivity values of AN and MAN copolymers show an increase of polarity which makes them candidates for some applications amongst advanced electrical materials such as dielectric layer for capacitors.     

Fourier transform microwave spectroscopy of vinyldiacetylene, vinyltriacetylene, and vinylcyanodiacetylene

The rotational spectra of the three carbon chain molecules vinyldiacetylene (hex-1-ene-3,5-diyne, C(6)H(4)), vinyltriacetylene (oct-1-ene-3,5,7-triyne, C8H4), and its cyano analog vinylcyanodiacetylene (1-cyanohex-5-ene-1,3-diyne, C7H3N) have been observed for the first time by Fourier transform microwave spectroscopy of a supersonic molecular beam. The molecules were observed as products of an electrical discharge through selected precursor mixtures: ethylene/diacetylene and vinylacetylene/diacetylene for the pure hydrocarbon molecules and vinylacetylene/cyanoacetylene for vinylcyanodiacetylene. The measurements yield precise sets of rotational constants that compare very well with theoretical constants obtained by quantum chemical calculations at the B3LYP/cc-pVTZ level of theory. Since these three carbon chains are similar in structure and composition to known astronomical molecules and because of their significant polarity, all three are candidates for radio astronomical detection.     

Determination of structural parameters for ferrocenecarboxaldehyde using Fourier transform microwave spectroscopy

Gas-phase structural parameters for ferrocenecarboxaldehyde have been determined using Fourier transform microwave spectroscopy. Rotational transitions due to a-, b-, and c-type dipole moments were measured. Eighteen rotational constants were determined by fitting the measured transitions of various isotopomers using a rigid rotor Hamiltonian with centrifugal distortion constants. Least-squares fit and Kraitchman analyses have been used to determine the gas-phase structural parameters and the atomic coordinates of the molecule using the rotational constants for various isotopomers. Structural parameters determined from the least-squares fit are the Fe-C bond lengths to the cyclopentadienyl rings, r(Fe-C)=2.047(4) A, and the distance between the carbon atoms of the cyclopentadienyl rings, r(C-C)=1.430(2) A and r(C1-C1')=1.46(1) A of ring carbon and aldehyde carbon atom. Structural parameters were also obtained using density-functional theory calculations, and these were quite helpful in resolving ambiguities in the structural fit analysis, and providing some fixed parameters for the structural analysis. The results of the least squares and the calculations indicate that the carbon atoms of the Cp groups for ferrocenecarboxaldehyde are in an eclipsed conformation in the ground vibrational state.     

Probing thymine with laser ablation molecular beam Fourier transform microwave spectroscopy

Laser ablation in combination with molecular beam Fourier transform microwave spectroscopy has been used to establish unambiguously the presence of the diketo form of thymine in the gas phase and to obtain its structure.     

Experimental and theoretical vibrational study of 2,2,2-trifluoroethyl trifluoromethanesulfonate, CF3SO2OCH2CF3

The infrared spectra of 2,2,2-trifluoroethyl trifluoromethanesulfonate (CF3SO2OCH2CF3) were obtained in the gaseous, liquid and solid states as well as the Raman spectrum of the liquid. Quantum chemistry calculations using the density functional theory were used to predict the most stable geometry and conformation of the studied molecule. Subsequently, the harmonic vibrational frequencies and force field were calculated. An assignment of the observed spectral features made after comparison with the related molecules and with the predicted frequencies was used as the basis of a scaling of the original force field in order to reproduce as well as possible the experimental frequencies. With this purpose a set of scale factors was calculated by a least square procedure, leading to a final root mean square deviation (RMSD) of 9.7 cm(-1).     

三氟乙氧基磷酸酯的合成与性能研究

为提高锂离子电池安全性,本文制备了锂离子电池阻燃添加剂-三氟乙氧基磷酸酯(TFP).通过红外(IR)光谱法鉴定了产物结构;讨论了反应时间、反应物浓度比与产率的关系;以及TFP的加入对1mol/LLiPF6EC/EMC/DMC(1:1:1Vol.)电解液的可燃性、分解电压和离子电导率的影响.结果表明:反应时间、反应物浓度比对TFP产率影响较为明显,当催化剂为15mol.%(相对于三氯氧磷),反应时间6h,三氟乙醇与三氯氧磷摩尔比为6:1时,TFP的产率可以达到94.00%;添加TFP对电解液阻燃效果显著,对电解液的分解电压无不利影响,电解液电导率会有所下降,对Li/LiCoO2电池的比容量影响不大.     

New Syntheses of 1,1-Dichloro-2,2,2-trifluoroethyl Isocyanate and Its Reaction with Triethyl Phosphite

Russian Journal of General Chemistry -     

The pure rotational spectrum of cyclobutane-d1 observed by microwave Fourier transform spectroscopy

Pure rotational transitions of both equatorial and axial conformers of cyclobutane-d₁ in their vibronic ground state have been observed between 12 and 40 GHz with a pulsed microwave Fourier transform (MWFT) spectrometer. Twenty-four transitions of the equatorial as well as 29 transitions of the axial conformer with J⩽40 have been measured. Their assignment has been confirmed by microwave-microwave double-resonance experiments. Rotational constants and the quartic centrifugal distortion constants have been determined for both conformers from the measured frequencies. The r₀ structure has been deduced from these rotational constants.