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1.
Acetone solutions of a cellulose diacetate fraction were studied by viscosity and light scattering methods over the range 12.6–50.32. The temperature dependences of the limiting viscosity number [η], the mean-square radius of gyration 〈s2〉, and the second virial coefficient A2 were determined. The unperturbed mean-square radius of gyration 〈s2o and the expansion factor α, were estimated by using theoretical relations to the interpenetration function. It was found that dln 〈s2o/dT is ?6.4 × 10?3 deg?1, while α, is close to unity over the whole temperature range studied. The viscosity results are interpreted to show that the draining effect is not negligible and the Flory viscosity parameter Φ slightly increases with increasing temperature. It is finally concluded that the value of ?6.9 × 10?3 deg?1 for dln [η]/dT can be ascribable to the rapid decrease in 〈s2o.  相似文献   

2.
The dimeric starting material [Ru(η6-p-cymene)(μ-Cl)Cl]2 reacts with the phosphino-amides o-Ph2P–C6H4CO–NH–R [R = iPr (a), Ph (b), 4-MeC6H4 (c), 4-FC6H4 (d)] to give the mononuclear compounds 1ad [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–NH–R)]Cl. The subsequent reaction of these complexes with KPF6 produced the cationic species 2ad [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–NH–R)][PF6] in which phosphino-amides also act as rigid P,O-chelating ligands. The molecular structures of 2bd were determined crystallographically. Amide deprotonation is achieved when complexes 2ad were made react with 1 M aqueous solution of KOH, affording the corresponding neutral species 3ad [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–N–R)] in which a P,N-coordination mode is suggested.  相似文献   

3.
1,4-Cyclohexadiene underwent monomer-isomerization polymerization to yield poly(1,3-cyclohexadiene) with a Ziegler-Natta catalyst comprising TiCl4–Al(C2H5)3 catalyst with Al/Ti molar ratios of 0.5–3.0 at 60°C for 96 hr. Good yields of polymer were obtained (49.5% yield at Al/Ti = 3.0; [η] = 0.04 dl/g). The infrared and NMR spectra of the polymer were identical to those of poly-(1,3-cyclohexadiene), confirming that 1,4-cyclohexadiene first isomerizes to 1,3-cyclohexadiene and then homopolymerizes to give poly-1,3-cyclohexadiene. 1,3-Cyclohexadiene polymerized without isomerization easily in the presence of TiCl3–Al(C2H5)3 catalyst at Al/Ti molar ratios of 0.5–3.0 at 60°C for 3 hr (76.3% yield at Al/Ti = 3.0; [η] = 0.06 dl/g).  相似文献   

4.
Synthesis, properties, and membrane-separation functions of a novel fluorine-containing poly(phenylacetylene) were examined. The monomer used was [o-n-(perfluorohexyl)phe-nyl]acetylene, which has a rigid rod-like ortho-substituent. Polymers, whose intrinsic vis-cosities ([η]) were ca. 0.4–2.2 dL/g, were obtained in high yields with various W and Mo catalysts. The MoCl5–Ph3Sb catalyst achieved the highest [η] of 2.25 dL/g corresponding to an Mw over one million. The polymer was a brown solid soluble only in F -containing solvents such as m-(CF3)2C6H4. The oxygen permeability coefficient of the polymer mem-brane was 90 barrers, which is the second highest among those of ortho-substituted poly(phenylacetylenes). In the pervaporation of an ethanol–water mixture, the poly-mer membrane showed ethanol permselectivity [α(EtOH/H2O) = 1.7]. © 1995 John Wiley & Sons, Inc.  相似文献   

5.
Kinetics of the reaction of [tetraamminediaquacobalt(III)] perchlorate ion with carbon dioxide in aqueous solution was studied at various temperatures (5–25 °C), variable concentration of CO2 (0.005M; 0.01M; 0.015M) and over the pH range 6.04–8.15 at a fixed ionic strength of solution (1 M NaClO4). Investigations were carried out using stopped‐flow spectrophotometry in the range of 300 – 700 nm. The results enabled determination of the number of steps of the reaction studied. Based on the kinetic equations, rate constants were determined for each step. Finally, the mechanism of carbon dioxide uptake by [tetraamminediaquacobalt(III)] perchlorate ion was proposed and discussed.  相似文献   

6.
The measurement of the apparent elongation viscosity (ηe) of several polyolefin melts was conducted in this study by using the isothermal fiber‐spinning method. The White–Metzner (W–M) model was used to analyze the spinning flow of the polymer melts and, thus, the elongation viscosity was predicted at elongation strain rates ranging from 0 to approximately 5 s?1. The values of the model parameters required in the W–M model were obtained by curve fitting the experimental data obtained from the shear measurements. The elongation viscosity predicted using the W–M model was in good agreement with the experimental results of fiber spinning. In addition, ηe could also be estimated directly from the measured shear viscosity (ηS) with a formulation using the W–M model; the subsequently obtained elongation viscosity and Trouton ratio (TR) were reasonable within a wide range of strain rates. Based on the experimental and theoretical results, the polyolefin with a high molecular weight was observed to have high elongation viscosity, and the polymer with a broad molecular weight distribution also possessed high ηe. The TR value of the commercial polypropylene (PP‐1040) began to increase from 3 at a deformation rate of 0.1 s?1 and grew up asymptotically to 10, whereas the TR of high‐density polyethylene (HDPE‐606) remained nearly at 3 within the entire range of strain rates. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

7.
《Tetrahedron: Asymmetry》1998,9(23):4219-4238
A wide variety of planar chiral cyclopalladated compounds of general formulae [Pd{[(η5-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}Cl(L)] (with L=py-d5 or PPh3), [Pd{[(η5-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}(acac)] or [Pd{[(R1–CC–R2)25-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}Cl] (with R1=R2=Et; R1=Me, R2=Ph; R1=H, R2=Ph; R1=R2=Ph; R1=R2=CO2Me or R1=CO2Et, R2=Ph) are reported. The diastereomers {(Rp,R) and (Sp,R)} of these compounds have been isolated by either column chromatography or fractional crystallization. The free ligand (R)-(+)-[{(η5-C5H4)–CHN–CH(Me)–C10H7}Fe(η5–C5H5)] (1) and compound (+)-(Rp,R)-[Pd{[(Et–CC–Et)25-C5H3)–CHN–CH(Me)–C10H7]Fe(η5-C5H5)}Cl] (7a) have also been characterized by X-ray diffraction. Electrochemical studies based on cyclic voltammetries of all the compounds are also reported.  相似文献   

8.
A series of 5,6-fused ring cyclopentadienyl tricarbonyl manganese and rhenium complexes, [M(CO)3{η 5-1,2-C5H3(1,4-(R)2N2C2}] (2a3d) were isolated by employing an off-metal ring closure route. Reacting thallium cyclopentadienide (Cp) salts (1ad) with [MBr(CO)5] (M = Mn, Re) provided pyridazyl complexes (2a3d) in high yield (75–99 %). Spectroscopic characterization (NMR, IR, MS) confirmed the identity of the desired organometallic pyridazines. The off-metal synthetic pathway employed did improve upon the isolation of these complexes as compared to previously reported routes. The molecular and electronic structure of complexes 2a3d and their optimal energy structures have been characterized with quantum chemistry calculations. Vibrational frequencies calculated were compared to their experimental counterparts. The excited state calculations predict that the dominant low-energy transition involves a ligand-to-metal charge transfer.  相似文献   

9.
Sodium poly(isoprenesulfonate) (NaPIS) fractions consisting of 1,4‐ and 3,4‐isomeric units (0.44:0.56) and ranging in molecular weight from 4.9 × 103 to 2.0 × 105 were studied by static and dynamic light scattering, sedimentation equilibrium, and viscometry in aqueous NaCl of a salt concentration (Cs) of 0.5‐M at 25 °C. Viscosity data were also obtained at Cs = 0.05, 0.1, and 1 M. The measured z‐average radii of gyration 〈S2z1/2, intrinsic viscosities [η], and translational diffusion coefficients D at Cs = 0.5‐M showed that high molecular weight NaPIS in the aqueous salt behaves like a flexible chain in the good solvent limit. On the assumption that the distribution of 1,4‐ and 3,4‐isomeric units in the NaPIS chain is completely random, the [η] data for high molecular weights at Cs = 0.5 and 1 M were analyzed first in the conventional two‐parameter scheme to estimate the unperturbed dimension at infinite molecular weight and the mean binary cluster integral. By further invoking a coarse‐graining of the NaPIS molecule, all the [η] and D data in the entire molecular weight range were then analyzed on the basis of the current theories for the unperturbed wormlike chain combined with the quasi‐two‐parameter theory. It is shown that the experimental 〈S2z, [η], and D are explained by the theories with a degree of accuracy similar to that known for uncharged linear flexible homopolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2071–2080, 2001  相似文献   

10.
The temperature dependence of the heat capacity of bis(η6-o-xylene)chromium(I) fulleride, [(η6-(o-xylene))2Cr]+?[C60]??, over the temperature range 6–340 K was measured on an adiabatic vacuum calorimeter. The low-temperature (20 K ≤ T ≤ 50 K) heat capacity was subjected to multifractal processing; conclusions about the heterodynamic character of the structure were drawn. The experimental data were used to calculate the standard thermodynamic functions C p ° (T), H °(T)-H °(0), S °(T), and G °(T)-H °(0) over the temperature range from T → 0 to 340 K and estimate the standard entropy of fulleride formation from simple substances at 298.15 K. The standard thermodynamic characteristics of [(η6-(o-xylene))2Cr]+?[C60]?? were compared with those of the initial fullerene C60.  相似文献   

11.
Three metal–organic coordination polymers, [M(2,6-bip)2] (M = Zn ( 1 ), Ni ( 2 )) and [Cu (tfbdc)(2,6-bipH)2]•2H2O ( 3 ), were obtained with the similar solvothermal reaction systems of bivalent transition metal salt, 6-(1H-imidazol-1-yl)-2(1H)-pyridinone (2,6-bipH) and 2,3,5,6-tetrafluoroterephthalic acid (H2tfbdc). The three coordination polymers show different framework features, namely 3D ( 1 ), 2D ( 2 ) and 1D ( 3 ) structures, which are resulted from different single-metal ion “node” and “linker” coordination modes. The [ZnO2N2] tetrahedron in 1 and [NiO2N4] octahedron in 2 as a node, is formed from Zn sp3 and Ni d2sp3 hybrid orbits, respectively, while the linker, 2,6-bip, adopts the μ21η1η0 in 1 and μ21η1η1 in 2 coordination modes. PLATON calculation suggests that 1 possesses the micropore structure with a pore volume of 14.2%. In 3 , the [CuO2N2] parallelogram as a node is derived from Cu dsp3 hybrid orbital, while the linkers of 2,6-bipH and tfbdc adopt the μ11η0η0 and μ11η011η0 coordination modes, respectively. Intriguingly, Zn(d10)-centre coordination polymer 1 shows strong blue emission, which are derived from the π* → π transition of the 2,6-bipH ligand. Moreover, 1 exhibits high stability and strong luminescence in both water and ethanol. At this point, the performance of 1 is studied as a chemical sensor for detecting fluoroquinolones drug. The results show that 1 can detect enoxacin in ethanol solution with a low detection limit of 3.61 × 10−5 M. The luminescent sensing mechanisms were investigated from experimental methods and theoretical calculation in detail as well.  相似文献   

12.
Chiral Half‐sandwich Pentamethylcyclopentadienyl Rhodium(III) and Iridium(III) Complexes with Schiff Bases from Salicylaldehyde and α‐Amino Acid Esters [1] A series of diastereoisomeric half‐sandwich complexes with Schiff bases from salicylaldehyde and L‐α‐amino acid esters including chiral metal atoms, [(η5‐C5H5)(Cl)M(N,O‐Schiff base)], has been obtained from chloro bridged complexes [(η5‐C5Me5)(Cl)M(μ‐Cl)]2 (M = Rh, Ir). Abstraction of chloride from these complexes with Ag[BF4] or Ag[SO3CF3] affords the highly sensitive compounds [(η5‐C5Me5)M(N,O‐Schiff base]+X? (M = Rh, Ir; X = BF4, CF3SO3) to which PPh3 can be added under formation of [(η5‐C5Me5)M(PPh3)(N,O‐Schiff base)]+X?. The diastereoisomeric ratio of the complexes ( 1 ‐ 7 and 11 ‐ 12 ) has been determined from NMR spectra.  相似文献   

13.
Aqueous–ionic liquid (A–IL) biphasic systems have been examined in terms of deuterated water, acid, and IL cation and anion mutual solubilities in the upper (water‐rich, in mole fraction) and lower phase of aqueous/IL biphasic systems at ambient temperature. The biphasic mixtures were composed of deuterated acids of various concentrations (mainly DCl, DNO3, and DClO4 from 10?2 to 10?4 M ) and five ionic liquids of the imidazolium family with a hydrophobic anion (CF3SO2)2N?, that is, [C1Cnim][Tf2N], (n=2, 4, 6, 8 and 10). The analytical techniques applied were 1H NMR, 19F NMR, Karl–Fischer titration, pH potentiometry for IL cations and anions, and water and acid determination. The effects of the ionic strength (μ=0.1 M NaCl and NaNO3 as well as μ=0.1 M , 0.2 M and 0.4 M NaClO4, according to the investigated acid), the nature of the IL cation, and the nature of the mineral acid on the solubilities of the (D2O, D+, Tf2N?, C1Cnim+) entities in the lower or upper phases were determined. The addition of sodium perchlorate was found to enhance the Tf2N? solubility while inhibiting the solubility of the ionic liquid cation. Differences in IL cation and anion solubilities of up to 42 mM were evidenced. The consequences for the characterization of the aqueous biphasic system, the solvent extraction process of the metal ions, and the ecological impact of the ILs are discussed.  相似文献   

14.
The Jones–Dole viscosity B-coefficients for various mono-, di-, and tri-saccharides in water and in (0.5, 1.0, 2.0, and 3.0) mol · kg?1 aqueous solutions of sodium acetate have been determined at different temperatures, T = (288.15, 298.15, 308.15, and 318.15) K from viscosity data. Densities used to determine viscosities have been reported earlier. The viscosity B-coefficients of transfer, ΔtB, has been estimated for the transfer of saccharides from water to aqueous sodium acetate solutions. The positive ΔtB values were obtained in all cases and their magnitudes increase with the increase in concentration of sodium acetate. Pair, ηAB and higher order, ηABB viscometric interaction coefficients (using McMillan–Mayer theory), and dB/dT coefficients have also been determined. Activation Gibbs free energies and other related thermodynamic activation parameters of viscous flow have been determined using Feakin’s transition-state theory. These parameters have been discussed in terms of solute–solute and solute–solvent interactions occurring in these solutions.  相似文献   

15.
Paramagnetic products of low-temperature X-ray radiolysis of aqueous poly(vinyl alcohol) solutions (2.5 and 5% by weight) were studied by ESR spectroscopy. Experimental spectra were ascribed to a superposition of signals from hydroxyl radicals and –CH2??C(OH)–CH2? macroradicals (Cα-macroradicals), respectively. No ESR signals corresponding to trapped electrons were observed that was attributed to the peculiarities of microheterogenous structure of the frozen aqueous polymer solutions. Annealing at 115 K resulted in partial conversion of OH radicals to Cα-macroradicals. It was suggested that main part of hydroxyl radicals was stabilized in phase of polycrystalline ice while macroradicals were formed in “mixed” water–polymer phase. The radiation–chemical yields of paramagnetic species stabilized in the systems under study were determined.  相似文献   

16.
Potassium reduction of iron– and ruthenium–penta(organo)[60]fullerene complexes, [M(η5‐C60R5)(η5‐Cp)] ( 1 a : M=Fe, R=Ph; 1 b : M=Fe, R=Me; 1 c : M=Ru, R=Ph; 1 d : M=Ru, R=Me; Cp=C5H5) gave mono‐ and dianions of these complexes. Treatment of the dianion 1 a with α‐bromodiphenylmethane gave three different iron–hepta(organo)[60]fullerenes, [Fe{η5‐C60Ph5(CHPh2)2}(η5‐Cp)], as a mixture of regioisomers. All three compounds were fully characterized by physical methods, including X‐ray crystallography and electrochemical measurements. One of the three compounds contains a new hoop‐shaped condensed aromatic system.  相似文献   

17.
The viscosity B-coefficients of mono-, di-, tri-saccharides and the derivatives (methyl glycosides) in mB = (0.5, 1.0, 2.0, and 3.0) mol · kg−1 aqueous solutions of magnesium chloride have been determined from viscosity data using the Jones–Dole equation at T = (288.15, 298.15, 308.15, and 318.15) K. The viscosity B-coefficients of transfer (ΔtB), the temperature derivatives of B-coefficients (dB/dT), pair and triplet viscometric interaction coefficients (ηAB, ηABB) have been determined. The viscosity B-coefficients data of systems studied in water have been reported earlier. The results have been interpreted in light of the solute–solute and solute–solvent interactions occurring in these systems. The comparison of results has been made with those reported in the presence of potassium chloride, ammonium sulphate, and sodium sulphate.  相似文献   

18.
The (conjugated diene) group 4 metallocenes 1ad (diene=butadiene, isoprene; metallocene=Cp2Zr, Cp2Hf, MeCp2Zr) add B(C6F5)3 to yield the metallacyclic M⋯F–C bridged metallocene–borate–betaine complexes 3ad. These add one equivalent of acetylene to give the chiral metallacyclic insertion products 5ad that can be described as either intramolecular ion-pair type complexes involving interaction of the negatively polarized terminal –CHCH–CH2–[B] group of the resulting σ-ligand system with the positively polarized metallocene moiety of the dipolar betaine product or η2-internal alkene metallocene complexes, respectively, as it is revealed by a comparison with the related acyclic THF-addition products 10 and 12. Propyne inserts unselectively into the terminal Zr–C bond of the complexes 3ac. In each case a 1:1 mixture of the regioisomers 6ac (methyl at C2) and 7ac (methyl group at C1) is obtained.  相似文献   

19.
Syntheses, Structure and Reactivity of η3‐1,2‐Diphosphaallyl Complexes and [{(η5‐C5H5)(CO)2W–Co(CO)3}{μ‐AsCH(SiMe3)2}(μ‐CO)] Reaction of ClP=C(SiMe2iPr)2 ( 3 ) with Na[Mo(CO)35‐C5H5)] afforded the phosphavinylidene complex [(η5‐C5H5)(CO)2Mo=P=C(SiMe2iPr)2] ( 4 ) which in situ was converted into the η1‐1,2‐diphosphaallyl complex [η5‐(C5H5)(CO)2Mo{η3tBuPPC(SiMe2iPr)2] ( 6 ) by treatment with the phosphaalkene tBuP=C(NMe2)2. The chloroarsanyl complexes [(η5‐C5H5)(CO)3M–As(Cl)CH(SiMe3)2] [where M = Mo ( 9 ); M = W ( 10 )] resulted from the reaction of Na[M(CO)35‐C5H5)] (M = Mo, W) with Cl2AsCH(SiMe3)2. The tungsten derivative 10 and Na[Co(CO)4] underwent reaction to give the dinuclear μ‐arsinidene complex [(η5‐C5H5)(CO)2W–Co(CO)3{μ‐AsCH(SiMe3)2}(μ‐CO)] ( 11 ). Treatment of [(η5‐C5H5)(CO)2Mo{η3tBuPPC(SiMe3)2}] ( 1 ) with an equimolar amount of ethereal HBF4 gave rise to a 85/15 mixture of the saline complexes [(η5‐C5H5)(CO)2Mo{η2tBu(H)P–P(F)CH(SiMe3)2}]BF4 ( 18 ) and [Cp(CO)2Mo{F2PCH(SiMe3)2}(tBuPH2)]BF4 ( 19 ) by HF‐addition to the PC bond of the η3‐diphosphaallyl ligand and subsequent protonation ( 18 ) and/or scission of the PP bond by the acid ( 19 ). Consistently 19 was the sole product when 1 was allowed to react with an excess of ethereal HBF4. The products 6 , 9 , 10 , 11 , 18 and 19 were characterized by means of spectroscopy (IR, 1H‐, 13C{1H}‐, 31P{1H}‐NMR, MS). Moreover, the molecular structures of 6 , 11 and 18 were determined by X‐ray diffraction analysis.  相似文献   

20.
The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C3), hexyl (C6), heptyl (C7), and octyl (C8)) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol · kg?1 were taken. The values of the compressibilities, expansivity and apparent molar properties for [Cnmim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich–Mayer and the Pitzer’s equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute–solvent and solute–solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made.  相似文献   

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