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1.
Acetate containing nickel-zinc hydroxysalts (LHS-Ni-Zn) have been synthesized by coprecipitation and hydrothermal treatment. The acetate anions were exchanged with PW12O403− anions, and optimum conditions to attain the maximum level of W in the compound have been identified. The W intercalated compound was characterized by powder X-ray diffraction, FT-IR spectroscopy, thermogravimetric and differential thermal analyses, scanning electron microscopy and transmission electron microscopy.The exchange of LHS-Ni-Zn with PW12O403− at pH=3 for 72 h leads to a solid with a basal spacing of 9.62 Å and a W content (weight) of 37%. The hydrothermal treatment at 90 °C for 24 h increases this value to 48% with a W/Zn molar ratio of 1.38, which corresponds to a layered compound with lacunary tungstophosphate anions in the interlayer space. The intercalated solid is stable up to 250 °C, the layer structure collapses on dehydroxylation and amorphous compounds were identified at 500 °C. Two crystalline phases, NiO (rock salt) and a solid solution (Zn1−xNix)WO4, were identified by powder X-ray diffraction at high temperature (ca. 1000 °C).  相似文献   

2.
In this study, the reaction conditions of poly-4-[(2-methylphenyl)iminomethyl]phenol (P-2-MPIMP) were studied by using oxidants such as air O2, H2O2 and NaOCl in an aqueous alkaline medium between 50 and 90 °C. The structures of the synthesized monomer and polymer were confirmed by FT-IR, UV-vis, NMR and elemental analysis. The characterization was made by TG-DTA, size exclusion chromatography (SEC) and solubility tests. At the optimum reaction conditions, the yield of poly-4-[(2-methylphenyl)iminomethyl]phenol (P-2-MPIMP) was found to be 20% (for air O2 oxidant), 33% (for H2O2 oxidant), and 74% (for NaOCl oxidant). According to the SEC analysis, the number-average molecular weight (Mn), weight-average molecular weight (Mw) and polydispersity index (PDI) values of P-2-MPIMP were found to be 3300, 4100 g mol−1 and 1.242, using H2O2, and 4550, 5150 g mol−1and 1.132, using air O2 and 5300, 5850 g mol−1 and 1.104, using NaOCl, respectively. According to TG analysis, the weight losses of 4-[(2-methylphenyl)iminomethyl]phenol (2-MPIMP) and P-2-MPIMP were found to be between 75.29% and 48.17% at 1000 °C, respectively. P-2-MPIMP was shown to have a higher stability against thermal decomposition. Also, electrical conductivity of the P-2-MPIMP was measured, showing that the polymer is a typical semiconductor. Electrochemically, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) and electrochemical energy gaps ( of 2-MPIMP and P-2-MPIMP were found to be −6.01, −6.03; −2.63, −2.82; 3.38 and 3.21 eV, respectively. According to UV-vis measurements, the optical band gap (Eg) of 2-MPIMP and P-2-MPIMP was found to be 3.40 and 2.97 eV, respectively.  相似文献   

3.
T. Wu  Y. Li  L. Song 《European Polymer Journal》2005,41(10):2216-2223
Thermal spectra of poly(trimethylene terephthalate) (PTT) were collected over a temperature range of 40-250 °C by FTIR micro-spectroscopy. Based on the changes of absorbance ratio corresponding to characteristic groups in low and high vibration energy states, the apparent enthalpy differences of vibration energy states transformation (ΔHv) in the melting process have been calculated by van’t Hoff equation at constant pressure. In comparison with the values of ΔHv, the status of participation for the vibration mode of various characteristic groups in PTT macromolecular chain segments was analyzed. It was found that the vibration modes related to the trimethylene glycol unit (O-CH2-CH2-CH2-O) of PTT behaved significant sensitivity and made prominent contribution in the melting process. By the summarization of corresponding data, it has shown that the melting course concerned amorphous phase began at as early as 218 °C, accompanied by the occurrence of crystallization to certain extent, and the ending point was at approximately 238 °C; whereas the melting course concerned crystalline phase began till 228 °C, with the top value of 238 °C, and ended at 242 °C. Besides, for the particular ordered arrangement of chain segments of aromatic polyesters in the melting course, FTIR analysis has provided a reasonable explanation on a molecular level.  相似文献   

4.
[(RR′-admpzp)2Ti(OPri)2] complexes (2a-c), synthesized from reaction of Ti(OPri)3Cl (0.5 equiv) with 1-dialkylamino-3-(3,5-dimethyl-pyrazol-1-yl)-propan-2-ol compounds in the presence of triethylamine (0.5 equiv), are pseudo-octahedral with each RR′-admpzp ligand κ2-O,N(pyrazolyl) coordinated to the titanium center. In solution, 2a-c adopt isomeric structures that are in dynamic equilibrium. At 23 °C, 2a-c/1000 MAO catalyst systems furnished high molecular weight polymers with narrow molecular weight distributions (Mw/Mn = 2.7-2.8). At 100 °C, 2a-c/MAO catalyst systems exhibited increased polymerization activity and 2c/1000 MAO system furnished high molecular weight polyethylene with a molecular weight distribution (Mw/Mn = 2.1) that is close to that found for single-site catalysts.  相似文献   

5.
Poly(propylene carbonate) (PPC) showed predominantly degradation under electron-beam irradiation, accompanied by deterioration of its mechanical performance due to sharp decrease of the molecular weight. Crosslinked PPC was prepared by addition of polyfunctional monomer (PFM) to enhance the mechanical performance of PPC. When 8 wt% of PFM like triallyl isocyanurate (TAIC) was added, crosslinked PPC with a gel fraction of 60.7% was prepared at 50 kGy irradiation dose, which showed a tensile strength at 20 °C of 45.5 MPa, whereas it was only 38.5 MPa for pure PPC. The onset degradation temperature (Ti) and glass transition temperature (Tg) of this crosslinked PPC was 246 °C and 45 °C, respectively, a significant increase related to pure PPC of 211 °C and 36 °C. Therefore, thermal and mechanical performances of PPC could be improved via electron-beam irradiation in the presence of suitable PFM.  相似文献   

6.
Asymmetrical flow field-flow fractionation (AsFlFFF) was coupled online with multiangle light scattering (MALS) to study the changes in the molecular weight and the size distribution of the corn starch during carboxymethylation. A corn starch was derivatized with sodium chloroacetate in alcoholic medium under alkaline condition to produce carboxymethyl starches (CMS) having various degrees of substitution (DS). The change in thermal characteristics and granule structure of the native corn starch and CMS were compared using Thermogravimetric analysis and scanning electron microscope. The ionic strength of the carrier liquid (water with 0.02% NaN3) was optimized by adding 50 mM NaNO3 to minimize the interactions among the starch molecules and between the starch molecules and the AsFlFFF membrane. A field-programmed AsFlFFF allowed determination of the molecular weight distribution (MWD) of starches within about 25 min. It was found that carboxymethylation of starch results in reduction in the molecular weight due to molecular degradation by the alkaline treatment. The weight-average molecular weight (Mw) was reduced down to about 4.4 × 105 from about 7.2 × 106 when DS was 0.14. It seems AsFlFFF coupled with MALS (AsFlFFF/MALS) is a useful tool for monitoring the changes taking place in the molecular weight and the size of starch during derivatization.  相似文献   

7.
Hyperbranched-linear star block copolymers, hyperbranched poly(siloxysilane)-block-polystyrene (HBPS-b-PSt), were prepared by atom transfer radical polymerization (ATRP) of styrene in xylene, using bromoester-terminated HBPS (HBPS-Br (P3), Mn = 7500, Mw/Mn = 1.76) as a macroinitiator. The number-average molecular weights of the obtained polymers (Mn) were in the range of 21,800-60,000 and molecular weight distributions were unimodal throughout the reaction (Mw/Mn = 1.28-1.40). These polymers showed 5 wt.% decomposition temperature (Td5) over 300 °C. The DSC thermograms of the resulting polymers indicated two glass transition temperatures (Tg). The Tg of HBPS segment shifted to higher value while the Tg of PSt segment shifted to lower value compared with those of the homopolymers. Preliminary physical characterization related to the solution viscosity of the resulting block copolymers is also reported.  相似文献   

8.
Isothermal melt-crystallization, glass transition and melting behavior of poly(l-lactide) (PLLA) with different molecular weights were investigated by using differential scanning calorimetry. Analysis by Avrami equation showed that crystallization was initiated by heterogeneous nucleation, followed by 3-dimensional growth. The maximum reciprocal half-time of crystallization (1/t1/2) was detected at 105 °C. Double endothermic peaks were observed around the glass transition for PLLA with intermediate crystallinities, indicating the coexistence of bulk-like and confined amorphous regions. Double-melting behavior was analyzed and combined with the equilibrium melting temperature evaluation by non-linear Hoffman-Weeks extrapolation, from which a value of 207.6 °C was deduced for PLLA of infinite molecular weight. Lauritzen-Hoffman theory was employed to analyze the crystallization kinetics. Regime II-III transition was found to occur at 120 °C for PLLA of lower molecular weight. The crystal morphology was also examined by scanning electron microscopy through chemical etching method.  相似文献   

9.
MgAl2O4 was successfully used as a crystalline host network for the synthesis of nickel-based nano cyan refractory ceramic pigments. Different compositions of NixMg1−xAl2O4 (0.1 ? x ? 0.8) powders have been prepared by using a low temperature combustion reaction (LTCR) of the corresponding metal nitrates with urea (U) as a fuel at 300 °C in an open air furnace. The as-synthesized samples were characterized by thermal analysis (TG-DTG/DTA), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). UV-Vis and diffuse reflectance spectroscopy (DRS) using CIE- Lab parameters methods have been used for color measurements. The results show that the NixMg1−xAl2O4 samples are the crystalline phase with a particle size of 8.85-43.66 nm in the temperature range 500-1200 °C. The density, particle size, shape and color are determined for all the prepared samples with different calcination times and temperatures.  相似文献   

10.
5-Vinyltetrazole (VT)-based polymer is mainly produced by ‘click chemistry’ from polyacrylonitrile due to the unavailability of 5-vinyltetrazole monomer, which usually produces copolymers of VT and acrylonitrile rather than pure poly(5-vinyltetrazole) (PVT). In present work, VT was synthesized from 5-(2-chloroethyl)tetrazole via dehydrochlorination. A series of PVT with different molecular weight were synthesized by normal free radical polymerization. The chemical structures of VT and PVT were characterized by 1H NMR and FTIR. PVT without any doped acid exhibits certain proton conductivity at higher temperature and anhydrous state. The proton conductivity of PVT decreases at least 2 orders of magnitude after methylation of tetrazole. PVT and PVT/H3PO4 composite membranes are thermally stable up to 200 °C. The glass transition temperature (Tg) of PVT/xH3PO4 composite membranes is shifted from 90 °C for x = 0.5 to 55 °C for x = 1. The temperature dependence of DC conductivity for pure PVT exhibits a simple Arrhenius behavior in the temperature range of 90–160 °C, while PVT/xH3PO4 composite membranes with higher H3PO4 concentration can be fitted by Vogel–Tamman–Fulcher (VTF) equation. PVT/1.0H3PO4 exhibits an anhydrous proton conductivity of 3.05 × 10−3 at 110 °C. The transmission of the PVT/xH3PO4 composite membrane is above 85% in the wavelength of visible light and changes little with acid contents. Thus, PVT/xH3PO4 composite membranes have potential applications not only in intermediate temperature fuel cells but also in solid electrochromic device.  相似文献   

11.
The heat capacity investigation of crystalline pentasodium zirconium tris(phosphate) was carried out in a vacuum adiabatic calorimeter between 7 and 340 K and in a differential scanning calorimeter of the heat bridge type between 330 and 620 K. Between 389 and 424 K, an isostructural solid-to-solid phase transition of Na5Zr(PO4)3, has been found, the nature of which is connected with a centering of off-centered zirconium atoms in octahedral sites and an occupation transfer between sodium sites in the structure. The results were used to calculate the characteristics of the phase transition and the thermodynamic functions of Na5Zr(PO4)3: the transition temperature T°trs, enthalpy of transition ΔtrsH°, entropy of transition ΔtrsS°; enthalpy H°(T)−H°(0), entropy S°(T) and Gibbs function G°(T)−H°(0) over the range from 0 to 620 K. From hydrofluoric acid solution microcalorimetry, the enthalpy of solution of Na5Zr(PO4)3 at 298.15 K has been determined and the standard enthalpy of formation has been derived. By combining the data obtained by the two techniques, the Gibbs function of formation of Na5Zr(PO4)3 at 298.15 K has been calculated.  相似文献   

12.
Isotactic 6-armed star-shaped poly(vinyl alcohol) (PVA) with a narrow molecular weight distribution was successfully prepared by the living cationic polymerization of 6-armed star-shaped poly(tert-butyl vinyl ether) (PTBVE) and subsequent acidic ether cleavage. The PTBVE was synthesized using hexa(chloromethyl) melamine (HCMM) as a hexafunctional initiator and ZnI2 or ZnCl2 as an activator in toluene/MC (1/1 v/v) at −70 °C. A better living stability of PTBVE was obtained in the ZnCl2 activator system. The number average molecular weight and the polydispersity index of the 6-armed star-shaped PTBVE polymerized with ZnCl2 at −70 °C for 24 h were 156,000 g/mol and 1.47, respectively. The fraction of the mm sequence of the resulting PVA was 52%.  相似文献   

13.
Poly(vinyl octadecanoate)-grafted porous silica (Sil-VODn, n = 23) was newly prepared to investigate the efficiencies of the carbonyl groups in the polymer chain for recognition of polycyclic aromatic hydrocarbons (PAHs) in RP-HPLC. In Sil-VOD23, the octadecyl side chains were connected to the polymer main chain through ester linkage in opposite direction to that in poly(octadecylacrylate)-grafted silica (Sil-ODAn, n = 25) which has been reported by us. Sil-ODAn performs enhanced molecular shape selectivity of PAHs in RP-HPLC through multiple carbonyl–π interaction of aligned carbonyl groups which are induced by the formation of highly oriented structure of side chains. Differential scanning calorimetry of VOD23 demonstrated that octadecyl alkyl chains showed crystalline to isotropic phase transition with endothermic peak at 48.7 °C which was similar to ODA25 (at 47.8 °C). After grafting of both polymers, phase transition phenomenon was completely disappeared in Sil-VOD23 whereas Sil-ODA25 still exhibits phase transition although at lower endothermic peak top temperature (38.5 °C). This indicates that the slight structural change in Sil-VODn and Sil-ODAn influence the ordered structure of side alkyl chains. Moreover, solid-state 13C NMR revealed that the long alkyl chain in Sil-VOD23 is highly disordered as compared with that of Sil-ODA25. Sil-VOD23 was applied to RP-HPLC stationary phase using PAHs as π-electron containing elutes, and compared with Sil-ODA25 and conventional monomeric octadecylated silica (ODS). Results confirmed that Sil-VOD23 showed much higher selectivity for PAH isomers than ODS, but lower than Sil-ODA25. For example, the separation factors for trans-/cis-stilbene were 1.47 (Sil-VOD23), 1.70 (Sil-ODA25) and 1.07 (ODS), respectively. These results indicate that carbonyl groups in Sil-VOD23 are effective for molecular shape recognition of PAHs through carbonyl–π interactions even in the disordered state.  相似文献   

14.
A new type macromonomeric azo initiators also named macroinimers, MIMs, based on polypropylene glycol, PPG, with molecular weight 400 and 2000, were synthesized. Self-condensing radical polymerization of the macroinimers gave cross-linked polypropylene glycols. The solubility parameters of the cross-linked polymers determined using swelling experiments in a series of solvents have been reported. Crosss-linked PPG-400 and cross-linked PPG-2000 indicated the same solubility parameter value. But their swelling ratios were different because of the differences of the chain lengths in between of the cross-points (Mc) of the gels. Therefore, while the largest swelling ratio exhibited by a cross-linked PPG-2000 in tetrahydrofurane was being 19.48, this ratio was 6.84 for the cross-linked PPG-400 in the same solvent. The solubility parameters and constant α for these cross-linked polymers were obtained as δcross-linked PPG-400 = 9.56 (cal cm−3)1/2, α = 0.123 cm3 cal−1 and δcross-linked PPG-2000 = 8.95 (cal cm−3)1/2, α = 0.107 cm3 cal−1 by using the least squares regression method.  相似文献   

15.
The amphiphilic π-shaped copolymers with narrow molecular weight distribution (Mw/Mn = 1.04-1.09) based on polystyrene (PSt) and poly(ethylene glycol) have been synthesized successfully. The reversible addition-fragmentation transfer (RAFT) polymerization of St in the presence of dibenzyl trithiocarbonate and N,N′-azobis(isobutyronitrile) (AIBN) yielded macro RAFT agent PSt-SC(S)S-PSt, subsequent reaction with excess maleic anhydride (MAh) at 80 °C in tetrahydrofuran afforded the PSt-MAh-SC(S)S-MAh-PSt. It was used as RAFT agent in the RAFT polymerization of St, and finally the amphiphilic π-shaped copolymers were obtained by the reaction of MAh with hydroxyl-terminated poly(ethylene glycol methyl ether) at 90 °C for 48 h. Their structures were confirmed by FT-IR and 1H NMR spectra, and their molecular weight and molecular weight distribution were measured by gel permeation chromatography.  相似文献   

16.
Chen Y  Su YH  Zheng LM  Xia XH 《Talanta》2010,83(1):145-148
The electrochemistry of a macrocyclic metal complex Fe(notpH3) [notpH6 = 1,4,7-triazacyclononane-1,4,7-triyl-tris(methylene-phosphonic acid)] reveals that the protonation/deprotonation of the non-coordinated P-OH groups in Fe(notpH3) affects its formal potential value (E0′) considerably. Plotting E0′ as function of solution pH gives a straight line with a slope of −585 mV pH−1 in the pH range of 3.4-4.0, which is about ten times larger than the theoretical value of −58 mV pH−1 for a reversible proton-coupled single-electron transfer at 20 °C. A sensitive pH responsive electrochemical switch sensor is thus developed based on Fe(notpH3) which shows an “on/off” switching at pH ∼ 4.0.  相似文献   

17.
The crystal structure of [Cu(Bic)2] (1) (Bic = N,N-bis(2-hydroxyethyl)glycinate), was determined by single-crystal X-ray diffraction techniques. [Cu(Bic)2]: monoclinic system, space group P21/n. In the complex, the copper atom is tetra coordinated by two oxygen atoms of the carboxylato groups and two nitrogen atoms of the bicinate ligand, forming a distorted square planar coordination geometry. The molecular structure of the complex in solution is the same as that of the crystalline state, as supported by ESR and electronic spectra in solution. The blue complex 1 on heating at ∼500 °C for 6 h results in the formation of black CuO (Tenorite) micro plates.  相似文献   

18.
To mimic the phosphate ester hydrolysis behavior of purple acid phosphatases the heterobimetallic complex [(BNPP)FeIIIL(μ-BNPP)NiII(H2O)](ClO4) (1) has been synthesized from the precursor complexes [FeIII(LH2)(H2O)2](ClO4)3·3H2O and [FeIII(LH2)(H2O)Cl](ClO4)2·2H2O. In these compounds, L2− is the anion of the tetraiminodiphenol macrocyclic ligand (H2L), while LH2 is the zwitterionic form in which the phenolic protons are shifted to the two metal-uncoordinated imine nitrogens, and BNPP is bis(4-nitrophenyl)phosphate. The X-ray crystal structure of compound 1 has been determined. The structure of 1 comprises of two edge-shared distorted octahedrons whose metal centers are bridged by two equatorial phenolate oxygens and two axially disposed oxygens of a BNPP ligand. The internuclear Fe?Ni distance is 3.083 Å. The high-spin iron(III) and nickel(II) in 1 are antiferromagnetically coupled (J = −7.1 cm−1; H = −2JS1·S2) with S = 3/2 spin ground state. The phosphodiesterase activity of 1 has been studied in 70:30 H2O-(CH3)2SO medium with NaBNPP as the substrate. The reaction rates have been measured by varying pH (3-10), temperature (25-50 °C), and with different concentrations of the substrate and complex at a fixed pH and temperature. Treatment of the rate data, obtained at pH 6.0 and at 35 °C, by the Michaelis-Menten approach have provided the following parameters: KM = 3.6 × 10−4 M, Vmax = 1.83 × 10−7 M s−1, kcat = 9.15 × 10−3 s−1. As compared to the uncatalyzed hydrolysis rate of BNPP, the kcat value is 8.3 × 108 times higher, showing that 1 behaves as an excellent model for phosphate ester hydrolysis.  相似文献   

19.
Phase diagrams for ternary system of the Gemini cationic surfactants, N,N-long chain alkyl-2-hydroxyl-N,N,N,N-tetramethyl diammonium dichloride (GnCl2) with butanol and water have been drawn based on experimental data at 25 °C. The phase diagrams show that L phase and different liquid crystalline phases are existent in the ternary system at different components. Electric conductivity of the L phase has been studied. Small-angle X-ray scattering (SAXS), 2H (deuterium) quadrupolar splitting (2H NMR) and the polarizing-light microscope were employed to confirm the characteristic texture structures and the microstructure of three different liquid crystalline phases.  相似文献   

20.
A new-type of sulfide containing diacid (1,1′-thiobis(2-naphthoxy acetic acid)) was synthesized from 2-naphthol in three steps. Reaction of 2-naphthol with sulfur dichloride afforded 1,1′-thiobis(2-naphthol) (TBN). 1,1′-Thiobis(2-naphthoxy acetic ester) (TBNAE) was successfully synthesized by refluxing the TBN with methylcholoroacetate in the presence of potassium carbonate. The related diacid was synthesized by basic solution reduction of TBNAE. The obtained diacid was fully characterized and used to prepare novel thermally stable poly(sulfide ether amide)s via polyphosphorylation reaction with different aromatic diamines. The properties of these new polyamides were investigated and compared with similar polyamides. These polyamides showed inherent viscosities in the range of 0.39-0.87 dL g−1 in N,N-dimethylacetamide (DMAc) at 30 °C and at a concentration of 0.5 g dL−1. All the polyamides were readily soluble in a variety of polar solvents such as DMAc and tetrahydrofuran (THF). These polyamides showed glass transition temperature (Tg) between 241-268 °C. Thermogravimetric analysis measurement revealed the decomposition temperature at 10% weight loss (T10) ranging from 441- 479 °C in argon atmosphere.  相似文献   

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