Synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK)

In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) are reported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along the nucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallization behavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallization from a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride (solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could be induced by the above methods, and no polymorphism was found. The differences in the crystallization of PEEKEK induced by the above methods are seen in their degree of crystallinity.

Morphology of conductive blend fibers of polyaniline and polyamide-11

Polyaniline (PANI), a member of the intrinsically conducting polymer (ICPs) family, was blended with polyamide-11 (polyco-aminoundecanoyle) in concentrated sulfuric acid. The above solution was used to spin conductive PANI/polyamide-11 fibers by wet-spinning technology. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were employed to study the two-phase morphology of the conductive PANI/polyamide-11 fibers. The micrographs of the cross-section, the axial section and the surface of the monofilament demonstrated that the two blend components were incompatible. The morphology of PANI in the fibers was of fibrillar form, which was valuable for producing conducting channels. The electrical conductivity of the fibers was from 10(-6) to 10(-1) S/cm with the different PANI fraction and the percolation threshold was about 5 wt.%. By comparing the two blend systems of PANI/Polyamide-11 fibers and carbon black filled poly(ethylene terephthalate) (PET) fibers, it was shown that the morphology of the conductive component had an influence on electrical conductivity, The former had higher conductivity and lower percolation threshold than the latter. (C) 2001 Elsevier Science B.V. All rights reserved.

Effects of pressure and molecular weight on the miscibility of polystyrene and cyclohexane

With the aid of Sanchez-Lacombe lattice fluid theory (SLLFT), the phase diagrams were calculated for the system cyclohexane (CH)/polystyrene (PS) with different molecular weights at different pressures. The experimental data is in reasonable agreement with SLLFT calculations. The total Gibbs interaction energy, g*(12) for different molecular weights PS at different pressures was expressed, by means of a universal relationship, as g(12)* =f(12)* + (P - P-0) nu*(12) demixing curves were then calculated at fixed (near critical) compositions of CH and PS systems for different molecular weights. The pressures of optimum miscibility obtained from the Gibbs interaction energy are close to those measured by Wolf and coworkers. Furthermore, a reasonable explanation was given for the earlier observation of Saeki et al., i.e., the phase separation temperatures of the present system increase with the increase of pressure for the low molecular weight of the polymer whereas they decrease for the higher molecular weight polymers. The effects of molecular weight, pressure, temperature and composition on the Flory Huggins interaction parameter can be described by a general equation resulting from fitting the interaction parameters by means of Sanchez-Lacombe lattice fluid theory.

Synthesis and characterization of metallocenes containing tert-butyl substituted cyclopentadienyl ligands and their activities in ethylene polymerization

The metallocene complexes ((BuC5H4)-Bu-t)(2)MCl2 (M=Ti (1a), Zr (1b), Hf (1c)) and (tBu2C5H3)(2)MCl2 (M=Ti (2a), Zr (2b), Hf (2c)) were synthesized by the react ions of Li (BuC5H4)-Bu-t and (LiBu2C5H3)-Bu-t with metal tetrachloride in THF solution. The complexes were characterized by their IR, H-1-NMR and EI-MS. The molecular structure of Ic was determined by X-ray single-crystal structure analysis. The complexes (1a similar to 2c) exhibited high activities for ethylene polymerizatin (up to 3.2x10(6) gPE/mol.h) in the presence of methylaluminoxane (MAO) at room temperature.

Crystal transitions of Nylon 11 under drawing and annealing

The crystal transitions of Nylon 11 annealed and drawn at different temperatures (T-d) with different drawing ratios (n) were investigated by wide-angle X-ray diffraction (WAXD). The alpha -form of Nylon Il could be transformed from the delta'-form by annealing at high temperature, The results showed that the crystal transitions of Nylon 11 strongly depended on the thermal history and the conditions of drawing. The delta'-form Nylon Il could he gradually transformed into the alpha -form when it was drawn at high temperature and the alpha -form was only partly transformed into the delta'-form when it was drawn at low temperature. This should be due to the effect of the competition between thermal inducement and drawing inducement. The thermal inducement was favorable to producing the alpha -form, while the drawing inducement was favorable to producing the delta'-form. (C) 2001 Elsevier Science Ltd. All rights reserved.

Theoretical study on the mechanisms of some elementary reactions catalyzed by modified carbonyl cobalt

All structural geometries of intermediates, transition states and product are, optimized at HF/ LANL2DZ level under the effective core potential approximation. The potential energy profile for some elementary reactions of hydroformylation catalyzed by Co-2(CO)(6)(PH3)(2), consisting of carbonyl insertion, H-2 oxidative addition and aldehyde reductive elimination, are calculated, The transition states are further confirmed by having one and only one imaginary vibrational frequency, The activation energies of carbonyl insertion, H-2 oxidative addition and aldehyde reductive elimination are 54, 02, 134, 02 and 43. 44 kJ/mol, respectively.

改性羰基钴催化氢甲酰化反应系列基元反应的理论研究

在 HF/LANL 2 DZ水平下 ,采用有效核势能近似 ( ECP)从头算方法 ,研究了有机膦配体改性羰基钴催化的氢甲酰化反应循环中部分基元反应步骤的微观反应机理 .优化了基态势能面上诸反应中间体、过渡态和产物的几何构型 .计算了反应活化位垒 .结果表明 ,羰基插入、加氢氧化和脱氢还原的基元反应步骤的活化位垒分别为 54.0 2 ,1 3 4 .0 2和 4 3 .4 4k J/mol

叔丁基取代的环戊二烯基钛、锆、铪二氯化物的合成及催化乙烯聚合

(tBuC5H4 ) 2 MCl2 (M =Ti(1a) ,Zr(1b) ,Hf(1c) )和 (tBu2 C5H3 ) 2 MCl2 (M =Ti(2a) ,Zr(2b) ,Hf(2c) )可以通过单叔丁基环戊二烯基锂或双叔丁基环戊二烯基锂与MCl4 (M =Ti,Zr,Hf)在四氢呋喃中反应制备得到 ,用IR、1H NMR和EI MS对这些化合物进行了表征 .采用X光单晶结构分析测定了 (tBuC5H4 ) 2 HfCl2 的晶体结构 .六个化合物均具有一定的催化乙烯聚合活性

Non-isothermal crystallization kinetics of the poly(3-alkylthiophenes)

According to the data obtained from Differential Scanning Calorimetry (DSC),the method of Jeziorny, BOPOXOBCKHH and a new approach proposed by our laboratry are applied to study the nonisothermal crystallization behavior of poly( 3-dodecylthiophene) (P3DDT) and poly(3-octadecylthiophene) (P3ODT),and Kissinger method is used to get the value of the crystallization activation energy. The effect of the different alkyl substitution on crystallization is also investigated. In comparison to the methods of Jeziorny and BOPOXOBCKHH in which it can be found that the deviation from the line occurs in the later stage of crystallization, the new approach appears applicable due to the better linear relation. The values of the crystallization activation energy of P3DDT and P3ODT are estimated as 184.78kJ/mol and 246.93kJ/mol, respectivley, which implies that it is easiser to crystallize P3DDT than P3ODT.

Crystallization behevior of poly(3-dodecylthiophene)

The crystallization behavior of poly (3-dodecylthiophene) (P3DDT) is studied bq differential scanning calorimetry (DSC) under different cooling rates. When the methods of Jeziorny., Ozawa and a new one proposed by our laboratory are applied to describe its nonisothermal crystallization behavior, the new one is confirmed to be the best and convenient. By determining kinetic parameters, the analysis of the nonisothermal crystallization behavior is performed. According to Kissinger method, the crystallization activation energy of P3DDT is also evaluated.

Separation of Th4+ and RE3+ with hollow fiber extraction

Separation of Th4+ and RE3+ was investigated by hollow fiber membrane extraction with N1923 in countercurrent recirculating operation. The effect of Hf concentration in aqueous phase and flow rates of aqueous and organic phases on mass transfer coefficient was tested. Then the extraction of Th4+ from RE sulfate obtained from Baotou ore was carried out. The results obtained show that the mass transfer coefficient of Th4+ changes with the flow rate of aqueous phase, but does not change with the flow rate of organic phase and H+ concentration in aqueous phase, which suggests that the mass transfer rate of Th4+ is controlled bg that in the water critical layer, The mass transfer rate of RE3+ does not change with the flow rate of water phase, changes a little with the flow rate of organic phase, and changes with H+ concentration, which suggests that the mass transfer rate is controlled by their reaction rate with N1923. Th4+ could be extracted completely in 8 h from RE sulfate solution of Baotou ore with relatively less extraction of RE3+. So the separation of radioactive element under the sealed condition could be done.

Disodium 4,4 '-difluoro-3,3 '-carbonyl-dibenzenesulfonate hydrofluoride tetrahydrate

The structure determination of the title compound, 2Na(+). C13H6F2O7S22-. HF . 4H(2)O, indicates that intermolecular physical crosslinking through Na+ ions exists in the crystal so that ionic aggregates are formed.

Conductive polyaniline poly-omega-aminoundecanoyle blending fiber

Conductive fibers were obtained by blending polyaniline with poly-omega-aminoundecanoyle in-concentrated H2SO4 Micro-fiber caused by non-compatibility between the two polymers was valuable for improving conductive property of the fibers. Abnormal effect on the crystallinity of polyaniline and poly-omega-aminoundecanoyle upon drawing stress was observed.