以葡辛胺为拆分剂拆分酮基布洛芬

The process of resolution of racemic ketoprofen using n-octyl-d-glucamine as an optical resolution agent was investigated. The process consists of preparation of the diastereomer salt of ketoprofen with n-octyl-d-glucamine, liberation of S-（＋）-ketoprofen from its diastereomer salt and recovery of the remaining ketoprofen and n-octyl-d- glucamine. The suitable conditions for preparation of the diastereomer salt were methanol and ethyl acetate （1：1 by volume） as the solvent, the ratio of solvent volume to ketoprofen mass at 8 ml：1 g, and the molar ratio of ketoprofen to n-octyl-d-glucamine at 1：1. The preferred approach to liberate S-（＋）-ketoprofen from its diastereomer salt was alkali dissolution, acid adjustment and ethyl acetate extraction. Racemization of the recovered ketoprofen could be achieved by reacting the recovered ketoprofen with 10% NaOH at 507kPa for 6h. The recovered n-octyl-d- glucamine could be refined by acid dissolution and alkali adjustment. S-（＋）-ketoprofen can be obtained with high optical purity and yield, showing that the present process is a practical and efficient one which can be used in industrial scale for preparation of S-（＋）-ketoprofen.     

Influence of synthesis parameters on the properties of LiFePO4/C cathode material☆

The influence of sintering temperature,carbon content and dispersive agent in ball-milling was investigated on the properties of Li Fe PO_4/C prepared using Fe_2O_3,NH_4H_2PO_4,Li_2CO_3 and glucose via solid state reaction.X-ray powder diffraction,scanning electron microscopy and charge–discharge test were applied to the characterization of the Li Fe PO_4/C samples synthesized under different conditions.Sintering temperature affects the crystallite/particle size and degree of crystallinity of LiF eP O_4,formation of Fe_2 P and maintenance of carbon in LiF e PO_4/C.Carbon maintenance is favored by low sintering temperature,and 700 °C is optimum for synthesis of LiF eP O_4/C with superior electrochemical performance.A higher carbon content in the range of 4.48%–11.03% results in a better rate capability for Li Fe PO_4/C.The dispersive agent used in ball-milling impacts the existent state of carbon in the final product which subsequently determines its charge–discharge behavior.The sample prepared at700 °C by using acetone as the dispersive agent in ball-milling exhibits an excellent rate capability and capacity retention without any fade at 0.1C,1C and 2C,with corresponding average discharge capacities of 153.8,128.3and 121.0 m A·h·g~(-1),respectively,in the first 50 cycles.     

Thermosensitive Poly(N-isopropylacrylamide-co-acrylonitrile) Hydrogels with Rapid Response

Acrylonitrile （AN） was copolymerized with N-isopropylacrylamide （NIPA） to synthesize thermosensitive hydrogels, and the on-off switch behavior of poly（NIPA-co-AN） hydrogels with different fraction of hydrophobic component （AN） was investigated. It is found that the lower critical solution temperature （LCST）, the swelling ratio at certain temperature and the reswelling rate of poly（NIPA-co-AN） hydrogels decreased as AN unit fraction in copolymers increased. In order to improve the responsive rate of poly（NIPA-co-AN） hydrogels, they were further treated by surface crosslinking using N, N′-methylene bisacrylamide （BIS） as a crosslinking agent. The swelling and deswelling behaviors of these copolymers were compared with those of the untreated hydrogels. The results indicated that the responsive rate of poly（NIPA-co-AN） hydrogel was improved by surface crosslinking. The resulting hydrogels bearing cyano groups with fast response have potential applications in the field of drug-controlled release and immobilization of biomolecules.     

Discussion on Wear Mechanism of High Chrome Brick Used in Coal Slurry Gasifier

The microstructure and phase composition of high chrome brick used in coal slurry gasifier has been analyzed by means of SEM and Energy Spectrum. The results indicate that the used brick can be divided into different zones as slag-adhered zone, reaction zone, penetration zone and unaltered zone. The phase composition and microstructure are different and cracks occurred in different degree at these zones. A dense ring belt was formed with complex spinel ( Mg, Fe)( Cr,Al, Fe2O4) in the reaction zone near the hot face. The wear mechanism of the brick during its employment has been discussed. It is considered that the reaction and penetration of coal slag and strong reduetant bring about the composition change of the brick and destroys its original network inlayed structure and consequently result in its structure spalling and weakening strength, which is the main wear mechanism of the brick and followed by temperature fluctuation and high mechanical im-pact of flowing fluid with high-speed.     

鼓泡塔中水合物法分离混合气体的数值模拟

To develop a new technique for separating gas mixtures via hydrate formation,a set of medium-sized experimental bubble column reactor equipment was constructed.On the basis of the structure parameters of the ex- perimental bubble column reactor,assuming that the liquid phase was in the axial dispersion regime and the gas phase was in the plug flow regime,in the presence of hydrate promoter tetrahydrofuran（THF）,the rate of hydrogen enrichment for CH4＋H2 gas mixtures at different operational conditions（such as temperature,pressure,concentra- tion of gas components,gas flow rate,liquid flow rate）were simulated.The heat product of the hydrate reaction and its axial distribution under different operational conditions were also calculated.The results would be helpful not only to setting and optimizing operation conditions and design of multi-refrigeration equipment,but also to hydrate separation technique industrialization.     

太阳能空气加热器管道中填充三角形小翅片扰流器的湍流传热的实验研究简

The paper presents an experimental study on the heat transfer and flow friction characteristics in a solar air heater channel fitted with delta-winglet type vortex generators （DWs）. The experiments are conducted by varying the airflow rate for Reynolds number in the range of 5000 to 24000 in the test section with a uniform heat-flux applied on the upper channel wall. Firstly, the DW pairs are mounted only at the entrance of the lower wall of the test channel （called DW-E） to create multiple vortex flows at the entry. The effect of two transverse pitches （Re= Pt/H= 1 and 2） at three attack angles （a= 30°, 45° and 60°） of the DW-E with its relative height, b/H= 0.5 （half height of channel） is examined. Secondly, the 30° DWs with three different relative heights （blH = 0.3, 0.4 and 0.5） are placed on the upper wall only （absorber plate, called DW-A） of the test channel. The experimental result reveals that in the first case, the 60° DW-E at Rp = 1 provides the highest heat transfer and friction factor while the 30° DW-E at Rp = 1 performs overall better than the others. In the second case, the 30° DW-A at b/H= 0.5 yields the highest heat transfer and friction factor but the best thermal performance is found at b/H = 0.4.     

热致相分离法iPP中空纤维微空膜结构与性能--稀释剂的作用

Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.     

Synthesis of texture-excellent mesoporous alumina using PEG1000 as structure-directing agent

By varying concentration of PEG1000 as a structure-directing agent,mesoporous alumina with excellent textural properties was synthesized.The prepared mesoporous alumina displays high thermal stability,as shown by its textural properties at different calcination temperatures of 600-850 °C.Characterization by SEM and TEM revealed that the added PEG surfactant induced the formation of petal-like alumina.XRD results clarified that all samples were amorphous and their peaks were around the peaks of γ-alumina.N_2 adsorption-desorption analysis showed that the prepared mesoporous alumina,if with PEG1000 in hydrolysis of aluminum isopropoxide,had excellent textural properties with large specific surface area,high pore volume and suitable pore size.The petal-like structure existing in the alumina samples improved their textural parameters,and the role and influential mechanism of PEG1000 were analyzed.     

Effect of Ionic Liquids on Organic Reactions Based on Activity Coefficients at Infinite Dilution

It is important to know how ILs（ionic liquids） influence organic reaction. In this paper, activity coefficients at infinite dilution of more than 80 organic compounds in ILs are collected and analyzed systematically. Through the study on typical organic reactions happened in ILs, such as Diels-Alder, esterification and Friedel-Crafts reaction, the ratio of activity coefficients at infinite dilution of products and reactants is employed to estimate different effects of different structural ILs on the rate and selectivity of reactions.     

一种新型含肉桂酸酯结构的螺吡喃光致变色染料的合成与性能研究

A novel bifunctional dye containing spirobenzopyran and cinnaznoyl moiety has been prepared and its photochromic behavior following irradiation at different wavelengths of monochrome UV light was investigated.The colourless bifunctional dye in film or solution exhibits unusual photochromism through structural and geometrical transformation from spirobenzopyran to merocyanine accompanying with photocrosslinking reaction in cinnamoyl moieties. Two kinds of photochemical reaction were achieved by irradiation at the different wavelengths of monochrome UV light (275 nm, 365 nm) selectively. The photochromic process of the bifunctional dye was discussed and the dynamic behaviors of the decolorization process were investigated.     

Mechanical and thermal characteristics and morphology of polyamide 6/isotactic polypropylene blends in the presence of a β‐nucleating agent

The mechanical and thermal characteristics and morphology of polyamide 6 (PA6)/isotactic polypropylene (iPP) blends (10/90 w/w) prepared with different processing procedures and incorporated with an aryl amide nucleating agent, a kind of β‐nucleating agent (β‐NA) for iPP, were investigated. The yield strength and flexural modulus of the blends decreased as β‐NA was introduced into the blends, whereas the impact strength and elongation at break improved. The crystalline structures of the blends closely depended on (1) the processing conditions and (2) competition between the β‐nucleating effect of β‐NA and the α‐nucleating effect of PA6 for iPP. Scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction were adopted to reveal the microstructures of the blends. At a low β‐NA content (<0.1 wt %), the α‐phase iPP dominated the blends, whereas the relative content of the β‐phase iPP increased remarkably when the β‐NA content was not less than 0.1 wt %. The processing conditions also showed profound influences on the supermolecular structures of iPP; this resulted in different mechanical properties of the blends. As for PA6, the crystallization behavior and crystalline structure did not exhibit obvious changes, but PA6 did play an important role in the epitaxial crystallization of iPP on PA6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nucleation effects of sodium and ammonium salts of 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene)phosphate in isotactic polypropylene

The nucleation ability of isotactic poly(propylene) (iPP) to ammonium 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene) phosphate (An) was investigated in the present work comparing with sodium 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene) phosphate (NA‐11). Scanning electron microscope (SEM) revealed the crystalline morphology of both An and NA‐11 with planar surface characteristics. The observation of the fracture surface of nucleation iPP samples by SEM showed An particles were dispersed uniformly in polymer and had a better compatibility with iPP matrix than NA‐11 particles. Differential scanning calorimeter (DSC) showed that the melting temperature of An was 262°C significantly lower than that measured from NA‐11 group (above 400°C). Crystallization behaviors of iPP/NA‐11 and iPP/An were also investigated by DSC analysis, respectively. The results showed the crystallization peak temperature and the crystallinity of iPP/An were almost near to that of iPP/NA‐11. Furthermore, mechanical and optical properties of iPP were strongly improved in the presences of An and NA‐11. The flexural strength of iPP was elevated 34 and 35% and the haze value was reduced from 40.4 to 15.1 and 14.9% by the addition of 0.15 wt% NA‐11 and An, respectively. These results demonstrate that the nucleating agent of An described here is a good nucleating agent for the crystallization of iPP as well as NA‐11. POLYM. ENG. SCI., 55: 22–28, 2015. © 2014 Society of Plastics Engineers     

Influence of a particulate nucleating agent on the quiescent and flow-induced crystallization of isotactic polypropylene

Flow induced crystallization of commercial isotactic polypropylene (iPP) and its blends with sodium 2,2′-methylene bis-(4,6-di-tert-butylphenyl) phosphate (also known as NA11) is studied by means of in-situ time resolved small-angle X-ray scattering (SAXS). The isothermal crystallization at 145 °C (i.e. well below melting temperature of polymer) is performed after the application of steady shear to probe the anisotropic structure formation. In order to separate the influence of shear rate and shear time on polymer crystallization, four different shear conditions (60 s⁻¹ for 1 s, 30 s⁻¹ for 2 s, 15 s⁻¹ for 4 s and 6 s⁻¹ for 10 s) are applied while maintaining the same imposed strain in the polymer melt. Further the effect of different concentration of nucleating agent on the crystallization kinetics of iPP is examined both under quiescent and shear flow conditions. For instance, under quiescent condition, the crystallization half-time (τ_1/2) decreases with the increasing concentration of nucleating agent in the polymer. Under shear flow conditions, our observations are as follows: In the case of neat iPP, τ_1/2 decreases significantly at higher shear rates (≥30 s⁻¹). Compared to the neat iPP, for the same concentration of NA11 in the NA11/iPP blends differences in τ_1/2 with the increase in applied shear rates are significantly smaller. In other words, the crystallization kinetics is dominated by the amount of nucleating agent in the NA11/iPP blends as opposed to shear rates in the neat iPP. The present study shows that the critical value of shear rate required for chain orientation in the molten polymer is lower in the presence of the nucleating agent compared to neat iPP. The self-nucleation process investigated with the aid of differential scanning calorimetry (DSC), indicates that the nucleating efficiency of NA11 on iPP is around 60%.     

有机磷酸盐成核剂粒径对PP性能的影响

通过调控反溶剂法中的转速、反溶剂与溶剂配比、溶液浓度等条件制备了不同粒径的2,2’–亚甲基双(4,6–二叔丁基苯基)磷酸钠(NA–40)成核剂,考察了NA–40粒径对等规聚丙烯(i PP)力学性能的影响,并利用差示扫描量热(DSC)仪研究了NA–40粒径对i PP结晶性能的影响。结果表明,随着NA–40粒径的增加,NA–40对i PP力学性能的改善作用变弱。NA–40平均粒径为(17.7±2.2)μm时,i PP/NA–40–1的弯曲弹性模量、弯曲强度和拉伸强度与纯i PP相比,分别提高了44.5%,20.5%和8.3%,相应的缺口冲击强度有所降低;当NA–40平均粒径为(52.6±1.1)μm时,i PP/NA–40–4的弯曲弹性模量、弯曲强度和拉伸强度的增幅分别降至16.8%,2.3%和6.4%。在较低的降温速率下,NA–40粒径对结晶峰值温度(Tc)的影响不明显,提高降温速率对Tc的影响开始显现。用扫描电子显微镜观察NA–40形貌发现,NA–40呈棒状,加工过程影响NA–40粒径,但对NA–40形貌没有影响。利用偏光显微镜观察NA–40在i PP熔体中的分散性,粒径较小的NA–40能够均匀分散在i PP熔体中,而粒径较大的分散性差,大大降低了NA–40的有效成核浓度,影响了NA–40对i PP力学性能及结晶性能的改善作用。     

A novel β‐nucleating agent for isotactic polypropylene

The nucleating ability of p‐cyclohexylamide carboxybenzene (β‐NA) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry, X‐ray diffraction, polarized optical microscopy and scanning electron microscopy. β‐NA is identified to have dual nucleating ability for α‐iPP and β‐iPP under appropriate kinetic conditions. The formation of β‐iPP is dependent on the content of β‐NA. The content of β‐phase can reach as high as 96.96% with the addition of only 0.05 wt% β‐NA. Under non‐isothermal crystallization the content of β‐iPP increases with increasing cooling rate. The maximum β‐crystal content is obtained at a cooling rate of 40 °C min^–1. The supermolecular structure of the β‐iPP is identified as a leaf‐like transcrystalline structure with an ordered lamellae arrangement perpendicular to the special surface of β‐NA. Under isothermal crystallization β‐crystals can be formed in the temperature range 80–140 °C. The content of β‐crystals reaches its maximum value at a crystallization temperature of 130 °C. © 2012 Society of Chemical Industry     

The correlation between crystal structure and nucleation efficiency of a lithium (I) complex on isotactic polypropylene

In this work, 2,2′-methylene-bis-(4,6-di-t-butylphenylene)phosphate lithium (NA03) was synthesized and its crystal structural characterization was obtained by single crystal X-ray diffusion. The crystal data showed geometrically the cell parameter of NA03 matched with isotactic polypropylene (iPP), the a cell dimension was about two times to the value of cell edge of (010)_iPP. The disregistry was 2.89%, which was under the upper limit between the lattice matching spacing of host and guest crystals. Then NA03 was proved to be a highly effective nucleating agent for iPP through studying crystallization behaviors, crystallization morphologies, and mechanical properties of iPP nucleated with NA03. The outstanding nucleation efficiency could be attributed to the lattice matching between nucleating agent and iPP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Improved conductivity and thermal stability by the formation of a charge‐transfer complex in β‐nucleation‐agent‐nucleated and MWCNT‐filled iPP composites

In this study, the influence of β‐nucleation agent (β‐NA) on the morphology and properties of multi‐walled carbon nanotube (MWCNT) filled isotactic polypropylene (iPP) composites was explored in details. The results show that the incorporation of β‐NA has promoted the dispersion of MWCNT in the iPP matrix, which is profitable for improving the thermal stability and conductivity properties of MWCNT‐iPP composites. Besides, the 0.05 wt % β‐NA nucleated samples exhibit higher impact toughness than that of un‐β‐NA‐nucleated ones. Further SEM observations show that the morphology of MWCNT changes from large agglomerations to small clusters with doping of β‐NA. The main reason is that the incorporation of β‐NA (TMB‐5) in MWCNT filled iPP matrix has led to the formation of a charge‐transfer complex. Some of these clusters act as nucleation sites for inducing crystallization of α spherulites, which have a compete growth with β‐NA induced β crystals. Meanwhile, other clusters exist in the inter‐lamella amorphous phase of β crystals, some of them even combine two adjacent β spherulites. Accordingly, a large conductive network comes into being. Based on the investigated results, a mechanism model is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of Nucleating Fillers on the Structure and Properties of Polypropylene Blends

The effect of three different fillers on the structure and properties of polypropylene blends were investigated. The β nucleating agent can successfully induce β crystal in modified iPP blends and the turning point of the properties appears at the content of 0.5 wt%. For the properties of carbon nanotube modified iPP blends, there is no turning point because of its dominant α-crystalline morphology. The β NA supported carbon nanotube shows better induction ability than the single β NA or single carbon nanotube, there is also a turning point existing at the content of 0.5 wt%.     

Crystallization morphologies and non-isothermal crystallization kinetics of isotactic polypropylene modified by α/β compounded nucleating agents

采用偏光显微镜(POM)及示差扫描量热(DSC)法考察了3种α/β复合成核剂NA40/NABW、NA40/HHPA-Ba、NA40/PA-03对成核等规聚丙烯(iPP)的结晶形态及非等温结晶动力学的影响。对成核iPP结晶形态的研究结果表明：α/β复合成核剂的加入能够减小iPP的球晶尺寸。影响α/β复合成核剂成核iPP结晶形态的主要因素是ΔT_Cp（ΔT_Cp为成核iPP结晶峰值温度与iPP结晶峰值温度的差值）,即复合体系中ΔT_Cp较大的成核剂在iPP结晶过程中起主导作用,最终的结晶形态与单独添加这一成核剂时iPP的结晶形态相类似;当两种成核剂的ΔT_Cp接近相同时,两者竞争成核,成核iPP的结晶形态表现为两种成核剂共同作用的结果。因此,通过改变α/β复合成核剂的复合比例即改变两种成核剂的添加浓度,进而改变其ΔT_Cp,可以得到结晶形态完全不同的iPP。采用Caze法对非等温动力学进行了研究,结果表明：添加α/β复合成核剂能够提高iPP的结晶温度,缩短半结晶时间。复合成核剂成核iPP的结晶行为也同样受成核剂ΔT_Cp的影响,复合成核iPP的Avrami指数接近于复合体系中ΔT_Cp较大的成核剂单独添加时iPP的Avrami指数。     

Combined effect of organic phosphate sodium and nanoclay on the mechanical properties and crystallization behavior of isotactic polypropylene

Combined effect of α‐nucleating agent (NA) sodium 2,2′‐methylene‐bis(4,6‐di‐tert‐butylphenyl) phosphate (NA11) and nanoclay (NC) on the mechanical properties and crystallization behavior of isotactic polypropylene (iPP) was investigated by mechanical testing, wide‐angle X‐ray scattering (WAXD), differential scanning calorimetry (DSC), polarized optical microscopy (POM), and scanning electron microscopy (SEM). The mechanical testing results indicated that the separate addition of NA11 and NC only increased the stiffness of iPP while the combined addition of NA11, NC, and maleic anhydride grafted polypropylene (PP‐g‐MA) simultaneously improved stiffness and toughness of iPP. Compared to pure iPP, the tensile strength, the flexural modulus, and impact strength of iPP composites increased 9.7, 38.6, and 42.9%, respectively. The result indicated good synergistic effects of NC, NA11, and PP‐g‐MA in improving iPP mechanical properties. WAXD patterns revealed NA11, and NC only induced the α‐crystals of iPP. SEM micrograph showed that the PP‐g‐MA could effectively improve the dispersing of NC in iPP. Finally, the nonisothermal crystallization kinetics of neat iPP and PP nanocomposites was described by Caze method. The result indicated that the addition of NA overcame the shortcoming of low crystallization rate of NC nanocomposites and maintained the excellent mechanical properties, which is another highlight of the combined addition of NAs and nanoclay. Meanwhile, the result showed that nuclei formation and spherulite growth of iPP were affected by the presence of NA and nanoclay. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011