Efficient Synthesis of Octacosanol Linoleate Catalyzed by Ionic Liquid and Its Structure Characterization

Octacosanol, as the major active policosanol, has attracted much attention due to the potential beneficial effects for human health. However, free octacosanol has a high melting point, poor oil solubility and low bioavailability, which greatly restricts its practical application. In this study, we report a highly efficient method for an ionic liquids (IL)‐catalyzed synthesis of octacosanol ester by direct esterification with linoleic acid. The synthesized product was purified, subsequently characterized by FT‐IR, MS and NMR and finally confirmed to be octacosanol linoleate. The reaction parameters were investigated and the conversion reached 91.3 ± 4.8 % under the optimum conditions: IL 1‐butylsulfonate‐3‐methylimidazolium hydrogen sulfate ([BSO₃HMim][HSO₄]) as catalyst, IL dose 1.5 % (related to the mass of both reactants), 1:1 molar ratio of octacosanol to linoleic acid, 80 °C, and 1 h. The melting point and oil solubility of octacosanol were greatly improved by esterification with linoleic acid, facilitating the incorporation into a variety of oil‐based systems.     

The effects of residual polymerization solvent on the physical properties of poly(2‐cyano‐p‐phenylene terephthalamide)

Poly(2‐cyano‐p‐phenylene terephthalamide) (CY‐PPTA) was obtained by the polycondensation of terephthaloyl dichloride and 2‐cyano‐p‐phenylene diamine in the mixture of N‐methyl‐2‐pyrrolidone (NMP) and calcium chloride (CaCl₂). Washing the polymerized product with water and drying at the elevated temperature inevitably left a small amount of polymerization residues which could be eliminated only by additional washing with acetone. The thermogravimetric and ¹H‐/¹³C‐NMR analyses revealed that the residues were largely composed of NMP which existed as a complex with the polymer. The complex was broken up between 200 and 300 °C and evolved 5 wt % of gaseous products, which had an adverse effect on the physical properties of as‐spun CY‐PPTA fibers obtained by dry jet‐wet spinning. The heat treatment of the as‐spun fibers including residual NMP exhibited some porous morphology on the fiber surface due to the evolved gases. However, the existence of the residual NMP had little effect on the intrinsic viscosity and liquid crystalline phase behavior of the polymer. Both rheological and optical properties exhibited the critical concentration at 3 wt % with the clear schlieren texture of nematic liquid crystalline phase. The inclusion of residual NMP decreased dynamic viscosity and yield stress. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43672.     

Synthesis,characterization, and photo‐responsive properties of Y‐shaped amphiphilic azo triblock copolymer

In this study, we report the synthesis, characterization, and photo‐responsive properties of a new Y‐shaped amphiphilic azo triblock copolymer composed of two isotropic polyethylene glycol (PEG) blocks and an azobenzene liquid crystalline block. The azo block, with two ending groups suitable for the azo coupling reaction, is polymerized by atom transfer radical polymerization with a synthesized initiator containing two functional terminal groups. The macromolecular diazonium salts are prepared by the diazotization of PEG terminated with an amino group. The triblock copolymer is obtained by the azo coupling reaction between the azo block and macromolecular diazonium salts in DMF under mild condition. The intermediates and the obtained triblock copolymer are characterized by ¹H NMR, FT‐IR, GPC, POM, DSC, TEM, and UV‐vis. The photoinduced isomerization behavior of the azo copolymer is investigated by UV‐vis. With the addition of water into the solution of the triblock copolymer, spherical aggregates with an average diameter of about 400 nm can be easily obtained. The aggregates are elongated when irradiated with polarized 365 nm UV light. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43695.     

改性Y型分子筛上苯与多乙基苯的液相烷基转移

为获得高性能的液相烷基转移反应催化剂,采用不同的方法对Y型分子筛进行改性处理。采用N_2吸附-脱附、程序升温脱附(NH_3-TPD)和吡啶吸附红外(Py-IR)等手段对样品进行了表征,并在连续微型固定床反应器中考察了改性Y型分子筛上苯和多乙基苯烷基转移反应的催化性能。结果表明,催化剂的烷基转移反应性能与Y型分子筛的孔道和B酸量有密切的关系。通过铵离子交换和酸处理改性均可以提高催化剂的B酸量、比表面积、孔容和孔径;水蒸汽处理会降低酸量;铵离子交换和酸处理复合改性的Y型分子筛催化性能最好。适宜的反应条件为:反应温度180~240℃,反应压力2.5~4.0 MPa,总物料重量空速3~5 h~(-1),苯与二乙苯的质量比2~4,在该条件下二乙苯转化率大于65%,乙基选择性大于98%。该催化剂性能稳定,1 000h运行后活性仍没有下降。     

酸性离子液体催化甲基环戊烷异构化反应

以三级胺、盐酸和AlCl_3为主要原料制备了氯铝酸盐型酸性离子液体催化剂,并优化了催化剂的配比。考察了催化剂用量、反应温度、反应时间以及原料杂质等对甲基环戊烷异构反应的影响。结果表明,提高催化剂用量和反应温度可加快反应速率,在反应温度70℃,油剂比3.0,反应4 h后,环己烷的产率达到70%以上,微量杂质(正己烷和苯)几乎不影响甲基环戊烷的异构化反应。离子液体催化剂在补充活性组分AlCl_3的情况下可以实现循环使用。     

马来酸酐法分析煤基液体产品二烯值的可行性研究

为研究马来酸酐法测定煤基液体产品中共轭二烯烃含量的可行性,考察了煤焦油、脱酚煤焦油、酚类物质和费托油中醇类物质对马来酸酐法分析煤基液体产品中二烯值的影响,结果表明,试验中低温煤焦油样品的二烯值为15.17 g/100 g,经过脱酚处理的煤焦油样品二烯值显著降低,为5.65g/100 g,而苯酚、甲酚、二苯酚等酚类物质对马来酸酐法测定结果没有明显影响,说明煤焦油中其他酸性组分对马来酸酐法测定的二烯值结果影响很大。费托油中的醇类物质可与马来酸酐发生反应,对马来酸酐法测定的结果影响较大。因此马来酸酐法不适用于费托油中共轭二烯烃含量的测定。     

Interaction dynamics of a spherical particle with a suspended liquid film

Hydrodynamics of collision interactions between a particle and gas‐liquid interface such as droplet/film is of keen interest in many engineering applications. The collision interaction between a suspended liquid (water) film of thickness 3.41 ± 0.04 mm and an impacting hydrophilic particle (glass ballotini) of different diameters (1.1–3.0 mm) in low particle impact Weber number ( ) range (1.4–33) is reported. Two distinct outcomes were observed—particle retention in the film at lower Weber number and complete penetration of the film toward higher Weber number cases. A collision parameter was defined based on energy balance approach to demarcate these two interaction regimes which agreed reasonably well with the experimental outcomes. It was shown that the liquid ligament forming in the complete penetration cases breaks up purely by “dripping/end pinch‐off” mechanism and not due to capillary wave instability. An analytical model based on energy balance approach was proposed to determine the liquid mass entrainment associated with the ligament which compared well with the experimental measurements. A good correlation between the %film mass entrained and the particle Bond number ( ) was obtained which indicated a dependency of Bo^1.72. Computationally, a three‐dimensional CFD model was developed to simulate these interactions using different contact angle boundary conditions which in general showed reasonable agreement with experiment but also indicated deficiency of a constant contact angle value to depict the interaction physics in entirety. The computed force profiles from computational fluid dynamics (CFD) model suggest dominance of the pressure force over the viscous force almost by an order of magnitude in all the Weber number cases studied. © 2015 American Institute of Chemical Engineers AIChE J, 62: 295–314, 2016     

Study on rheology and thermal stability of mixed (nonionic–anionic) surfactant based fracturing fluids

Mixed surfactant systems have gained significant importance in the development of fracturing fluid due to polymorphism of self‐assembly structures that have combined properties of the surfactants in the mixture. In this article, a comparative study on the phase behavior and viscoelastic properties of mixed surfactant based fluids, prepared from Tween 80+NaOA/2‐ethyl hexanol/clove oil/water and Tween 20+NaOA/2‐ethyl hexanol/clove oil/water quaternary system is investigated in details. The viscoelastic surfactant (VES) based fluids prepared from the former system offered superior rheological properties than the latter system. The addition of 0.1% NaOH and 500 ppm ZnO nano‐particles in the VES fluids presented enhanced viscoelastic properties as concluded by static and dynamic rheological tests. Miscibility test indicated the miscibility of the VES fluids with water, unlike in the presence of diesel oil and satisfactory proppant suspension capabilities were exhibited by the developed fluids. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2177–2187, 2016     

Analysis of particle cloud height dynamics in a stirred tank

Local and temporal variations of the particle cloud formed in a cylindrical mixing vessel were investigated experimentally. Different particle sizes (0.5, 1, and 2 mm) and volumetric concentration up to 20 vol % were evaluated at different impeller speeds. The time‐averaged cloud height was linear with impeller frequency and with volume concentration. Suspensions with larger particles had a lower average cloud height, while the standard deviation for the temporal cloud height variation was larger. Two strong periodic phenomena were identified to be dominating the particle cloud height variations. The frequencies were linear with impeller speed, resulting in dimensionless frequencies of S₁=0.02–0.03 and S₂=0.05–0.06. The frequencies were affected by neither the particle size nor the volumetric concentration. The amplitude showed no dependency on the particle size, but the S₂ amplitude significantly decreases and S₁ increases with increasing solid concentration. The results were compared to LES/discrete element method simulations and showed a fair agreement. © 2015 American Institute of Chemical Engineers AIChE J, 62: 338–348, 2016