Synthesis, characterization and properties of chitosan modified with poly(ethylene glycol)-polydimethylsiloxane amphiphilic block copolymers

Synthesis of poly(ethylene glycol)-polydimethylsiloxane amphiphilic block copolymers is discussed herein. Siloxane prepolymer was first prepared via acid-catalyzed ring-opening polymerization of octamethylcyclotetrasiloxane (D₄) to form polydimethylsiloxane (PDMS) prepolymers. It was subsequently functionalized with hydroxy functional groups at both terminals. The hydroxy-terminated PDMS can readily react with acid-terminated poly(ethylene glycol) (PEG diacid) to give PEG-PDMS block copolymers without using any solvent. The PEG diacid was prepared from hydroxy-terminated PEG through the ring-opening reaction of succinic anhydride. Their chemical structures and molecular weights were characterized using ¹H NMR, FTIR and GPC, and thermal properties were determined by DSC. The PEG-PDMS copolymer was incorporated into chitosan in order that PDMS provided surface modification and PEG provided good water swelling properties to chitosan. Critical surface energy and swelling behavior of the modified chitosan as a function of the copolymer compositions and contents were investigated.     

Smart polyion complex micelles for targeted intracellular delivery of PEGylated antisense oligonucleotides containing acid-labile linkages

A novel pH-sensitive and targetable antisense ODN delivery system based on multimolecular assembly into polyion complex (PIC) micelles of poly(L-lysine) (PLL) and a lactosylated poly(ethylene glycol)-antisense ODN conjugate (Lac-PEG-ODN) containing an acid-labile linkage (beta-propionate) between the PEG and ODN segments has been developed. The PIC micelles thus prepared had clustered lactose moieties on their peripheries and achieved a significant antisense effect against luciferase gene expression in HuH-7 cells (hepatoma cells), far more efficiently than that produced by the nonmicelle systems (ODN and Lac-PEG-ODN) alone, as well as by the lactose-free PIC micelle. In line with this pronounced antisense effect, the lactosylated PIC micelles showed better uptake than the lactose-free PIC micelles into HuH-7 cells; this suggested the involvement of an asialoglycoprotein (ASGP) receptor-mediated endocytosis process. Furthermore, a significant decrease in the antisense effect (27 % inhibition) was observed for a lactosylated PIC micelle without an acid-labile linkage (thiomaleimide linkage); this suggested the release of the active (free) antisense ODN molecules into the cellular interior in response to the pH decrease in the endosomal compartment is a key process in the antisense effect. Use of branched poly(ethylenimine) (B-PEI) instead of the PLL for PIC micellization led to a substantial decrease in the antisense effect, probably due to the buffer effect of the B-PEI in the endosome compartment, preventing the cleavage of the acid-labile linkage in the conjugate. The approach reported here is expected to be useful for the construction of smart intracellular delivery systems for antisense ODNs with therapeutic value.     

Pt-modulated Cu/SiO2 catalysts for efficient hydrogenation of CO2-derived ethylene carbonate to methanol and ethylene glycol

Copper-based catalysts were widely used in the heterogeneous selective hydrogenation of ethylene car-bonate (EC),a key step in the indirect conversion of CO2 to methanol.However,a high H2/EC molar ratio in feed is required to achieve favorable activity and the methanol selectivity still needs to be improved.Herein,we fabricated a series of Pt-modulated Cu/SiO2 catalysts and investigated their catalytic perfor-mance for hydrogenation of EC in a fixed bed reactor.By modulating the Pt amount,the optimal 0.2Pt-Cu/SiO2 catalyst exhibited the highest catalytic performance with ～99％ EC conversion,over 98％ selectiv-ity to ethylene glycol and 95.8％ selectivity to methanol at the H2/EC ratio as low as 60 in feed.In addition,0.2Pt-Cu/SiO2 catalyst showed excellent stability for 150 h on stream over different H2/EC ratios of 180-40.It is demonstrated a proper amount of Pt could significantly lower the H2/EC molar ratio,promote the reducibility and dispersion of copper,and also enhance surface density of Cu+ species.This could be due to the strong interaction of Cu and Pt induced by formation of alloyed Pt single atoms on the Cu lattice.Meanwhile,a relatively higher amount of Pt would deteriorate the catalytic activity,which could be due to the surface coverage and aggregation of active species.These findings may enlighten some fundamen-tal insights for further design of Cu-based catalysts for the hydrogenation of carbon-oxygen bonds.     

煤制乙二醇关键单元技术与低碳集成工艺的研究进展

我国乙二醇对外依存度居高不下,而富煤少油的资源特性使得我国煤制乙二醇技术具有较好的成本与原料优势,发展迅速。本文综述了国内外煤制乙二醇技术的技术现状和发展趋势,重点介绍了煤气化、草酸二甲酯合成和乙二醇合成与精制等关键单元技术的技术特征、工艺流程和技术进展,并分析了相关单元对整个煤制乙二醇系统技术经济性能的影响。针对现有煤制乙二醇技术存在能耗高、质能效率低和CO₂排放大的问题,着重讨论了集成CO₂高效利用的煤与富氢资源联供制乙二醇集成工艺的进展,包括耦合焦炉气、页岩气和绿氢等资源的新工艺等。以焦炉气为例,集成不同重整技术的新工艺使得传统工艺的碳效率和?效率分别提升了23.35%~39.17%和4.25%~10.12%,生产成本降低了8.73%~19.88%,内部收益率提高了3.6%~9.6%。因此,集成富氢资源与CO₂高效利用的煤制乙二醇创新工艺是该行业向高效-经济-清洁可持续发展的重要方向。     

酚醛树脂基新戊二醇磷酸酯阻燃剂的合成及其性能研究

通过用新戊二醇磷酰氯对线型酚醛树脂(PF)酚羟基实行磷酰化封端处理,制备了线型PF基新戊二醇磷酸酯(NDMPP)阻燃剂,将其应用于阻燃PA6。采用核磁共振氢谱(1H NMR)、核磁共振磷谱(31P NMR)和傅立叶变换红外光谱(FTIR)表征了NDMPP的结构,采用热重(TG)分析研究其热分解行为,采用极限氧指数(LOI)和UL 94测试其阻燃PA6材料的阻燃性能,采用万能材料试验机和冲击试验机测试阻燃材料的力学性能。1H NMR,31P NMR和FTIR结果表明,线型PF中大约82%的羟基被磷酰化,NDMPP中的磷含量约为11.9%。TG分析结果表明,NDMPP阻燃剂在氮气气氛下起始分解温度超过250℃,600℃的残炭率达到43.5%,显示出良好的热稳定性。当NDMPP质量分数为25%时,其阻燃的PA6达到UL 94 V–0等级,LOI达到33.4%,而拉伸强度、缺口冲击强度、弯曲强度和弯曲弹性模量分别为纯PA6的76%,41%,72%和71%。     

不同拓扑结构PEG-PCL嵌段共聚物的结晶研究

合成了不同拓扑结构的聚乙二醇-聚己内酯(PEG-PCL)嵌段共聚物,共聚物结构分别为AB型线性两嵌段(diblock)、ABA型线性三嵌段(triblock)、AB_2型星形(star shape)嵌段共聚物。通过表征发现嵌段共聚物的分子量与设计的分子量接近,且相对分子量分布窄。通过XRD、DSC、热台偏光显微镜(HSPOM)研究了拓扑结构对共聚物结晶的影响。ABA聚合物中间的PEG亲水链受到两端PCL链段阻碍,其结晶衍射峰最弱。三者的等温结晶速率按AB、AB_2、ABA的速率递减,形成的球晶结构规整度则逐渐增加。     

乙二醇溶液水平新型多头内螺纹管内流阻特性

建立了水平管内绝热流动阻力特性试验系统,试验研究了乙二醇溶液在两种新型多头内螺纹管内的流动特性。试验中,乙二醇体积分数为15%,两种试验管公称内径为22 mm与16 mm、螺纹头数为60头与38头、螺旋升角为45°与60°、相对粗糙高为0.022与0.053,测试段长度分别为2643 mm与2945 mm,Pr范围13.9～23.2,Re范围4000～33000。结果表明:多头内螺纹管阻力系数达到极大值之前的变化趋势与均匀粗糙管显著不同,而且无法通过既有多头内螺纹管经验模型准确描述;多头内螺纹管内达到阻力系数极大值的分界点Re为内肋结构参数的函数;入口效应对内螺纹管阻力系数的影响随Re增加而增大,传统的判别入口段可忽略的判据(l/d_i>60)并不适用于多头内螺纹管,尤其是在Re>20000的工况;既有多头内螺纹管经验模型适用工况条件有待进一步拓宽,多头内螺纹结构流动阻力的作用机制、阻力系数出现极大值的分界点的变化规律有待进一步试验探索。     

Design and optimization of an integrated process for the purification of propylene oxide and the separation of propylene glycol by-product

It is difficult to separate the methanol and hydrocarbons in the propylene oxide (PO) purification process due to their forming azeotrope. As for this, a novel PO separation process, in that the deionized water is employed as extractant and 1,2-propylene glycol (MPG) that is formed from the PO hydrolysis reaction is recovered, is presented in this work. The salient feature of this process is that both the non-catalyzed reactions of PO hydrolysis to form MPG and dipropylene glycol (DPG) are simultaneously considered and MPG by-product with high purity is obtained in virtue of the deionized water as reflux liquid and side take-off in MPG column. In addition, the ionic liquid (IL) extractant is screened through the conductor-like screening model for segment activity coefficient (COSMO-SAC) and the comparisons of separation efficiency between the IL and normal octane (nC₈) extractant for the separation of PO and 2-methylpentane are made. With the non-random two-liquid (NRTL) thermodynamic model, the simulation and optimization design for the full flow sheet are performed and the effects of the key operation parameters such as solvent ratio, theoretical stages, feeding stage etc. on separation efficiency are detailedly discussed. The results show that the mass purity and the mass yield of PO can be up to 99.99% and 99.0%, and the condenser duty, reboiler duty and PO loss in the process with IL extractant can be decreased by 69.66%, 30.21% and 78.86% compared to ones with nC₈. The total annual cost (TAC) calculation also suggests that the TAC would be significantly reduced if using IL in replace of nC₈ for the investigated process. The presented results would provide a useful guide for improving the quality of PO product and the economic efficiency of industrial plant.     

The effect of monoethylene glycol on the stability of water-in-oil emulsions

It is important from both a strategic and economic standpoint to study the mechanism of formation of water/oil emulsions, to predict their increase of viscosity with respect to that of the crude oil, and to obtain information about the stability vs separation of these substances (since their presence can impair oil processing and distribution). The objective of this work was to ascertain the influence of monoethylene glycol (MEG) on these parameters and its action mechanism. The addition of MEG in different proportions in the oil emulsions significantly changed the flow curve of the emulsion, passing from a quasi-Newtonian one to a shear thinning behaviour. Besides this, when MEG was present at low concentrations, the demulsification process was slow and an increase in concentration made the emulsions more stable than samples containing the same aqueous phase proportion. Under the conditions studied, the addition of MEG did not reduce the quantity of the aqueous phase separated compared to the emulsions free of MEG, but significantly delayed the demulsification process. Rheology provided important information regarding the phase separation process of the aqueous phase in oil phase emulsions, and dynamic testing suggested that the most relevant effect of the addition of MEG is an increase of the emulsion elasticity that can be correlated with the increase in the emulsion stability observed by bottle test and Turbiscan.     

Synthesis and characteristics of nanocrystalline YSZ powder by polyethylene glycol assisted coprecipitation combined with azeotropic-distillation process and its electrical conductivity

Nanoscale 8 mol% yttria stabilized zirconia (YSZ) powders were prepared by polyethylene glycol (PEG-1540) assisted coprecipitation coupling with azeotropic distillation drying process. The role of PEG and azeotropic-distillation on the morphology and particle size of YSZ was studied. Thermogravimetry and X-ray diffraction results showed that azeotropic-distillation could reduce the formation temperature of YSZ phase. X-ray patterns of the YSZ powders revealed that the crystallite size of the powders increases with increasing calcination temperature, which is consistent with transmission electron microscopy observations. The sintering behavior and the ionic conductivity of the pellets prepared from YSZ powders calcined at 800 °C were also studied. At sintering temperatures ≥1400 °C, more than 99% of the relative density was obtained. The alternating-current impedance spectroscopy results showed that the YSZ pellet sintered at 1450 °C has ionic conductivity of 0.0726 S cm⁻¹ at 800 °C in air. The present work results have indicated that the PEG assisted coprecipitation combined with azeotropic-distillation drying process is an alternative method to synthesize yttria stabilized zirconia powders with a high sinterability and a good ionic conductivity.