Synthesis of propylene carbonate from urea and 1,2-propanediol

The production of propylene carbonate （PC） from urea and 1,2-propanediol （PG） was investigated in a batch process. The catalytic performances of zinc chloride and magnesium chloride were investigated for this reaction system. The influences of various operation conditions on the PC yield were explored. In this work, MgCl2 and ZnCl2 showed the excellent catalytic activity toward PC synthesis, and the yields of propylene carbonate reached 96.5% and 92.4%, respectively. The optimum reaction conditions were as follows： ethanol/urea molar ratio of 4, catalyst concentration of 1.5%, reaction temperature of 160 ℃, reaction time of 3 h, respectively. The route from urea and 1,2-propanediol shows advantages, such as mild reaction condition and safe operation. The catalytic system is environmentally benign.

Electrocatalytic Synthesis of Propylene Carbonate from CO_2 and Propylene Oxide

The electrocatalytic synthesis of propylene carbonate（PC） from CO2 and propylene oxide（PO） was studied under mild conditions（PCO2=1.01×105 Pa, t=25 ℃）. Influences of solvents, supporting electrolytes, the passed charge, the nature of electrodes and the current density（j） on the yield of PC were investigated to optimize the electrolytic conditions, with the maximal yield to be 46.2%, the selectivity of propylene carbonate is 100%. The reduction of propylene oxide in the absence and presence of CO2 was examined by cyclic voltammetry. The mechanism of the reaction initiated by the synergistic effect of halides ions of supporting electrolytes with nucleophilicity and the metal ions from scarification anode with Lewis acid acidity was proposed on the basis of our results.

Direct synthesis of propylene carbonate from propylene and carbon dioxide catalyzed by quaternary ammonium heteropolyphosphatotungstate–TBAB system

In this paper,we have developed a highly efficient method for the direct preparation of propylene carbonate from propylene and carbon dioxide（CO2） using quaternary ammonium heteropolyphosphatotungstate–quaternary ammonium halide catalytic system with anhydrous hydrogen peroxide as an oxidant through one-pot two-step process.The effects of the amount of tetrabutylammonium bromide（TBAB）,the concentration of hydrogen peroxide and other reaction conditions were investigated.The catalyst system gave an optimum propylene oxide yield（91%） at75°C in oxidation step and the highest propylene carbonate yield（99%） at 140°C and 3.0 MPa in cycloaddition step.Based on the results,a reaction mechanism has been proposed.

Catalytic Formation of Propylene Carbonate from Supercritical Carbon Dioxide/Propylene Oxide Mixture

Propylene carbonate was synthesized from supercritical carbon dioxide (SC-CO2)/ propylene oxide mixture with phthalocyaninatoaluminium chloride (ClAlPc)/ tetrabutylstmmonium bromide (n-Bu4NBr) as catalyst. The high rate of reaction was attributed to rapid diffusion and the high miscibility of propylene oxide in SC-CO2 under employed conditions. Various reaction periods present different formation rate of propylene carbonate, mainly due to the existence of phase change during the reaction. The experimental results demonstrate that SC-CO2 could be used as not only an environmentally benign solvent but also a carbon precursor in synthesis.

Zn–Ca–Al mixed oxide as efficient catalyst for synthesis of propylene carbonate from urea and 1,2-propylene glycol

A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.

Abnormal Polarity Effects of Streamer Discharge in Propylene Carbonate under Microsecond Pulses

Propylene carbonate （PC） has a great potential to be used as an energy storage medium in the compact pulsed power sources due to its high dielectric constant and large resistivity. We investigate both the positive and negative breakdown characteristics of PC. The streamer patterns are obtained by ultra-high-speed cameras. The experimental results show that the positive breakdown voltage of PC is about 135% higher than the negative one, which is abnormal compared with the common liquid. The shape of the positive streamer is filamentary and branchy, while the negative streamer is tree-like and less branched. According to these experimental results, a charge layer structure model at the interface between the metal electrode and liquid is presented. It is suggested that the abnormal polarity effect basically arises from the electric field strength difference in the interface between both electrodes and PC. What is more, the recombination radiation and photoionization also play an important role in the whole discharge process.

Preparation of poly(propylene carbonate)/organophilic rectorite nanocomposites via direct melt intercalation

The completely degradable nanocomposites comprised of poly(propylene carbonate)(PPC) and organo-modified rectorite (OREC) were prepared by direct melt intercalation. The structure and mechanical properties of PPC/OREC nanocomposites were investigated. The wide-angle X-ray diffraction (WAXD) results show that the galleries distance of OREC is increased after PPC and OREC melt intercalation, which indicates that PPC molecular chain has intercalated into the layers of OREC. The PPC/OREC nanocomposites with lower OREC content show an increase in thermal decomposition temperature compared with pure PPC. The tensile strength and impact strength of PPC/OREC nanocomposites are improved. When the mass fraction of OREC is 4%, the tensile strength and impact strength of the PPC/OREC nanocomposite increase by 22.86% and 48.58% respectively, compared with pure PPC.

Activation of Carbon Dioxide and Synthesis of Propylene Carbonate

Cycloaddition of carbon dioxide and propylene oxide to propylene carbonate catalyzed by tetra-tert-butyl metal phthalocyanine in the presence of tributylamine (TBA) shows higher yield than catalyzed by unsubstituted metal phthalocyanine. Comparing different catalysts of diverse metals, (t-Bu)4PcMg is more active than (t-Bu)4PcFe. But (t-Bu)4PcCo and (t-Bu)4PcNi only have low catalytic activities towards the reaction. Moreover, the yield will increase as the temperature increases.

CHARACTERISTICS OF CATION—CONDUCTIVE BLENDS PLASTICIZED WITH PROPYLENE CARBONATE

The cation—conductive blends plasticized with propylene carbonate were prepared. The blends exhibited good mechanical strength and single—cation conduction over a wide range of plasticizer composition. The plasticizer not only increases the conductivity of the blends but also decreases the electrochemical interface resistance between the blend and lithium electrode. The carrier in the blends obviously grows in number.

Adsorption of propylene carbonate on the LiMn2O4(100)surface investigated by DFT+U calculations

Understanding the mechanism of the interfacial reaction between the cathode material and the electrolyte is a significant work because the interfacial reaction is an important factor affecting the stability,capacity,and cycling performance of Li-ion batteries.In this work,spin-polarized density functional theory calculations with on-site Coulomb energy have been employed to study the adsorption of electrolyte components propylene carbonate(PC)on the LiMn2O4(100)surface.The findings show that the PC molecule prefers to interact with the Mn atom on the LiMn2O4(100)surface via the carbonyl oxygen(Oc),with the adsorption energy of−1.16 eV,which is an exothermic reaction.As the adsorption of organic molecule PC increases the Mn atoms coordination with O atoms on the(100)surface,the Mn3+ions on the surface lose charge and the reactivity is substantially decreased,which improves the stability of the surface and benefits the cycling performance.

INFLUENCE OF DIALKYLZINC IN RARE-EARTH TERNARY CATALYST ONTHE COPOLYMERIZATION OF CARBON DIOXIDE AND PROPYLENE OXIDE

Rare-earth ternary catalysts Y（CCl3COO）3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide （PO）, where dialkylzincs （ZnR2） were diethylzinc, di（n-propyl）zinc, di（n-butyl）zinc, di（i-propyl）zinc, di（i-butyl）zinc, di（s-butyl）zinc,respectively. The Y（CCl3COO）3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y（CCl3COO）3：ZnR2：glycerin = 1：20：10. In the same copolymerization condition, catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence： Y（CCl3COO）3-ZnEt2-glycerin 〉 Y（CCl3COO）3-Zn（n- Pr）2-glycerin〉Y（CCl3COO）3-Zn（n-Bu）2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end.

PPC/PBS复合生物膜的屏障功能及其对兔胫骨骨缺损模型的促成骨作用

目的:探讨聚碳酸1,2-丙二酯(PPC)/聚丁二酸丁二醇酯(PBS)复合生物膜在兔胫骨骨缺损模型中的空间支撑能力及其对成骨效果的影响,阐明其屏障功能的可靠性和体内促成骨作用。方法:制备PPC/PBS和PPC/PBS/Ⅰ型胶原(Col-Ⅰ)(PPC/PBS/Co)复合生物膜。选用18只日本大耳白兔,于兔每侧胫骨制备2处骨缺损,随机选择6只兔于骨缺损处放置PPC/PBS复合生物膜,术后4、8和12周各处死2只兔,扫描电子显微镜(SEM)观察兔骨缺损区PPC/PBS复合生物膜表面微观结构。实验分为空白对照组、PPC/PBS复合生物膜组、BME-10X胶原膜组和PPC/PBS/Co复合生物膜组,分别行手术将上述生物膜放置于兔相应骨缺损处,空白对照组兔不放置复合生物膜,于术后2、4、8和12周时分别处死3只兔,采用软X线检测各组兔骨缺损区再生骨组织灰度值,荧光标记后采用激光共聚焦显微镜观察各组兔骨缺损区再生骨组织荧光强度,采用HE染色和改良Gomori三色染色法观察各组兔骨缺损区再生骨组织病理形态表现,免疫组织化学染色法检测各组兔骨缺损区再生骨组织中骨形态发生蛋白2(BMP-2)和骨桥蛋白(OPN)蛋白表达水平。结果:大体观察,PPC/PBS复合生物膜紧密覆盖于骨缺损区,未见移位及塌陷。SEM观察,PPC/PBS复合生物膜多孔面随时间延长表面出现微孔结构并数量增多,而光滑面基本未形成微孔样结构。软X线检测,各组兔骨缺损区再生骨组织灰度值均随时间延长而升高,12周时PPC/PBS/Co复合生物膜组兔骨缺损区再生骨组织灰度值明显高于其他各组(P<0.05)。共聚焦显微镜观察,4、8和12周时PPC/PBS/Co复合生物膜组兔骨缺损区再生骨组织荧光强度与空白对照组相近;与PPC/PBS复合生物膜组和BME-10X胶原膜组比较,4周时PPC/PBS/Co复合生物膜组兔骨缺损区再生骨组织荧光强度升高(P<0.05),8和12周时PPC/PBS/Co复合生物膜组兔骨缺损区再生骨组织荧光强度降低(P<0.05)。HE染色和改良Gomori染色,与PPC/PBS复合生物膜组和BME-10X胶原膜组比较,2和4周时PPC/PBS/Co复合生物膜组和空白对照组兔骨缺损区形成新骨的速度较快,在12周时骨缺损区形成的层板状骨矿化程度较高。免疫组织化学染色,2和4周时,与空白对照组、PPC/PBS复合生物膜组和BME-10X胶原膜组比较,PPC/PBS/Co复合生物膜组兔骨缺损区再生骨组织中BMP-2和OPN蛋白表达水平升高(P<0.05或P<0.01);与空白对照组和PPC/PBS复合生物膜组比较,BME-10X胶原膜组兔骨缺损区再生骨组织中BMP-2和OPN蛋白表达水平均降低(P<0.05或P<0.01)。结论:PPC/PBS复合生物膜具有较好的空间支撑能力,物理屏障功能可靠,且PPC/PBS/Co复合生物膜具有良好的体内促成骨作用。

Boosting reversible charging of Li-ion batteries at low temperatures by a synergy of propylene carbonate-based electrolyte and defective graphite

Propylene carbonate(PC)-based electrolytes have exhibited significant advantages in boosting the low-temperature discharging of graphite-based Li-ion batteries.However,it is still unclear whether they can improve the charging property and suppress lithium plating.Studying this topic is challenging due to the problem of electrochemical compatibility.To overcome this issue,we introduced graphite with phase defects.The results show that the pouch-type full batteries using PC-based electrolyte exhibit steady performance over 500 cycles and can be reversibly charged over 30 times at-20℃ with an average Coulombic efficiency of 99.95%,while the corresponding value for the conventional ethylene carbonate(EC)-based electrolyte sample is only 31.20%.This indicates that the use of PC-based electrolyte significantly suppresses lithium plating during low-temperature charging.We further demonstrate that the improved performance is mainly attributed to the unique solvation structure,where PF-6more anions participate in solvation,leading to the formation of a stable F-rich solid state electrolyte interface on the graphite surface and a lower reduction tendency of Li+ions.This work inspires new ideas for the design of PC-based electrolytes for low-temperature charging and fast-charging batteries.

EC、PC溶剂在石墨表面反应的第一性原理研究

基于第一性原理利用密度泛函理论对溶剂EC、PC和EMC的电子性质及其与石墨负极的反应进行了理论计算。相较于EC和EMC溶剂,PC具有更小的带隙,最容易发生电子跃迁进而发生氧化还原反应。EC和EMC溶剂分子嵌入石墨层中仅仅扩大了石墨的层间距,而PC嵌入后与石墨发生了反应,破坏了石墨结构。随着充电程度的增加,PC与石墨的反应能减小,石墨结构更容易被破坏。比较了锂离子和钠离子的溶剂化能和嵌入石墨的反应能。计算结果显示:电解液中的杂质钠离子具有更小的去溶剂化能,在石墨负极表面与锂离子发生竞争,优先嵌入到石墨中,阻碍锂离子嵌入。

ELECTROCHEMICAL AND OPTICAL STUDY ON C_(60) FILM IN LiClO_4 POLYPROPYENE CARBONATE (PC) SOLUTION

For the first time we observed the electrochromism of C_(60) film intercalated by lithium and obtained some amount of intercalate Li_3C_(60) with cyclic voltammetry. The optical absorption properties of this intercalate have been studied.

琥珀酸酐封端PPC对PLA共混体系性能的影响

采用琥珀酸酐封端的聚碳酸亚丙酯(SA-PPC)对聚乳酸(PLA)进行改性,在二月桂酸二丁基锡(DBTD)的催化作用下,通过熔融酯交换反应制备PLA/SA-PPC共混物,利用电子万能试验机、悬臂梁冲击试验机、差示扫描量热仪(DSC)和扫描电子显微镜(SEM)对其进行表征。分析了熔融反应机理及催化剂含量对共混物的力学性能、热性能及形貌的影响。结果表明,加入DBTD后,促进了PLA和SA-PPC间的酯交换反应,生成的共聚物和齐聚物分别具有增容作用及增塑作用。DSC和SEM结果表明,PLA与PPC的相容性显著提高。当DBTD含量为2份时,PLA/SA-PPC共混物的冲击强度和断裂伸长率分别由PLA的1.8 kJ/m^(2)和8.7%提高至5.7 kJ/m^(2)和318.6%,并且,拉伸强度下降不显著。

PBAT/PPC可生物降解薄膜的性能及其自然老化行为

为提升聚己二酸‒对苯二甲酸丁二酯(PBAT)共混物的水蒸气阻隔性和耐候性能,通过熔融共混和吹塑方法制备了不同配比的PBAT/聚碳酸亚丙酯(PPC)共混物薄膜,研究了材料组成对共混物薄膜水蒸气阻隔性、力学性能、热性能、微观形貌、透光率等影响,并对其进行了自然老化表征。结果表明,PPC的加入提高了PBAT基薄膜的水蒸气阻隔性,但力学性能和热稳定性有所下降,加入质量分数为20%的PPC可使薄膜的水蒸气透过系数下降54.5%;自然老化试验表明,PPC能够提升PBAT基薄膜的耐候性。