The Oxyalkylation of Hydrophilic Black Alder Bark Extractives with Propylene Carbonate with a Focus on Green Polyols Synthesis

The isolated hydrophilic black alder(Alnus glutinosa)bark extractives were characterized in terms of component and functional composition and converted at 150℃-170℃ into liquid green polyols using solvent-free and lowtoxic base-catalyzed modification with propylene carbonate(PC).FTIR spectroscopy,HP-LC,GC,GPC,and wet chemistry methods were used to characterize the starting constituents,intermediate and final products of the reaction and to monitor the different pathways of PC conversion.The reaction of extractives as well as the model compounds,including catechol,xylose,PEG 400,and benzoic acid,with PC indicated the ability of OH groups of different origins present in the extractives to condense with equivalent amounts of PC.The polyols obtained consist of a copolymer fraction with one oxypropyl unit grafted per OH functionality of extractive components on average and oligo oxypropyl diols with a small number of carbonate linkages in the chain,obtained as a result of remaining PC homopolymerization.The domination of the oxypropylation mechanism vs.transcarbonation for PC ring opening was observed for both copolymerization and homopolymerization processes,making the process of oxypropylation with PC similar to that of conventional oxypropylation.At optimal reaction conditions,including a PC/OH ratio of 3.0 and a 24-h duration at 150°C,uniform polyols with low viscosity of~900 mPa·s^(-1),a biomass content of~27%,and an OHV of~500 mg KOH·g^(-1) were obtained.Increasing the temperature of modification allows shortening the process but drastically increases the polyol viscosity.At fixed temperature values,increasing the PC/OH ratio not only decreases the biomass content but also strongly prolongs the processing.The significantly increased duration of the process using PC as an alternative oxyalkylation agent compared to that of oxyalkylation with propylene oxide is a reasonable trade-off for using a safer and more environmentally friendly technology.

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.

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.

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.

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.

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.

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.

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.

Synthesis of Urea by Ammonolysis of Propylene Carbonate

Studying urea formation by ammonolysis of propylene carbonate in a liquid phase showed that this process is two-stage, and proceeds through preferred formation of 2-hydroxypropyl carbamate, besides, the rate of the first stage is much higher than the rate of the second stage （urea formation）. With the aid of the HPLC and HPLC/MS methods found some other intermediate products and offered consecutive-parallel scheme of the process. The obtained results explain the composition of impurities obtained during the production of the 13C-urea for diagnostic breath tests.

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.

Biodegradable Foaming Material of Poly(butylene adipate-co-terephthalate)(PBAT)/Poly(propylene carbonate)(PPC)

A biodegradable blend foaming material of poly(butylene adipate-co-terephthalate)(PBAT)/poly(propylene carbonate)(PPC)was successfully prepared by chemical foaming agent and screw extrusion method.First,PBAT was modified by bis(tert-butyl dioxy isopropyl)benzene(BIBP)for chain extension,and then the extended PBAT(E-PBAT)was foamed with PPC using a twin(single)screw extruder.By analyzing the properties of the blends,we found that Young’s modulus increased from 58.8 MPa of E-PBAT to 244.7 MPa of E-PBAT/PPC 50/50.The viscosity of the polymer has a critical influence on the formation of cells.Compared with neat PBAT(N-PBAT),the viscosity of E-PBAT increased by 3396 Pa·s and E-PBAT/PPC 50/50 increased by 8836 Pa·s.Meanwhile,the dynamic mechanical analysis(DMA)results showed that the storage modulus(E’)at room temperature increased from 538 MPa to 1650 MPa.The various phase morphologies(“sea-island”,“quasi-co-continuous”and“cocontinuous”)and crystallinity of the blends affected the spread velocity of gas and further affected the foaming morphology in E-PBAT/PPC foam.Therefore,through the analysis of phase morphology and foaming mechanism,we concluded that the E-PBAT/PPC 70/30 component has both excellent strength and the best foaming performance.

Biocompatibility evaluation of electrospun aligned poly(propylene carbonate) nanofibrous scaffolds with peripheral nerve tissues and cells in vitro

Background Peripheral nerve regeneration across large gaps is clinically challenging. Scaffold design plays a pivotal role in nerve tissue engineering. Recently, nanofibrous scaffolds have proven a suitable environment for cell attachment and proliferation due to similarities of their physical properties to natural extracellular matrix. Poly（propylene carbonate） （PPC） nanofibrous scaffolds have been investigated for vascular tissue engineering. However, no reports exist of PPC nanofibrous scaffolds for nerve tissue engineering. This study aimed to evaluate the potential role of aligned and random PPC nanofibrous scaffolds as substrates for peripheral nerve tissue and cells in nerve tissue engineering. Methods Aligned and random PPC nanofibrous scaffolds were fabricated by electrospinning and their chemical characterization were carried out using scanning electron microscopy （SEM）. Dorsal root ganglia （DRG） from Sprague-Dawley rats were cultured on the nanofibrous substrates for 7 days. Neurite outgrowth and Schwann-ceU migration from DRG were observed and quantified using immunocytochemistry and SEM. Schwann cells derived from rat sciatic nerves were cultured in electrospun PPC scaffold-extract fluid for 24, 48, 72 hours and 7 days. The viability of Schwann cells was evaluated by 3-[4,5-dimethyl（thiazol-2-yl）-2,5-diphenyl] tetrazolium bromide （M]-F） assay. Results The diameter of aligned and random fibers ranged between 800 nm and 1200 nm, and the thickness of the films was approximately 10-20 IJm. Quantification of aligned fiber films revealed approximately 90% alignment of all fibers along the longitudinal axis. However, with random fiber films, the alignment of fibers was random through all angle bins. Rat DRG explants were grown on PPC nanofiber films for up to 1 week. On the aligned fiber films, the majority of neurite outgrowth and Schwann cell migration from the DRG extended unidirectionally, parallel to the aligned fibers. However, on the random fiber films, neurite outgrowth and Schwann cell migration were randomly distributed. A comparison of cumulative neurite lengths from cultured DRGs indicated that neurites grew faster on aligned PPC films （（2537.6±987.3） μm） than randomly-distributed fibers （（493.5±50.6） μm）. The average distance of Schwann cell migration on aligned PPC nanofibrous films （（2803.5±943.6） μm） were significantly greater than those on random fibers （（625.3±47.8） pm）. The viability of Schwann cells cultured in aligned PPC scaffold extract fluid was not significantly different from that in the plain DMEM/F12 medium at all time points after seeding. Conclusions The aligned PPC nanofibrous film, but not the randomly-oriented fibers, significantly enhanced peripheral nerve regeneration in vitro, indicating the substantial role of topographical cues in stimulating endogenous nerve repair mechanisms. Aligned PPC nanofibrous scaffolds may be a promising biomaterial for nerve regeneration.

Rheological, Thermal and Mechanical Properties of Biodegradable Poly(propylene carbonate)/Polylactide/Poly(1,2-propylene glycol adipate) Blown Films

Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.

Sustainable Blends of Poly(propylene carbonate)and Stereocomplex Polylactide with Enhanced Rheological Properties and Heat Resistance

Sustainable blends of poly(propylene carbonate)(PPC)and stereocomplex polylactide(sc-PLA)were prepared by melt blending equimolar poly(L-lactic acid)(PLLA)and poly(D-lactide acid)(PDLA)with PPC to form sc-PLA crystals in situ in the melt blending process.Differential seanning calorimetry analysis revealed that only sc-PLA,no homo-crystallization of PLLA or PDLA,formed in the PPC matrix as the sc-PLA con tent was more than 10 wt%.Very in triguingly,scan ning electronic microscopy observati on showed that sc-PLA was evenly dispersed in the PPC phase as spherical particles and the sizes of sc-PLA particles did not obviously increase with in creasing sc-PLA con tent.As a con seque nee,the rheological properties of PPC were greatly improved by incorporation of sc-PLA.When the sc-PLA con tent was 20 wt%,a percolati on n etwork structure was formed,and the blends showed solid-like behavior.The sc-PLA particles could reinforce the PPC matrix,especially at a temperature above the glass transition temperature of PPC.Moreover,the Vicat softening temperature of PPC/sc-PLA blends could be increased compared with that of neat PPC.

Thermal,Mechanical and Rheological Properties of Biodegradable Poly(propylene carbonate) and Poly(butylene carbonate) Blends

Poly（propylene carbonate） （PPC） was melt blended in a batch mixer with poly（butylene carbonate） （PBC） in an effort to improve the toughness of the PPC without compromising its biodegradability and biocompatibility. DMA results showed that the PPC/PBC blends were an immiscible two-phase system. With the increase in PBC content, the PPC/PBC blends showed decreased tensile strength, however, the elongation at break was increased to 230% for the 50/50 PPC/PBC blend. From the tensile strength experiments, the Pukanszky model gave credit to the modest interfacial adhesion between PPC and PBC, although PPC/PBC was immscible. The impact strength increased significantly which indicated the toughening effects of the PBC on PPC. SEM examination showed that cavitation and shear yielding were the major toughening mechanisms in the blends subjected the impact tests. TGA measurements showed that the thermal stability of PPC decreased with the incorporation of PBC. Rheological investigation demonstrated that the addition of PBC reduced the value of storage modulus, loss modulus and complex viscosity of the PPC/PBC blends to some extent. Moreover, the addition of PBC was found to increase the processability of PPC in extrusion. The introduction of PBC provided an efficient and novel toughened method to extend the application area of PPC.

Additives to propylene carbonate-based electrolytes for lithium-ion capacitors

Nowadays,lithium-ion capacitors(LICs) have become a type of important electrochemical energy storage devices due to their high power and long cycle life characteristics with fast response time.As one of the essential components of LICs,the electrolytes not only provide the anions and cations required during charge and discharge processes,but also supply the liquid environment for ions to migrate between anodes and cathodes in LIC cells.It is well accepted that propylene carbonate(PC) cannot be used as a single solvent for Li-ion electrolyte due to the failure to form stable SEI film on graphite surface.In this work,the compatibility of PC-based electrolyte with commercial soft carbon anode and activated carbon cathode has been validated by using the laminated pouch LIC cells.The effects of additives on the electrochemical properties of PC-based LICs have been systematically investigated.Ethylene sulfite(ES) was proved to be an effective additive to promote capacity retention at high C-rate,which is superior to vinylene carbonate and fluoroethylene carbonate.The addition of 5 wt% ES plays an important role in reducing internal resistance,as well as improving electrochemical stability and low-temperature performances.This study is expected to be beneficial to explore robust electrolyte/additive combinations for LICs to reduce the internal resistance and to improve the lowtemperature performances.

Preparation of Chlorinated Poly(propylene carbonate) and Its Distinguished Properties

Poly（propylene carbonate） （PPC）, the copolymerization product of carbon dioxide and propylene oxide, was chlorinated for the first time in our laboratory. Nuclear magnetic resonance （NMR） spectroscopy and ion chromatography test showed that chlorine atoms were successfully introduced onto the polymer chains of PPC. We named this newborn polymer material as chlorinated poly（propylene carbonate） （CPPC）. It is worth noting that the reaction conditions of the chlorination of PPC were quite mild, which could be easily and simply realized at industrial level. What is more important is that CPPC possessed many more distinguished properties in solubility, wettability, adhesiveness, and gas barrier compared with PPC. For example, the bonding strength of CPPC as thermal adhesive is nearly four times higher than that of PPC for wood, stainless steel and glass. The oxygen permeability coefficient of CPPC exhibits a decrease of 33% compared with that of PPC. Moreover, CPPC is quite stable in air, whereas it could be well biodegraded in soil compared with PPC. These results indicated that CPPC could be widely used in the fields of coating, adhesive, barrier materials and so on, which could greatly promote the development of PPC industry.