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.

Tuning the cross-linked structure of basic poly(ionic liquid)to develop an efficient catalyst for the conversion of vinyl carbonate to dimethyl carbonate

Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.

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.

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.

Manipulating Zn^(2+)solvation environment in poly(propylene glycol)-based aqueous Li^(+)/Zn^(2+)electrolytes for high-voltage hybrid ion batteries

Compared with aqueous single-ion batteries,rechargeable aqueous hybrid ion batteries,especially Li^(+)/Zn^(2+)hybrid ion batteries,are receiving extensive interest owing to their low cost,high operating voltage,and energy density.However,their working voltage and lifespan are limited by the decomposition of water and the growth of Zn dendrites.Herein,detrimental side reactions induced by the water reduction and the Zn dendrite growth are successfully suppressed by a poly(propylene glycol)(PPG)-based hybrid ion electrolyte[(1 m Zn(TFSI)2+10 m LiTFSI)in PPG/H2O].The addition of PPG in the electrolyte can not only enhance the bonding strength of hydrogen-bond in water but also tailor the solvation sheath of Zn2+as revealed by synchrotron X-rays.The participated solvation of PPG with Zn^(2+)can weaken Zn-H_(2)O interactions and redistribute Zn^(2+)flux on the surface of the Zn anode,thus inducing favorably even deposition of Zn.In addition,the decomposition of TFSI-contributes a ZnF_(2)-enriched solid electrolyte interface at the Zn anode to further prevent water decomposition and restrain Zn dendrites.The PPG-based electrolyte enables 2.1 V LiMnO_(2)//Zn batteries to deliver high specific capacities(121.7 mAh g^(-1)for a coin cell and 90 mAh g^(-1)for a pouch cell),and maintain 80%of the capacity over 700 cycles at 0.5 C,suggesting a promising pathway for highly reversible aqueous hybrid ion batteries.

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.

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.

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.

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.

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.

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.

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.

Studies on the Simultaneous Synthesis of Dimethyl Carbonate and Poly(ethylene terephthalate): I. Catalytic Activity of Metal Acetate in Transesterification of Ethylene Carbonate with Dimethyl Terephthalate

A novel direct method for preparation of dimethyl carbonate and poly（ethylene terephthalate） from ethylene carbonate and dimethyl terephthalate has been demonstrated in the presence of metal acetate catalysts, lithium acetate dihydrate showed highest catalytic activity with 47.9% yield of dimethyl carbonate. This method was a green chemical process.

Preparation and Electrocatalytic Activity of Polyaniline-poly(propylene oxide)

A novel copolymer of polyaniline-poly(propylene oxide) (PAN-PPO) was prepared by cyclic voltammetry (CV) and characterized by FTIR and SEM. It showed good electroactivity for methanol oxidation in H2SO4 solution.

Depolymerization of Poly(bisphenol A carbonate) in Subcritical and Supercritical Toluene

The depolymerization of poly（bisphenol A carbonate）（PC） in subcritical and supercritical toluene was studied. The experimental parameters, which influence the depolymerization reaction such as temperature （570-633 K）, pressure （4.0-7.0 MPa）, reaction time （5-60 min）, and toluene to PC weight ratio （3.0-11.0）, were investigated, and the reaction products were determined by CrC, GC/MS and FT-IR spectrometer. It was found that the main product of the depolymerization reaction was bisphenol A（BPA）. BPA accounted for over 55.7% of the depolymerization products at reaction temperature 613 K, pressure 5.0-6.0 MPa, reaction time 15 min and toluene/PC weight ratio of around 7.0.