Propylene Carbonate Research Articles

Extraction of poly(3-hydroxybutirate) from Priestia megaterium using non-halogenated solvents: A comparative performance analysis

Solvent extraction using chloroform is the most common industrial process for poly(3-hydroxybutyrate) (P(3HB)) recovery from dried biomass, and still a major barrier to expanding the commercial application of this biodegradable biopolymer. Consequently, there is great interest in alternative non-halogenated solvents for this process and some relevant related results are available in the literature for P(3HB) recovery from Gram-negative bacteria. This work evaluated the potential of a set of non-halogenated solvents for the extraction of P(3HB) from Priestia megaterium, a Gram-positive bacterium of great potential for P(3HB) production. Ethyl acetate (EtAc), methyl ethyl ketone (MEK), dimethyl carbonate (DMC), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (NNDA), 2-heptanone (2-Hp), propylene carbonate (PC), and isoamyl propionate (IAP) were tested. Preliminary solubilization tests using commercial P(3HB) showed that EtAc, MEK, DMC and IAP had lower P(3HB) solubilization capacity (below 0.08 g/L for EtAc, MEK, and DMC; 1.3–2.5 g/L for IAP) than DMSO (65–70 g/L) and PC, 2-Hp and NNDA (>100 g/L). Then, only DMSO, PC, 2-Hp, and NNDA were evaluated in recovery tests with intracellular P(3HB). DMSO was not selective for P(3HB), causing digestion of cell wall components. PC, 2-Hp, and NNDA outperformed chloroform, but NNDA stood out for its remarkably higher recovery (98.5 %, 30 min, 140 ºC).

Enhancing the stability of sodium-ion capacitors by introducing glyoxylic-acetal based electrolyte

Sodium-ion Capacitors (SICs) are becoming increasingly important energy storage devices. This study presents an in-depth comparison of a largely used electrolyte for said application, sodium hexafluorophosphate in ethylene carbonate:propylene carbonate (NaPF6 in EC:PC), with the novel electrolyte sodium bis(trifluoromethanesulfonyl)imide in 1,1,2,2-tetraethoxyethane:propylene carbonate (NaTFSI in TEG:PC). Firstly, half-cells of the SIC standard electrode materials, hard carbon (HC) and activated carbon (AC), are shown to perform comparably well with the two electrolytes. However, the use of the novel electrolyte in SICs allows for an improved stability during float tests. All in all, the novel electrolyte NaTFSI in TEG:PC appears to be a very promising alternative electrolyte for SIC application.

Rational Optimization of Ammonium and Phosphonium Cations of Bifunctional Organoborane Catalysts for Copolymerization of Propylene Oxide with CO2 to Afford Poly(propylene carbonate)

Rational Optimization of Ammonium and Phosphonium Cations of Bifunctional Organoborane Catalysts for Copolymerization of Propylene Oxide with CO₂ to Afford Poly(propylene carbonate)

Combination of nanoparticles with single-metal sites synergistically boosts co-catalyzed formic acid dehydrogenation

The development of hydrogen technologies is at the heart of a green economy. As prerequisite for implementation of hydrogen storage, active and stable catalysts for (de)hydrogenation reactions are needed. So far, the use of precious metals associated with expensive costs dominates in this area. Herein, we present a new class of lower-cost Co-based catalysts (Co-SAs/NPs@NC) in which highly distributed single-metal sites are synergistically combined with small defined nanoparticles allowing efficient formic acid dehydrogenation. The optimal material with atomically dispersed CoN2C2 units and encapsulated 7-8 nm nanoparticles achieves an excellent gas yield of 1403.8 mL·g−1·h−1 using propylene carbonate as solvent, with no activity loss after 5 cycles, which is 15 times higher than that of the commercial Pd/C. In situ analytic experiments show that Co-SAs/NPs@NC enhances the adsorption and activation of the key intermediate monodentate HCOO*, thereby facilitating the following C-H bond breaking, compared to related single metal atom and nanoparticle catalysts. Theoretical calculations show that the integration of cobalt nanoparticles elevates the d-band center of the Co single atoms as the active center, which consequently enhances the coupling of the carbonyl O of the HCOO* intermediate to the Co centers, thereby lowering the energy barrier.

Volatile organic compound (VOC) emissions from no-added-formaldehyde lignosulphonate/pMDI particleboards and their effect on indoor air quality

ABSTRACT Wood-based panels, for example particleboards, are responsible for releasing formaldehyde and volatile organic compounds (VOCs), consequently polluting indoor air. Thus, the demand for eco-friendly wood adhesives, such as lignosulphonates (LS), has increased in detriment of the traditionally used urea-formaldehyde resins. However, combination with polymeric 4,4′-diphenylmethane diisocyanate (pMDI) is commonly proposed to minimize pressing times. In this study, particleboards were manufactured using a low lab-scale press factor of 7.5 s/mm. The adhesive contents were: 1.3% pMDI with 2.2% propylene carbonate (PC) solvent in the core layer and 15% LS in the surface layers. The VOC emissions of these boards were evaluated against those of commercial urea-formaldehyde boards. Headspace gas chromatography-mass spectrometry analysis indicated that the total VOC emissions were 66% higher for the LS/pMDI boards, comprising mainly of PC and furfural. After 14-days in a 25 L chamber, VOC emissions were examined according to ISO 16000-9:2006. LS/pMDI particleboards emitted four times more VOCs than standard boards, with 80% corresponding to PC and furfural, a suspected carcinogen. Consequently, the need for VOC quantification, even for bio-based boards is highlighted. An extension of EN 16516:2017 + A1:2020 to furniture products is also advised.

Fluorinated ester additive to regulate nucleation behavior and interfacial chemistry of room temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT Na-S) batteries are considered as advanced energy storage technology due to their low cost and high theoretical energy density. However, challenges such as the growth of sodium dendrite and dissolution of sodium polysulfides significantly hinder the electrochemical performance. Herein, we developed a propylene carbonate (PC)-based electrolyte with Methyl 2-Fluoroisobutyrate (MFB) as an additive. The ester group in the MFB additive is capable of participating in and reconfiguring the coordination of their Na+ solvated structures, thereby lowering the desolvation barrier and regulating the Na anode’s interfacial reaction and nucleation behavior. The polar C−F bond at the other end helps to reduce the lowest unoccupied molecular orbital (LUMO) energy of the MFB additive, enabling the preferential decomposition of MFB to form the F-rich inorganic phase strong polar solid electrolyte interphase (SEI), contributing to the inhibition of Na dendrite growth, the accumulation of dead Na. In addition, NaF-riched cathode electrolyte interphase (CEI) was also observed on sulfur-based cathode, which can effectively inhibited the shuttle effect. Consequently, the developed RT Na-S battery exhibit excellent electrochemical performance.

Dielectric and Shear-Mechanical "Humps" in the Nonlinear Response of Polar Glassformers.

Many glassformers display electrorheological effects and a pronounced maximum in their frequency dependent nonlinear dielectric response. The latter so-called "hump" feature was often linked to correlated-particle motions and, so far, was not explored in the large-perturbation mechanical response of viscous liquids. To first clarify the electro-viscoelastic coupling in the linear domain, using the modified Gemant, DiMarzio, and Bishop model, it is demonstrated how the small-amplitude shear mechanical response of S-methoxy-PC, a derivative of propylene carbonate, can be related to its complex dielectric permittivity. Then, in the nonlinear regime, a "hump" feature is identified in the rheological third-order shear modulus of S-methoxy-PC and of another polar glassformer, propylene glycol. Thus, the observation of a "hump" in the cubic response of viscous liquids does not necessarily rely on the application of electrical fields.

Colloidal dispersions of cobalt ferrite nanoparticles in EMIM TFSI, propylene carbonate and their mixtures

Liquid thermocells are promising devices for the recovery of low-grade waste heat and its conversion into electricity. The present study proposes dispersing charged magnetic nanoparticles in liquids to improve thermoelectric conversion, due to their thermodiffusive and magnetic properties. Core@shell cobalt ferrite@maghemite nanoparticles (NPs) of various sizes with three different kinds of coatings are tested for dispersion in EMIM TFSI (ethyl-methylimidazolium bistriflimide), an ionic liquid (IL) of high electrical conductivity. Among the tested ligands, PAC6MIM±Br− (1-(6-hexylphosphonate) 3-methyl imidazolium bromide) emerges as the most efficient due to its phosphonic group. This ligand leads to dispersions of clusters of a few dozen NPs in water and a few NPs in EMIM TFSI. For improving both the viscosity and the electrical conductivity, dispersions in binary mixtures of propylene carbonate (PC), a polar medium, and EMIM-TFSI are further investigated with the sample based on NPs of ∼ 9 nm diameter. Through a pumping and heating procedure, stable dispersions are obtained with a subsequent reduction of the size of the NP clusters, down to 1 to 2 NPs in EMIM TFSI and a few NPs in PC and their binary mixtures. The mixture with an IL mole fraction ∼0.2–0.3 and maximal electrical conductivity is a promising candidate for further thermoelectric investigations.

Highly Efficient Carbonylation of Propylene Oxide into β‐Butyrolactone Catalyzed over Co‐Al Bimetallic Species†

AbstractRational designation of the catalyst for efficient atom‐economic conversion of propylene oxide (PO) and carbon monoxide (CO) into β‐butyrolactone is of current significance. By employing the O,N,O‐tridentate ligands R1,R2LH2 (1–4), the aluminium compounds (R1,R2LAlCl)2 (R1,R2=H,H (5), tBu,tBu (6), Cl,Cl (7), Br,Br (8)) and the derived anion‐cation pairs [H,HLAl(THF)3]+[Co(CO)4]− (9) and [(R1,R2LAl)2Cl(THF)2]+[Co(CO)4]− (R1,R2=tBu,tBu (10), Cl,Cl (11), Br,Br (12)) as well as the aluminium‐cobalt bimetallic cluster compounds [(R1,R2LAl)2Cl(THF)][Co3(CO)10] (R1,R2=tBu,tBu (13), Cl,Cl (14), Br,Br (15)) were prepared. Compounds 9–12 efficiently catalyzed the PO carbonylation into β‐butyrolactone to achieve up 93.4–98.9 % yields while 13–15 gained 95.2–99.0 % yields all at 25 °C and 0.1 MPa CO pressure. The Lewis acidic property of the aluminium compounds 5–8 was investigated. The kinetic of the catalytic reaction using compound 10 was studied. The cooperatively catalytic reaction mechanism by the Co−Al bimetallic species is proposed.

Propylene carbonate synthesis routes using CO2: DFT and thermodynamic analysis

Propylene carbonate (PC) is utilized to improve performance and stability in lithium-ion batteries as an electrolyte component and as a high-performance solvent in paints, varnishes, and adhesives. It is a versatile chemical used in many different industries. It also functions as a plasticizer in polymers and a solvent in pharmaceutical and cosmetic formulations. In the current work, chemical equilibrium analyses of a number of potential processes involved in the synthesis of PC were conducted. To examine the thermodynamic viability of all five approaches, the fluctuation of ΔGmo with temperature for the key processes of PC synthesis was investigated in a specific temperature range of 25 °C-180 °C and at 1 bar and 60 bar pressures. The heat capacity values were estimated using the Rozicka-Domalski method. Benson Group-Increment Theory (BGIT) was used to evaluate the unknown ΔfH for a molecule. By examining the impact of temperature (25 °C-180 °C) and pressure (0–100 bars) on chemical equilibrium constant and equilibrium conversion of reactants, the main reactions of PC synthesis pathways were compared. It was discovered that the one-pot synthesis route and the o-chloropropanol and CO2 approach were superior. The DFT calculations were performed to study the energy changes taking place to convert propylene, glycerol, and propylene glycol (PG) into PC. Both thermodynamic and DFT calculations proved that the PG and urea route is the least favorable for synthesizing PC.

Large scale atomistic and quantum mechanical study of Na+ ion transport in liquid electrolytes for batteries

Lithium–ion batteries (LIBs) have long dominated energy storage markets due to their high energy density and reliability. However, concerns over lithium scarcity and geographic distribution necessitate alternatives. Sodium-ion batteries (SIBs) offer a promising solution due to sodium's abundance, cost-effectiveness, and favorable electrochemical properties. This study investigates Na+ ion transport, aggregation, and performance in various organic electrolytes using molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The electrolytes studied include ethylene carbonate (EC), propylene carbonate (PC), dimethoxyethane (DME), and dimethyl carbonate (DMC) at 320 K. We focused on conductivity, diffusivity, and survival probability of Na+ ions at different salt concentrations. Furthermore, the solvation structure and the binding energy of ions in the electrolytes are thoroughly analyzed. Key findings reveal that at 2 M salt concentration, Na+ ion diffusivity and ionic conductivity follow the order EC>PC>DME>DMC. Increasing salt concentration decreases self–diffusion coefficients of Na+ and PF6− ions across all electrolytes, affecting conductivity. EC shows the highest ionic conductivity at both 1 M and 2 M salt concentrations. These insights suggest that a 2 M NaPF6 concentration in EC optimizes ionic conductivity, making it ideal for high–performance SIBs. This study provides crucial understanding for optimizing electrolytes in SIBs, advancing their development for scalable energy storage solutions.

The polytannic acid‐Fe(III) functionalized graphene oxide in poly (propylene carbonate) nanocomposite enabling enhanced shape memory, UV‐resistance, and self‐healing performance

AbstractPolypropylene carbonate (PPC) is a promising candidate of substrate materials used for human wearable devices due to its excellent ductility and biocompatibility. However, PPC is prone to be deformed, thus resulting in poor shape recovery property. One effective solution is to construct composites. In this work, poly (tannic acid) with Fe3+ (FPTA) @ graphene oxide (GO) was added to fabricate FPTA@GO/PPC composites. The results show that FPTA@GO can construct a tight network of hydrogen bonds into PPC to improve shape memory and self‐healing properties. By varying the FPTA@GO content, the composites exhibit tunable shape memory property. Dynamic mechanical analysis confirms that FPTA@GO/PPC composites show better shape memory properties compared with pure PPC. 5 wt% FPTA@GO/PPC composite demonstrates superior shape fixation ratio (Rf = 99%) as well as superior shape recovery ratio (Rr = 94%) in 37°C. Moreover, 5 wt% FPTA@GO/PPC composite possesses great self‐healing efficiency of 81% and tensile strength (17.2 MPa). The UV absorption capacity of 5 wt% FPTA@GO/PPC is increased by 150% (far and mid‐UV regions) and 400% (near‐UV region) compared with pure PPC. Thus, FPTA@GO/PPC composites have potential applications in developing shape memory, self‐healing, and UV‐resistant materials for human wearable devices.

Kinetic insights into energy-saving and low-carbon reactive distillation processes for the transesterification to dimethyl carbonate

The transesterification of propylene carbonate (PC) or ethylene carbonate (EC) to dimethyl carbonate (DMC) by using catalytic reactive distillation (RD) is a promising approach for carbon dioxide utilization. However, there is still scarcity of comprehensive comparison between the two RD processes. Hence, using the UNIQUAC model and kinetics calibrated by literature and our experiments, we conduct an extensive comparison of the two RD processes. Based on the kinetic insights, laboratory RD processes for both reactions are modeled, analyzed, and experimentally validated. Consequently, two RD processes designed to produce 60 ktpy of DMC are optimized and compared. The interplay and control factors between reaction and separation are elucidated and clarified via investigating variations of the actual chemical equilibrium constant profile compared with theoretical values along the reactive section at various pressures, liquid holdups, etc. The results reveal that the optimized EC RD process achieves almost 50 % reductions in both total annual cost and carbon dioxide emission compared to the PC RD process. This work facilitates the carbon neutrality and provides an essential guide for quantitatively assessing the two routes.

Impact of functional groups on lithium salt dispersion and mobility in polymer electrolytes

AbstractSolid Polymer electrolytes are versatile, highly processible and electrochemically compatible with solid electrode materials. The versatility of these materials is a result of the existence of many possible conductive polymer‐salt, polymer‐polymer and salt‐salt combinations. Despite the wide array of available lithium salts, most polymer electrolyte materials are made using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) due to its long history of achieving relatively high ionic conductivities in polymer electrolyte systems with the most famous being poly(ethylene oxide) (PEO). It is however possible that better ionic conductivities can be achieved with different salts and/or in polymer matrices containing different functional groups. This is because ionic conductivity in polymer electrolytes is partially based on the ability of the polymer matrix to dissolve and bond to the salt. These interactions impact local‐scale ion mobility which can be measured via NMR spectroscopy using pulsed field gradient experiments. In this work, polymer electrolytes are prepared using PEO, hydrogenated nitrile butadiene rubber and poly(propylene) carbonate. Ion mobility, lithium conductivity and salt‐polymer interactions are investigated to compare interactions between LiTFSI and lithium cyano(trifluorosulfonyl)imide in polymers with common salt‐dissociating functional groups such as ethyl, nitrile and carbonate to determine the impact of these interactions on ionic conductivity.

Crystallization kinetics as a tool to fine-tune the catalytic activity of Na-LTA zeolite precursors in the transesterification of glycerol to glycerol carbonate

Glycerol carbonate is a versatile molecule used as a fuel additive and a chemical building block. It is a prominent route for glycerol valorization, improving the biodiesel production chain. This base-catalyzed reaction can be carried out using sodium-type zeolites if accessibility to the basic sites is ensured. Herein, we report a facile strategy to fine-tune the number and access to basic sites of Na-LTA zeolite precursors via monitoring the crystallization kinetics of the microporous material. It is demonstrated that an optimal glycerol to glycerol carbonate conversion is obtained when using the solid obtained at the beginning of the crystallization (90 min at 100 °C of hydrothermal step). Textural and spectroscopy characterization reveals that semicrystalline material presents many basic aluminate anions in a very open structure, allowing facile access to glycerol and propylene carbonate. Moreover, it is shown that this catalyst is stable in four successive reaction cycles and active in different reactions conditions

Propylene carbonate activated electrochemical performances of in situ polymerized ionogel electrolytes

Ionogel electrolytes show great potential in solid-state batteries attributed to their outstanding characteristics. However, because of the strong ionic nature of ionic liquids, ionogel electrolytes generally exhibit low lithium-ion transference number and poor inferior interfacial contact, limiting their practical applications. In present research, propylene carbonate (PC) is added to form solvation separated ion pair with lithium ions in the conventional pyrrolidinium ionogel electrolytes, which comprehensively improves electrochemical properties of ionogels in lithium metal batteries. An astonished improvement is observed in an abrupt increase of the lithium-ion transference number from 0.1 to 0.41, thereby elevating ionic conductivities from 4.7 × 10−4 S/cm to 1.72 × 10−3 S/cm and reducing the activation energies of ion transport from 0.036eV to 0.018eV. As a result, PC highly activates electrochemical performances in assembled LiFePO4|Li batteries, exhibiting high discharging specific capacities: 134 mAh/g (1C), while that of PC free ionogel is 5 mAh/g (1C), respectively. The PC assisted LiFePO4|Li cell could retain 90 % of its initial specific capacity after 200 cycles and could work at a wide temperature range from 0 °C to 100 °C. The results demonstrate a new strategy to improve lithium-ion transference number in ionogel electrolytes for achieving improved performance in solid-state lithium metal batteries.

Study on structural, electrical, morphological, thermal and mechanical properties of P(VdC-co-AN)/PEG polymer electrolyte for energy storage applications

Electrochemical devices play pivotal roles in fostering a sustainable future. In modern technologies, the research and development of solid electrolytes are effectively utilized in electrochemical devices. Here in, we report a solid polymer electrolyte as a separator for lithium-ion batteries. Novel synthetic polymers [ Poly (vinylidene chloride- co– acrylonitrile), Poly Ethylene Glycol] are blended with constant weight percentage of salt [lithium perchlorate (LiClO4)] and different concentrations of plasticizer [propylene carbonate (PC)] using solvent casting method. As polymer electrolyte’s ionic conductivity enhanced up to 10-4 S/cm with 4.5 V electrochemical stability at ambient temperature. Furthermore, these polymer electrolytes restrain the growth of lithium dendrites, which were entrenched via temperature-dependent impedance method. The PC influence enhances the tensile strength of polymer electrolyte (upto 56.76 MPa). Dielectric study shows the non-Debye behaviour of the prepared electrolytes. To sum up, PEG and PC incorporated polymer membrane opt-out as a separator in lithium-ion batteries.

Synthesis and Characterization of High-Performance UV-Curable Resins Derived from Propylene Carbonate

Synthesis and Characterization of High-Performance UV-Curable Resins Derived from Propylene Carbonate

Construction of CO2‐based thermoplastic elastomer via combining aliphatic polycarbonate and polyamide: A multiblock copolymer PPC‐mb‐PA6

AbstractA CO2‐based thermoplastic elastomer, poly(propylene carbonate)‐multiblock‐polyamide6 (PPC‐mb‐PA6) copolymer, was constructed through coupling amorphous/soft PPC blocks with crystalline/hard PA6 blocks. The PPC‐mb‐PA6 copolymers with different block length pairs were designed and synthesized, and then fully characterized by structural, thermal, and mechanical analysis. The proton nuclear magnetic resonance (1H‐NMR), diffusion ordered spectroscopy (DOSY), heteronuclear multiple‐bond correlation (HMBC) and gel permeation chromatography (GPC) results confirm that the multiblock sequence structure of PPC‐mb‐PA6. The differential scanning calorimetry (DSC) tests show that all PPC‐mb‐PA6s possess melting points around 179–206°C. The thermal and mechanical analysis indicates improved service temperatures (T5% up to 270°C) and tensile strength ranging from 15.8 to 39.6 MPa with higher PA6 content. The dynamic mechanical analysis demonstrates excellent shape memory effect of PPC‐mb‐PA6 with thermal stimuli responsiveness derived from the micro phase separation between soft PPC and hard PA6 domains. And the characteristic strain fixity parameter (Rf) and deformation recovery rate (Rr) are 98% and 100%, respectively, which are comparable with other excellent shape memory polymers.

Optimizing ion transport, mechanical integrity, and thermal stability: poly (propylene carbonate)/poly (vinylidene fluoride) blend electrolytes for electrochemical applications

Optimizing ion transport, mechanical integrity, and thermal stability: poly (propylene carbonate)/poly (vinylidene fluoride) blend electrolytes for electrochemical applications