Synthesis, Characterization, and Energetic Properties of Nitrate Ester Acrylate Polymer
Ontology highlight
ABSTRACT:
SUBMITTER:
PROVIDER: S-EPMC10601433 | biostudies-literature | 2023 Oct
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Digital light processing (DLP) is an accurate and fast additive manufacturing technique to produce a variety of products, from patient-customized biomedical implants to consumer goods. However, DLP's use in tissue engineering has been hampered due to a lack of biodegradable resin development. Herein, a library of biodegradable poly(esters) capped with urethane acrylate (with variations in molecular weight) is investigated as the basis for DLP printable resins for tissue engineering. The synthesized oligomers show good printability and are capable of creating complex structures with mechanical moduli close to those of medium-soft tissues (1-3 MPa). While fabricated films from different molecular weight resins show few differences in surface topology, wettability, and protein adsorption, the adhesion and metabolic activity of NCTC clone 929 (L929) cells and human dermal fibroblasts (HDFs) are significantly different. Resins from higher molecular weight oligomers provide greater cell adhesion and metabolic activity. Furthermore, these materials show compatibility in a subcutaneous in vivo pig model. These customizable, biodegradable, and biocompatible resins show the importance of molecular tuning and open up new possibilities for the creation of biocompatible constructs for tissue engineering.
| S-EPMC11481055 | biostudies-literature
Project description:In order to enhance the application performance of glycidyl azide polymer (GAP) in solid propellant, an energetic copolyurethane binder, (poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol-block-glycidylazide polymer (PBFMO-b-GAP) was synthesized using poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol (PBFMO), which was prepared from cationic polymerization with GAP as the raw material and toluene diisocyanate (TDI) as the coupling agent via a prepolymer process. The molecular structure of copolyurethanes was confirmed by attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR-FTIR), nuclear magnetic resonance spectrometry (NMR), and gel permeation chromatography (GPC). The impact sensitivity, mechanical performance, and thermal behavior of PBFMO-b-GAP were studied by drop weight test, X-ray photoelectron spectroscopic (XPS), tensile test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA), respectively. The results demonstrated that the introduction of fluoropolymers could evidently reduce the sensitivity of GAP-based polyurethane and enhance its mechanical behavior (the tensile strength up to 5.75 MPa with a breaking elongation of 1660%). Besides, PBFMO-b-GAP exhibited excellent resistance to thermal decomposition up to 200 °C and good compatibility with Al and cyclotetramethylene tetranitramine (HMX). The thermal performance of the PBFMO-b-GAP/Al complex was investigated by a cook-off test, and the results indicated that the complex has specific reaction energy. Therefore, PBFMO-b-GAP may serve as a promising energetic binder for future propellant formulations.
| S-EPMC8399772 | biostudies-literature
Project description:High-temperature polymerizations involving self-initiation of the monomer are attractive because of high reaction rate, comparable lower viscosities, and no need for an additional initiator. However, the polymers obtained show a more complex microstructure, e.g., with specific branching levels or significant amounts of macromonomer. Simulations of the polymerization processes are powerful tools to gain a deeper understanding of the processes and the elemental reactions at the molecular level. However, simulations can be computationally demanding, requiring significant time and memory resources. Therefore, this study aims at applying AI-based forecasting of tailored polymer properties and using a kinetic Monte Carlo simulator for the generation of training and test data. The applied machine learning (ML) models (random forest and kernel density (KD) regression) predict monomer concentration, macromonomer content, and full molar mass distributions as a function of time, as well as the average branching level with an excellent performance (R 2 (coefficient of determination) > 0.99, MAE (mean absolute error) < 1% for kernel density regression). This study explores the number of training data needed for reliable and accurate predictions in ML models. Explainability methods reveal that the importance of input variables in ML models aligns with expert knowledge.
| S-EPMC11468519 | biostudies-literature
Project description:This study examines the synthesis of two geminal bisphosphonate ester-supported Ln3+ complexes [Ln(L3)2(NO3)3] (Ln = Nd3+ (5), La3+ (6)) and optical properties of the neodymium(III) complex. These results are compared to known mono-phosphonate ester-based Nd3+ complexes [Nd(L1/L2)3X3]n (X = NO3-, n = 1; Cl-, n = 2) (1-4). The optical properties of Nd3+ compounds are determined by micro-photoluminescence (µ-PL) spectroscopy which reveals three characteristic metal-centered emission bands in the NIR region related to transitions from 4F3/2 excited state. Additionally, two emission bands from 4F5/2, 2H9/2 → 4IJ (J = 11/2, 13/2) transitions were observed. PL spectroscopy of equimolar complex solutions in dry dichloromethane (DCM) revealed remarkably higher emission intensity of the mono-phosphonate ester-based complexes in comparison to their bisphosphonate ester congener. The temperature-dependent PL measurements enable assignment of the emission lines of the 4F3/2 → 4I9/2 transition. Furthermore, low-temperature polarization-dependent measurements of the transitions from R1 and R2 Stark sublevel of 4F3/2 state to the 4I9/2 state for crystals of [Nd(L3)2(NO3)3] (5) are discussed.
| S-EPMC9822372 | biostudies-literature
Project description:The search for alternative, biodegradable, and sustainable raw materials to replace finite petrochemicals is an area of great interest. Triglycerides obtained from oilseed crops are such potential raw materials. In this study, sesame oil was trans-esterified to sesame fatty methyl esters (SEFAMEs) that were used as precursors in the synthesis of sesame fatty methyl esters sulfonate (SEFAMESO) surfactant. SEFAME and SEFAMESO surfactants were characterized by high-performance liquid chromatography-mass spectrometry (HPLC-MS), 1H NMR, and Fourier transform infrared (FTIR) spectra. HPLC-MS, 1H NMR, and FTIR spectra indicated successful trans-esterification and conversion of SEFAMEs to SEFAMESO. Solution properties of the SEFAMESO surfactant including hydrophilic-lipophilic balance (HLB) value, Krafft point, foam-ability, critical micelle concentration (CMC), counterion degree of binding and thermodynamic parameters such as ΔG°mic, ΔH°mic, ΔS°mic, ΔH°mic,* and T C were evaluated. The CMC values of SEFAMESO at 298.15 K were relatively lower than that of the sodium dodecyl sulfate (SDS) standard, and these values decreased to a minimum at 303.15 K and then increased with an increase in temperature. ΔG°mic values were negative indicating a spontaneous micellization process. ΔH°mic and ΔS°mic values revealed that micellization was entropy-driven at low temperatures and both entropy- and enthalpy-driven at high temperatures. ΔH°mic,* values were negative suggesting formation of stable micelles. The evaluated properties revealed the potential application of the synthesized surfactant as a cleansing agent.
| S-EPMC7658934 | biostudies-literature
Project description:Two polymerizable ionic liquids (or monomeric ionic liquids, mILs) namely 1-butyl-3-methylimidazolium and choline acrylates ([C4mim]A and ChA, respectively) were synthesized using the modified Fukumoto method from corresponding chlorides. The chemical structure of the prepared mILs was confirmed with FTIR and NMR study. Investigation of the thermal properties with DSC demonstrates that both mILs have a Tg temperature of about 180 K and a melting point around 310 K. It was shown that the temperature dependence of FTIR confirm the Tg to be below 200. Both mILs exhibited non-Newtonian shear thinning rheological behavior at shear rates >4 s-1. It was shown that [C4mim]A is able to dissolve bacterial cellulose (BC) leading to a decrease in its degree of polymerization and recrystallisation upon regeneration with water; although in the ChA, the crystalline structure and nanofibrous morphology of BC was preserved. It was demonstrated that the thixotropic and rheological properties of cellulose dispersion in ChA at room temperature makes this system a prospective ink for 3D printing with subsequent UV-curing. The 3D printed filaments based on ChA, containing 2 wt% of BC, and 1% of N,N'-methylenebisacrylamide after radical polymerization induced with 1% 2-hydroxy-2-methylpropiophenone, demonstrated Young's modulus 7.1 ± 1.0 MPa with 1.2 ± 0.1 MPa and 40 ± 5% of strength and ultimate elongation, respectively.
| S-EPMC9736722 | biostudies-literature
Project description:Vinyl-capped cationic waterborne polyurethane (CWPU) was prepared using isophorone diisocyanate (IPDI), polycarbonate diol (PCDL), N-methyldiethanolamine (MDEA), and trimethylolpropane (TMP) as raw materials and hydroxyethyl methacrylate (HEMA) as a capping agent. Then, a crosslinked FPUA composite emulsion with polyurethane (PU) as the shell and fluorinated acrylate (PA) as the core was prepared by core-shell emulsion polymerization with CWPU as the seed emulsion, together with dodecafluoroheptyl methacrylate (DFMA), diacetone acrylamide (DAAM), and methyl methacrylate (MMA). The effects of the core-shell ratio of PA/PU on the surface properties, mechanical properties, and heat resistance of FPUA emulsions and films were investigated. The results showed that when w(PA) = 30~50%, the stability of FPUA emulsion was the highest, and the particles showed a core-shell structure with bright and dark intersections under TEM. When w(PA) = 30%, the tensile strength reached 23.35 ± 0.08 MPa. When w(PA) = 50%, the fluorine content on the surface of the coating film was 14.75% and the contact angle was as high as 98.5°, which showed good hydrophobicity; the surface flatness of the film was observed under AFM. It is found that the tensile strength of the film increases and then decreases with the increase in the core-shell ratio and the heat resistance of the FPUA film is gradually increased. The FPUA film has excellent properties such as good impact resistance, high flexibility, high adhesion, and corrosion resistance.
| S-EPMC10780964 | biostudies-literature
Project description:1,2,4,5-tetrazine ring is a common structure for the construction of energy-containing compounds, and its high nitrogen content and large conjugation effect give it the advantage of a good balance between energy and mechanical stability as a high-nitrogen energy-containing material. However, most of the reported works about tetrazine energetic materials (EMs) are symmetrically substituted tetrazines due to their easy accessibility. A small number of reports show that asymmetrically substituted tetrazines also have good properties, such as high density and generation of enthalpy and energy. Herein, two asymmetrically substituted tetrazines and their five energetic salts were prepared and fully characterized by IR spectroscopy, NMR spectra, elemental analysis, and differential scanning calorimetry (DSC). The structure of the two compounds was further confirmed by single-crystal X-ray diffraction studies. The thermal behaviors and thermodynamic parameters were determined and calculated. In addition, the energetic properties and impact sensitivities of all the compounds were obtained to assess their application potential. The results show that compounds 2–4 and 7–9 show higher detonation velocities than TNT, and the hydrazinium salt 9 possesses the best detonation properties (D = 8,232 m s−1 and p = 23.6 GPa). Except for 4 and 3, all the other compounds are insensitive, which may be applied as insensitive explosives. Noncovalent interaction analysis was further carried out, and the result shows that the strong and high proportion of hydrogen bonds may contribute to the low-impact sensitivity.
| S-EPMC9574065 | biostudies-literature
Project description:Pyridine derivatives based on the addition of trinitromethyl functional groups were synthesized by the reaction of N₂O₄ with the corresponding pyridinecarboxaldoximes, then they were converted into dinitromethylide hydrazinium salts. These energetic compounds were fully characterized by IR and NMR spectroscopy, elemental analysis, differential scanning calorimetry (DSC), and X-ray crystallography. These pyridine derivatives have good densities, positive enthalpies of formation, and acceptable sensitivity values. Theoretical calculations carried out using Gaussian 03 and EXPLO5 programs demonstrated good to excellent detonation velocities and pressures. Each of these compounds is superior in performance to TNT, while 2,6-bis(trinitromethyl)pyridine (D = 8700 m·s-1, P = 33.2 GPa) shows comparable detonation performance to that of RDX, but its thermal stability is too low, making it inferior to RDX.
| S-EPMC5943950 | biostudies-literature
Project description:The sensitivity of explosives is controlled by factors that span from intrinsic chemical reactivity and chemical intramolecular effects to mesoscale structure and defects, and has been a topic of extensive study for over 50 years. Due to these complex competing chemical and physical elements, a unifying relationship between molecular framework, crystal structure, and sensitivity has yet to be developed. In order to move towards this goal, ideally experimental studies should be performed on systems with small, systematic structural modifications, with modeling utilized to interpret experimental results. Pentaerythritol tetranitrate (PETN) is a common nitrate ester explosive that has been widely studied due to its use in military and commercial explosives. We have synthesized PETN derivatives with modified sensitivity characteristics by substituting one -CCH2ONO2 moiety with other substituents, including -CH, -CNH2, -CNH3X, -CCH3, and -PO. We relate the handling sensitivity properties of each PETN derivative to its structural properties, and discuss the potential roles of thermodynamic properties such as heat capacity and heat of formation, thermal stability, crystal structure, compressibility, and inter- and intramolecular hydrogen bonding on impact sensitivity. Reactive molecular dynamics (MD) simulations of the C/H/N/O-based PETN-derivatives have been performed under cook-off conditions that mimic those accessed in impact tests. These simulations infer how changes in chemistry affect the subsequent decomposition pathways.
| S-EPMC5941197 | biostudies-literature