Search

The introduction and removal of protecting groups is ubiquitous in multi-step synthetic schemes. From a green chemistry standpoint, however, alternative strategies that employ in situ and reversible protection and deprotection sequences would be attractive. The reversible reactions of CO2 with amines could provide a possible vehicle for realizing this strategy. Herein, we present (1) the products of reaction of benzylamines with CO2 in a variety of solvents with and without the presence of basic additives, (2) new adducts associated with CO2 protected benzylamine in acetonitrile containing 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and (3) the intermolecular competitive acylation of benzylamine and benzyl alcohol and the intramolecular competitive acylation of (4-aminomethyl)phenyl) methanol with isopropenyl acetate in acetonitrile containing DBU in the absence and presence of CO2.

Above certain temperatures, untreated PVC undergoes dehydrochlorination to produce conjugated polyenes in the polymer backbone. This is accompanied by formation of color in the polymer. In order to address both the thermally induced dehydrochlorination process and the accompanying color formation the dienophilic zinc and calcium salts of 11-maleimidoundecanoic acid (Zn11M and Ca11M, respectively) were synthesized and employed as stabilizing additives. The stabilizing effect of the Zn11M and Ca11M on PVC was studied at 170 °C in air. Evidence is presented which shows that this combination of salts performs a dual role of reducing both the rates of dehydrochlorination and formation of color in plasticized PVC.

A series of silylated amines have been synthesized for use as reversible ionic liquids in the application of post-combustion carbon capture. We describe a molecular design process aimed at influencing industrially relevant carbon capture properties, such as viscosity, temperature of reversal, and enthalpy of regeneration, while maximizing the overall CO2 -capture capacity. A strong structure-property relationship among the silylamines is demonstrated in which minor structural modifications lead to significant changes in the bulk properties of the reversible ionic liquid formed from reaction with CO2 .

Capturing CO2 from flue gas streams under near ambient conditions—e.g. coal-fired power plants—has traditionally involved the use of aqueous alkanol amine solutions. Aqueous solvent-based processes are energy intensive, as solvent regeneration can be costly. With growing concern over climate change, alternative CO2 capture technologies that are energy and cost efficient are required. We have established that nonaqueous silylamines can be used to efficiently and reversibly capture and release CO2 via the formation of reversible ionic liquids. We now report their unique, enhanced CO2 uptake at room temperature under 1 atm of CO2, as silylamines exhibit CO2 capture capacities greater than that expected from the conventional stoichiometry of a 2:1 amine to CO2 mole ratio. Experimental evidence is presented supporting the formation of a carbamic acid species in equilibrium with an ionic liquid network of ammonium–carbamate ion pairs to give a 3:2 amine to CO2 mole ratio. This is the first report of the stabili...

The quantum-chemical approach COSMO-RS was used to develop structure–property relationships of reversible ionic-liquid (RevIL) solvents for CO2 capture. Trends predicted for the thermodynamic properties of the RevILs using COSMO-RS, such as CO2 solubility, solvent regeneration enthalpy, and solvent reversal temperature, were verified by experimental data. This method was applied to a range of structures, including silylamines with varying alkyl chain lengths attached to the silicon and amine functionality, silylamines with fluorinated alkyl chains, sterically hindered silylamines and carbon-based analogues. The energetics of CO2 capture and release and the CO2 capture capacities are compared to those of the conventional capture solvent monoethanolamine. The results of this study suggest that the simple COSMO-RS computational approaches reported herein can act as a guide for designing new RevILs. COSMO-RS allows for the determination of the relative thermodynamic properties of CO2 in these and related systems.

Silylamine reversible ionic liquids were designed to achieve specific physical properties in order to address effective CO₂ capture. The reversible ionic liquid systems reported herein represent a class of switchable solvents where a relatively non-polar silylamine (molecular liquid) is reversibly transformed to a reversible ionic liquid (RevIL) by reaction with CO₂ (chemisorption). The RevILs can further capture additional CO₂ through physical absorption (physisorption). The effects of changes in structure on (1) the CO₂ capture capacity (chemisorption and physisorption), (2) the viscosity of the solvent systems at partial and total conversion to the ionic liquid state, (3) the energy required for reversing the CO₂ capture process, and (4) the ability to recycle the solvents systems are reported.

Calcium and zinc salts of epoxidized linolenic acid were synthesized and used as multifunctional additives, to minimize or prevent the reaction of epoxidized soybean oil (ESO) with liberated hydrochloric acid (HCl) during the thermal degradation of poly(vinyl chloride) (PVC) in particular. These metal epoxy salts were incorporated as thermal stabilizers for both diisodecyl phthalate and ESO–plasticized PVC blends that underwent thermal degradation studies at 170°C. The overall performance of these metal epoxy salts was examined by thermal gravimetric analysis and visual color retention of the PVC blends. The weight loss profiles of the metal salt stabilized PVC were comparable to those of blends containing metal stearates. There were, however, vast improvements in color retention of the plasticized PVC using these novel additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41736.

Heats of formation at 0 and 298 K are predicted for PF3, PF5, PF3O, SF2, SF4, SF6, SF2O, SF2O2, and SF4O as well as a number of radicals derived from these stable compounds on the basis of coupled cluster theory [CCSD(T)] calculations extrapolated to the complete basis set limit. In order to achieve near chemical accuracy (+/-1 kcal/mol), additional corrections were added to the complete basis set binding energies based on frozen core coupled cluster theory energies: a correction for core-valence effects, a correction for scalar relativistic effects, a correction for first-order atomic spin-orbit effects, and vibrational zero-point energies. The calculated values substantially reduce the error limits for these species. A detailed comparison of adiabatic and diabatic bond dissociation energies (BDEs) is made and used to explain trends in the BDEs. Because the adiabatic BDEs of polyatomic molecules represent not only the energy required for breaking a specific bond but also contain any reorganization energies of the bonds in the resulting products, these BDEs can be quite different for each step in the stepwise loss of ligands in binary compounds. For example, the adiabatic BDE for the removal of one fluorine ligand from the very stable closed-shell SF6 molecule to give the unstable SF5 radical is 2.8 times the BDE needed for the removal of one fluorine ligand from the unstable SF5 radical to give the stable closed-shell SF4 molecule. Similarly, the BDE for the removal of one fluorine ligand from the stable closed-shell PF3O molecule to give the unstable PF2O radical is higher than the BDE needed to remove the oxygen atom to give the stable closed-shell PF3 molecule. The same principles govern the BDEs of the phosphorus fluorides and the sulfur oxofluorides. In polyatomic molecules, care must be exercised not to equate BDEs with the bond strengths of given bonds. The measurement of the bond strength or stiffness of a given bond represented by its force constant involves only a small displacement of the atoms near equilibrium and, therefore, does not involve any reorganization energies, i.e., it may be more appropriate to correlate with the diabatic product states.