The molecular basis of CO2 interaction with polymers containing fluorinated groups: computational chemistry of model compounds and molecular simulation of poly[bis(2,2,2-trifluoroethoxy)phosphazene]

Fried, Joel; Hu, Naiping

doi:10.1016/s0032-3861(03)00285-4

Cited by 86 publications

(65 citation statements)

References 35 publications

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“…An ab initio calculation was applied and the favourable interaction between carbon dioxide and the polar fluoromethyl group of trifluoroethane and of trifluoropropane was indicated by Fried and Hu [1]. They also suggested that quadrupole-dipole interaction is an important contribution to the total energy of interaction.…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Higashi

Iwai

Miyazaki

et al. 2005

Molecular Simulation

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A molecular dynamics simulation was applied to carbon dioxide + trifluoromethylbenzoic acid isomer and carbon dioxide + methylbenzoic acid isomer systems to investigate the interactions between carbon dioxide and the solutes. The pair correlation functions between the carbon dioxide and trifluoromethyl group or methyl group in the solutes were calculated to study the fluorination effect of solvation. As a result, it was found that the interactions between carbon dioxide and trifluoromethyl group in trifluoromethylbenzoic acid isomers were stronger than those between carbon dioxide and the methyl group in methylbenzoic acid isomers. The simulation results had the same tendency as the experimental solubility enhancements and coincided with the trend of the interaction parameters of the Peng-Robinson equation of state that were determined from the solubility data.

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Section: Introductionmentioning

confidence: 99%

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Higashi

Iwai

Miyazaki

et al. 2005

Molecular Simulation

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“…5 Ab initio molecular orbital energy calculations have been used to predict the formation of a favorable CO 2 -fluorine quadrupole-dipole interaction with a magnitude less than that typically observed for hydrogen bonding but greater than that found with dispersion type interactions. 6 Experimental studies have shown that partially or fully fluorinating a hydrocarbon polymer, such as poly(ethylene-co-propylene) (EP), does indeed make the resultant fluorinated EP polymer soluble in CO 2 . Hence, fluorinating a polymer enhances its solubility in supercritical CO 2 although the polymer also must have a measurable polar moment to ensure that the polymer dissolves at low pressures and at low temperatures.…”

Section: Introductionmentioning

confidence: 99%

Impact of hexafluoroisopropylidene on the solubility of aromatic‐based polymers in supercritical fluids

Shen

McHugh

Smith

et al. 2005

J of Applied Polymer Sci

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ABSTRACT:Three different supercritical fluids (SCF), CO 2 , dimethyl ether (DME), and propane, are investigated as potential solvents for processing two lactide-based terpolymers and two perfluorocyclobutyl (PFCB) aryl ether polymers. The repeat unit of the lactide-based terpolymers consists of a 1:1:1 ratio of l-lactide, diglycidyl ether of bisphenol A (DGEBA), and, in one case, 4,4Ј-hexafluoroisopropylidenediphenol (6F-Bis-A) and, in the other case, 4,4Ј-isopropylidenediphenol (6H-Bis-A). The PFCB-based polymers are synthesized from 1,1-bis[4-[(trifluorovinyl)oxy]phenyl]hexafluoroisopropylidene (6FVE) and from bis(trifluorovinyloxy)biphenyl (BPVE). For both classes of polymer the steric effect of the hexafluoroisopropylidene (6F) group reduces chain-chain interactions, disrupts electronic resonance between adjacent aromatic groups, and improves solubility. The two lactide-based terpolymers do not dissolve in CO 2 or propane, but dissolve in DME. At room temperature the poly(lactide 6F-BisA DGEBA) terpolymer dissolves at 700 bar lower pressure in DME compared to the poly(lactide 6H-Bis-A DGEBA) terpolymer. Although the 6FVE polymer dissolves in all three SCF solvents, pressures in excess of 800 bar are needed to dissolve this polymer in CO 2 and propane while 6FVE dissolves in DME at pressure below 150 bar. The other PFCB-based polymer (BPVE) only dissolves in DME, again at low pressure, although BPVE drops out of solution as the system temperature is raised above ϳ40°C, whereas 6FVE remains in solution in DME for temperatures up to 90°C.

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“…When carbon dioxide passed through the preheater, it became a supercritical fluid. Then supercritical carbon dioxide entered into equilibrium cells (11,12). The preheater and equilibrium cells were immersed into a water bath(15) which was controlled within ±0.1 K. The details of equilibrium cells are given in the previous paper [13].…”

Section: Methodsmentioning

confidence: 99%

“…No reveal specific interaction was observed by a IR spectroscopic study [8] and a NMR study [9], while another NMR study [10] concluded that the specific interaction between carbon dioxide and fluorine existed. Fried and Hu [11] applied an ab initio calculations and indicated the favourable interaction between carbon dioxide and polar fluoromethyl group of trifluoroethane and trifluoropropane and suggested that quadrupole-dipole interaction is an important contribution to the total energy of interaction.…”

Section: Introductionmentioning

confidence: 99%

Measurement and correlation of solubilities for trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Higashi

Iwai

Miyazaki

et al. 2005

The Journal of Supercritical Fluids

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The molecular basis of CO2 interaction with polymers containing fluorinated groups: computational chemistry of model compounds and molecular simulation of poly[bis(2,2,2-trifluoroethoxy)phosphazene]

Cited by 86 publications

References 35 publications

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Molecular dynamics simulation of fluorination effect for solvation of trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

Impact of hexafluoroisopropylidene on the solubility of aromatic‐based polymers in supercritical fluids

Measurement and correlation of solubilities for trifluoromethylbenzoic acid isomers in supercritical carbon dioxide

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