Interactions carbon-dioxide-polymer

Carbon Dioxide Adsorption on Dried Polymer. Other unexpected interactions of these hydrolytic polymers have been noted previously during the measurement of infrared spectra of dried Pu(IV) polymers (like those used for diffraction studies). Vibrational bands first attributed to nitrate ion were observed in samples exposed to room air however, these bands were not present in samples prepared under nitrogen atmospheres (see Fig. 4) (6). Chemical analyses established enough carbon in the exposed samples to confirm the assignment of the extraneous bands to the carbonate functional group... 

The presence of -S02(OH) groups reduced the carbon dioxide permeability by a factor of three. This can be explained (15) by the decrease in local segmental mobility of the polymer chains due to the interactions arising from hydrogen bonding. However, the overall transport process for this polymer membrane is more complicated and involves a more pronounced discrimination against methane molecules due to the highly polar nature of the polymer. 

Zhang Z, Mo Z, Zhang H, Zhang Y, Na T, An Y, Wang X, Zhao X (2002) Miscibility and hydrogen-bonding interactions in blends of carbon dioxide/epoxy propane copolymer with poly(p-vinylphenol). J Polym Sci, Part B Polym Phys 40 1957-19M... 

Polycyclic aromatic hydrocarbons (PAHs) have been extracted from contaminated land samples by supercritical fluid extraction jSFE) with both pure and modified carbon dioxide. Removing an analyte from a matrix using SFE requires knowledge about die solubility of the solute, the rate of transfer of the solute from the solid to the solvent phase, and interaction of the solvent phase with the matrix. These faclors collectively control the effectiveness of the SFF process, if not of the extraction process in general. The range of samples for which SFE has been applied continues to broaden. Applications have been in the environment, food, and polymers. 

The gas-polymer-matrix model for sorption and transport of gases in polymers is consistent with the physical evidence that 1) there is only one population of sorbed gas molecules in polymers at any pressure, 2) the physical properties of polymers are perturbed by the presence of sorbed gas, and 3) the perturbation of the polymer matrix arises from gas-polymer interactions. Rather than treating the gas and polymer separately, as in previous theories, the present model treats sorption and transport as occurring through a gas-polymer matrix whose properties change with composition. Simple expressions for sorption, diffusion, permeation and time lag are developed and used to analyze carbon dioxide sorption and transport in polycarbonate. 

In Section I we introduce the gas-polymer-matrix model for gas sorption and transport in polymers (10, LI), which is based on the experimental evidence that even permanent gases interact with the polymeric chains, resulting in changes in the solubility and diffusion coefficients. Just as the dynamic properties of the matrix depend on gas-polymer-matrix composition, the matrix model predicts that the solubility and diffusion coefficients depend on gas concentration in the polymer. We present a mathematical description of the sorption and transport of gases in polymers (10, 11) that is based on the thermodynamic analysis of solubility (12), on the statistical mechanical model of diffusion (13), and on the theory of corresponding states (14). In Section II we use the matrix model to analyze the sorption, permeability and time-lag data for carbon dioxide in polycarbonate, and compare this analysis with the dual-mode model analysis (15). In Section III we comment on the physical implication of the gas-polymer-matrix model. 

The importance of the interaction with photons in the natural world can hardly be overstated. It forms the basis for photosynthesis converting carbon dioxide and water into more complex plant-associated structures. This is effectively accomplished employing chlorophyll as the catalytic site (this topic will be dealt with more fully later in the chapter). Chlorophyll contains a metal atom within a polymeric matrix, so it illustrates the importance of such metal-polymer combinations. T oday, with the rebirth of green materials and green chemistry use of clean fuel—namely, sunlight—is increasing in both interest and understanding. 

Kazarian SG, Vincent MF, Bright FV et al (1996) Specific intermolecular interaction of carbon dioxide with polymers. J Am Chem Soc 118(7) 1729-1736... 

Two classes of polymeric materials, amorphous fluoropolymers and silicones, are the only commercially available polymers to exhibit appreciable solubility in SCCO2 at readily accessible temperatures and pressures (Figure 4.3). It has been proposed that this results from a special interaction between fluorine and carbon dioxide due to the polarity of both species. Silicones are also thought to dissolve because they have weak intermolecular interactions and flexible backbones. 

In this chapter, we present results of the testing of a broad spectrum of polymers in carbon dioxide over a range of temperatures and pressures and evaluation of the effect of the high pressure carbon dioxide on the chemical/physical properties of materials tested. The testing was performed in a static manner with four controlled variables, namely temperature, pressure, treatment time and decompression time. The evaluation of the interaction of high pressure carbon dioxide with polymers included sorption and swelling behavior, solubility issue, plasticization and crystallization, and mechanical properties. The results of these evaluations are discussed in three sections Sorption, Swelling and Dissolution of Carbon Dioxide in Polymers at Elevated Pressure, Thermal Properties, and Mechanical Properties. ... 

Because of this highly variable nature of potential interactions of polymers with such a cleaning solvent, there is a considerable need to characterize any such adverse interactions and to define suitable conditions under which a wide variety of materials may be reasonably processed with little or no damage to the materials of construction. Therefore, an assessment of the interaction of pure polymeric materials with super- and subcritical carbon dioxide is an absolutely essential first step in understanding such interactions that will provide information in the appropriate design and implementation of widely acceptable cleaning strategies. 

Potential interactions of a supercritical fluid with a polymeric material may include the following (i) sorption of carbon dioxide by polymers (ii) swelling of polymers by carbon dioxide (Hi) dissolution of polymers in carbon dioxide (iv) dissolution of carbon dioxide in polymers (v) plasticization and decrease of the glass transition... 

Supercritical or high pressure carbon dioxide can induce polymer crystallization and plasticize polymers. The systematic study on the interaction of carbon dioxide with twenty different crystalline and amorphous polymers has been performed and various influencing parameters have been determined. Through the examination, analysis and comparison of the yield strength, ultimate elongation and modulus both before and after treatments in supercritical carbon dioxide at 3000 psi and 70°C, it was found that two main factors, i.e., degree of crystallinity and the presence of a polar side chain group, e g., ester. 

More universal is the method of Cp determination using selective tracers such as carbon monoxide and carbon dioxide which interact only with active metal = polymer bondsUsing tagged CO and CO2 as quenching agents systematic data have been accumulated so far on the influence of the composition of catalysts (titanium chlorides with various organometallic compounds) and polymerization conditions on Cp and kp values for the polymerization of ethylene and propylene IS)... 

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