Solubility of Poly(ethylene-co-acrylic acid) in Low Molecular Weight Hydrocarbons and Dimethyl Ether. Effect of Copolymer Concentration, Solvent Quality, and Copolymer Molecular Weight

Lee, Sang-Ho; LoStracco, Minna A.; Hasch, Bruce M.; McHugh, Mark A.

doi:10.1021/j100066a025

Cited by 46 publications

(72 citation statements)

References 10 publications

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“…The cloud-point loci exhibit a maximum value at about 5 wt% PMA at each temperature. The maximum in cloud-point pressure near 5 wt% which characterizes the PMA-CO 2 and PVAc-CO 2 mixtures has been previously observed for other polymer-solvent mixtures Meilchen, et al 1991;Allen and Baker, 1965;Irani and Cozewith 1986;Lee. et al 1994).…”

Section: Resultssupporting

confidence: 65%

INEXPENSIVE CO{sub 2} THICKENING AGENTS FOR IMPROVED MOBILITY CONTROL OF CO{sub 2} FLOODS

Enick¹,

Beckman²,

Hamilton³

2004

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The objective of this research was the design, synthesis and evaluation of inexpensive, nonfluorous carbon dioxide thickening agents. We followed the same strategy employed in the design of fluorinated CO 2 polymeric thickeners. First, a highly CO 2 -philic, hydrocarbon-based monomer was to be identified. Polymers or oligomers of this monomer were then synthesized. The second step was to be completed only when a CO 2 -soluble polymer that was soluble in CO2 at pressures comparable to the MMP was identified. In the second step, viscosity-enhancing associating groups were to be incorporated into the polymer to make it a viable thickener that exhibited high CO 2 solubility at EOR MMP conditions. This final report documents the CO 2 solubility of a series of commercial and novel polymers composed of carbon, hydrogen, oxygen and, in some cases, nitrogen.In the first section of the report, we demonstrate that poly(vinyl acetate), PVAc, is the most CO 2 soluble, inexpensive, commodity polymer that has yet been identified. The pressure required to dissolve PVAc in CO 2 was 6000 -9000 psia; thousands of psi greater than the range of MMP values. Therefore PVAc was not soluble enough in CO 2 to serve as the "base polymer" from which CO 2 thickeners would be developed. The next objective of this investigation was to determine if any polymer (composed of C, H, O, N and/or S) could exhibit CO 2 solubility greater than that of PVAc.The second section is a report on the comparison of CO 2 -philicity of oxygenated hydrocarbon side groups on a PDMS polymer. These side-functionalized PDMS polymers are not candidates for a CO 2 thickener because they contain silicon, nonetheless the PDMS backbone provides a highly CO 2 -soluble molecular framework onto which the side chains composed of C, H, O and N can be grafted. The side groups that interacted most favorably with CO 2 caused the functionalized PDMS molecule to have the greatest miscibility with CO 2 . These results provided a useful tool for comparing the CO 2 -philicity of various side chains, and the most promising side groups were incorporated into a polymer containing neither silicon nor fluorine. Both ethers and acetates appeared particularly promising. To date, these polymers have not been more CO 2 -soluble than PVAc.The third section is a report on a novel class of highly CO 2 soluble compounds known as sugar acetates. Low molecular weight sugar acetates are remarkably CO 2 soluble. Although we were successful in designing CO 2 soluble hydrogen bonding compounds, they were not capable of thickening the CO2. High molecular weight sugar acetate polymers, cellulose triacetate and peracetlyated xanthan gum, were insoluble in CO2.The fourth section is a report on a novel type of phase behavior that was discovered while studying the sugar acetates. Highly CO 2 -philic solids, including small molecules and polymers, can exhibit melting point depression in dense CO 2 , i.e. these solids melt instantly in dense CO 2 . This phenomenon is symptomatic of a favorable thermody...

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Section: Resultssupporting

confidence: 65%

INEXPENSIVE CO{sub 2} THICKENING AGENTS FOR IMPROVED MOBILITY CONTROL OF CO{sub 2} FLOODS

Enick¹,

Beckman²,

Hamilton³

2004

View full text Add to dashboard Cite

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“…The cloud-point loci exhibit a maximum value at about 5 wt% PMA at each temperature. The maximum in cloud-point pressure near 5 wt% which characterizes the PMA-CO 2 and PVAc-CO 2 mixtures has been previously observed for other polymer-solvent mixtures Meilchen, et al 1991;Mertdogan et al 1996; Allen and Baker, 1965; Irani and Cozewith 1986; Lee. et al 1994).…”

Section: Resultssupporting

confidence: 60%

Inexpensive CO2 Thickening Agents for Improved Mobility Control of CO2 Floods

Enick¹,

Beckman²,

Hamilton³

2005

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The objective of this research was the design, synthesis and evaluation of inexpensive, nonfluorous carbon dioxide thickening agents. We followed the same strategy employed in the design of fluorinated CO 2 polymeric thickeners. First, a highly CO 2 -philic, hydrocarbon-based monomer was to be identified. Polymers or oligomers of this monomer were then synthesized. The second step was to design a CO 2 -thickener based on these CO 2 -philic polymers. Two types of thickeners were considered. The first was a copolymer in which the CO 2 -philic monomer was combined with a small proportion of CO 2 -phobic associating groups that could cause viscosityenhancing intermolecular interactions to occur. The second was a small hydrogen-bonding compound with urea groups in the core to promote intermolecular interactions that would cause the molecules to "stack" in solution while the arms were composed of the CO 2 -philic oligomers. Although we were not able to develop a viable thickener that exhibited high enough CO 2 solubility at EOR MMP conditions to induce a viscosity increase, we made significant progress in our understanding of CO 2 -soluble compounds that can be used in subsequent studies to design CO 2 -soluble thickeners or CO 2 -soluble surfactant-based foaming agents. These findings are detailed in this final report.In summary, we assessed many polymers and verified that the most CO 2 -soluble oxygenated hydrocarbon polymer is poly(vinyl acetate), PVAc. This is primarily due to the presence of both ether and carbonyl oxygens associated with acetate-rich compounds. In addition to polymers, we also made small acetate-rich molecules that were also capable of associating in solution via the inclusion of hydrogen-bonding groups in hopes of forming viscosity-enhancing macromolecules. Despite the presence of multiple acetate groups in these compounds, which can impart incredible CO 2 -solubility to many compounds, our attempts to make acetate-rich high molecular weight polymers and small hydrogen-bonding compounds did not yield a highly CO 2 -soluble polymer or hydrogen-bonding associative thickener. The conclusions of our molecular modeling calculations confirmed that although acetates are indeed "CO 2 -philic", nitrogen-containing amines also interact favorably with CO 2 and should also be examined. Therefore we obtained and synthesized many N-rich (e.g. amine-containing) polymers. Unfortunately, we found that the intermolecular polymer-polymer interactions between the amines were so strong that the polymers were essentially insoluble in CO 2 . For the convenience of the reader, a table of all of the polymers evaluated during this research is provided. Executive SummaryThe objective of this research was the design, synthesis and evaluation of inexpensive, nonfluorous carbon dioxide thickening agents. We followed the same strategy employed in the design of fluorinated CO 2 polymeric thickeners. First, a highly CO 2 -philic, hydrocarbon-based monomer was to be identified. Polymers or oligomers of this monomer wer...

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“…[1][2][3][4][5][6][7][8] The work presented herein demonstrates the impact of a nonpolar cosolvent, sulfur hexafluoride (SF 6 ), on the phase behavior of a nonpolar fluorocopolymer, poly(tetrafluoroethylene-co-19.3 mol % hexafluoropropylene) (FEP 19 ), in two SCF solvents, CO 2 and fluoroform (CHF 3 ). A cosolvent can enhance copolymer solubility if it possesses physical properties that increase favorable energetic interactions with the copolymer of interest.…”

Section: Introductionmentioning

confidence: 99%

“…A cosolvent can enhance copolymer solubility if it possesses physical properties that increase favorable energetic interactions with the copolymer of interest. Dispersion-type forces are expected to be the dominant attractive forces between segments of FEP 19 given that tetrafluoroethylene and hexafluoropropylene repeat units exhibit characteristics of nonpolar fluorinated alkanes. The FEP 19 used in this study has a weight-average molecular weight of Ϸ210,000 9 and is end-capped with carboxylic acid groups that amount to approximately 1000 mass-ppm groups, which should have only a modest effect on the phase behavior of this copolymer.…”

Section: Introductionmentioning

confidence: 99%

“…The FEP 19 used in this study has a weight-average molecular weight of Ϸ210,000 9 and is end-capped with carboxylic acid groups that amount to approximately 1000 mass-ppm groups, which should have only a modest effect on the phase behavior of this copolymer. 10 Mertdogan et al 11 have also shown that CO 2 is a rather weak solvent for FEP 19 due to the CO 2 quadrupolar self-interactions that are much greater than FEP 19 -CO 2 or FEP 19 -FEP 19 interactions at temperatures below 185°C. The experimental study described herein is similar in principle to data reported by Kiran and coworkers for polyethylene-alkane-CO 2 mixtures.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Cosolvency effect of SF6 on the solubility of poly(tetrafluoroethylene-co-19 mol % hexafluoropropylene) in supercritical CO2 and CHF3

Mertdogan

McHugh

Tuminello

1999

J. Appl. Polym. Sci.

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Solubility of Poly(ethylene-co-acrylic acid) in Low Molecular Weight Hydrocarbons and Dimethyl Ether. Effect of Copolymer Concentration, Solvent Quality, and Copolymer Molecular Weight

Cited by 46 publications

References 10 publications

INEXPENSIVE CO{sub 2} THICKENING AGENTS FOR IMPROVED MOBILITY CONTROL OF CO{sub 2} FLOODS

INEXPENSIVE CO{sub 2} THICKENING AGENTS FOR IMPROVED MOBILITY CONTROL OF CO{sub 2} FLOODS

Inexpensive CO2 Thickening Agents for Improved Mobility Control of CO2 Floods

Cosolvency effect of SF6 on the solubility of poly(tetrafluoroethylene-co-19 mol % hexafluoropropylene) in supercritical CO2 and CHF3

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