CO2-solubility of oligomers and polymers that contain the carbonyl group

Abstract Poly(vinyl acetate) (PVAc) is miscible with CO 2 over a broad range of molecular weights at 298 K. The cloud-point pressures needed to dissolve ∼5 wt% poly(methyl acrylate) (PMA) at 298 K are significantly greater than those needed to dissolve PVAc, even though a PMA repeat group has the same number of carbon, hydrogen, and oxygen atoms as in PVAc. This large difference in dissolution pressures is attributed to the lack of accessibility of the carbon dioxide to the carbonyl group in PMA. In addition, experimental data for poly(dimethyl siloxane) (PDMS) copolymers with readily accessible side groups suggest that an acetate group is slightly more CO 2 -philic than an acrylate group. PVAc is more CO 2 -soluble than other hydrocarbon homopolymers, including poly(propylene oxide) (PPO) and poly(lactide) (PLA). However, PVAc is significantly less miscible with CO 2 than PDMS and poly(fluoroalkyl acrylate) (PFA).

[1]  V. Krukonis,et al.  Supercritical fluid technology , 1985 .

[2]  A. Hamilton,et al.  Peracetylated sugar derivatives show high solubility in liquid and supercritical carbon dioxide. , 2002, Organic letters.

[3]  M. Paulaitis,et al.  Swelling and sorption in polymer-CO2 mixtures at elevated pressures , 1987 .

[4]  Poovathinthodiyil Raveendran,et al.  Sugar acetates as novel, renewable CO(2)-philes. , 2002, Journal of the American Chemical Society.

[5]  F. Mandel,et al.  Poly(lactide-co-glycolide) solution behavior in supercritical CO2, CHF3, and CHClF2 , 2001 .

[6]  K. Matyjaszewski,et al.  Polymerization of vinyl acetate promoted by iron complexes , 1999 .

[7]  M. McHugh,et al.  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 , 1994 .

[8]  E. Kiran,et al.  Miscibility, phase separation, and volumetric properties in solutions of poly(dimethylsiloxane) in supercritical carbon dioxide , 2000 .

[9]  Z. Guan,et al.  Synthesis of Fluoropolymers in Supercritical Carbon Dioxide , 1992, Science.

[10]  M. McHugh,et al.  Comparison of the Solubility of PVF and PVDF in Supercritical CH2F2 and CO2 and in CO2 with Acetone, Dimethyl Ether, and Ethanol , 1999 .

[11]  Frank V. Bright,et al.  Specific Intermolecular Interaction of Carbon Dioxide with Polymers , 1996 .

[12]  W. Wagner,et al.  A New Equation of State for Carbon Dioxide Covering the Fluid Region from the Triple‐Point Temperature to 1100 K at Pressures up to 800 MPa , 1996 .

[13]  E. Beckman,et al.  Phase behavior of polymers containing ether groups in carbon dioxide , 2002 .

[14]  Michael R. Nelson,et al.  Ab Initio Calculations on CO 2 Binding to Carbonyl Groups , 1998 .

[15]  M. McHugh,et al.  Effect of copolymer composition on the phase behavior of mixtures of poly(ethylene-co-methyl acrylate) with propane and chlorodifluoromethane , 1991 .

[16]  Mark A. McHugh,et al.  Solubility of Polymers and Copolymers in Supercritical CO2 , 1996 .

[17]  K. Johnston,et al.  Formation of poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) submicron fibers and particles from supercritical carbon dioxide solutions , 1995 .

[18]  H. Masuoka,et al.  Solubilities and diffusion coefficients of carbon dioxide in poly(vinyl acetate) and polystyrene , 2001 .

[19]  E. Beckman,et al.  Toward the Development of “CO2-philic” Hydrocarbons. 1. Use of Side-Chain Functionalization to Lower the Miscibility Pressure of Polydimethylsiloxanes in CO2 , 1999 .

[20]  Eric J. Beckman,et al.  Non-fluorous polymers with very high solubility in supercritical CO 2 down to low pressures , 2000, Nature.

[21]  J. Heller,et al.  Direct Thickeners for Mobility Control of CO2 Floods , 1985 .

[22]  K. Johnston,et al.  Dispersion Polymerization of Methyl Methacrylate Stabilized with Poly(1,1-dihydroperfluorooctyl acrylate) in Supercritical Carbon Dioxide , 1995 .

[23]  G. Allen,et al.  Lower critical solution phenomena in polymer-solvent systems , 1965 .

[24]  M. McHugh,et al.  Solubility of Poly(tetrafluoroethylene-co-19 mol % hexafluoropropylene) in Supercritical CO2 and Halogenated Supercritical Solvents , 1996 .

[25]  K. Johnston,et al.  Solubility of homopolymers and copolymers in carbon dioxide , 1998 .

[26]  C. Cozewith,et al.  Lower critical solution temperature behavior of ethylene propylene copolymers in multicomponent solvents , 1986 .

[27]  M. Thies,et al.  Effect of Concentration and Degree of Saturation on RESS of a CO2-Soluble Fluoropolymer , 2002 .

[28]  M. Z. Yates,et al.  Poly(vinyl acetate) and poly(vinyl acetate-co-ethylene) latexes via dispersion polymerizations in carbon dioxide , 1998 .