DOI: 10.1126/science.265.5170.356. Dispersion Polymerizations in Supercritical Carbon Dioxide

Dispersion Polymerizations in Supercritical Carbon Dioxide

10.1126/science.265.5170.356

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

Conventional heterogeneous dispersion polymerizations of unsaturated monomers are performed in either aqueous or organic dispersing media with the addition of interfacially active agents to stabilize the colloidal dispersion that forms. Successful stabilization of the polymer colloid during polymerization results in the formation of high molar mass polymers with high rates of polymerization. An environmentally responsible alternative to aqueous and organic dispersing media for heterogeneous dispersion polymerizations is described in which supercritical carbon dioxide (CO 2 ) is used in conjunction with molecularly engineered free radical initiators and amphipathic molecules that are specifically designed to be interfacially active in CO 2 . Conventional lipophilic monomers, exemplified by methyl methacrylate, can be quantitatively (>90 percent) polymerized heterogeneously to very high degrees of polymerization (>3000) in supercritical CO 2 in the presence of an added stabilizer to form kinetically stable dispersions that result in micrometer-sized particles with a narrow size distribution.

Bibliography

DeSimone, J. M., Maury, E. E., Menceloglu, Y. Z., McClain, J. B., Romack, T. J., & Combes, J. R. (1994). Dispersion Polymerizations in Supercritical Carbon Dioxide. Science, 265(5170), 356â359.

Authors 6

J. M. DeSimone (first)
E. E. Maury (additional)
Y. Z. Menceloglu (additional)
J. B. McClain (additional)
T. J. Romack (additional)
J. R. Combes (additional)

References 26 Referenced 605

ARSHADY, R, SUSPENSION, EMULSION, AND DISPERSION POLYMERIZATION - A METHODOLOGICAL SURVEY, COLLOID AND POLYMER SCIENCE 270: 717 (1992). (10.1007/BF00776142) / COLLOID AND POLYMER SCIENCE (1992)
Barrett K. E. J. Dispersion Polymerization in Organic Media (1975).
COMBES, J.R., HOMOGENEOUS FREE-RADICAL POLYMERIZATIONS IN CARBON-DIOXIDE .3. TELOMERIZATION OF 1,1-DIFLUOROETHYLENE IN SUPERCRITICAL CARBON-DIOXIDE, MACROMOLECULES 27: 865 (1994). (10.1021/ma00081a036) / MACROMOLECULES (1994)
CONDO, P.D., GLASS TRANSITIONS OF POLYMERS WITH COMPRESSED FLUID DILUENTS - TYPE-II AND TYPE-III BEHAVIOR, MACROMOLECULES 27: 365 (1994). (10.1021/ma00080a008) / MACROMOLECULES (1994)
CONSANI, K.A., J SUPERCRIT FLUID 3: 51 (1990). (10.1016/0896-8446(90)90008-A) / J SUPERCRIT FLUID (1990)
DESIMONE, J.M., POLYM PREPR AM CHEM 68: 41 (1993). / POLYM PREPR AM CHEM (1993)
10.1126/science.257.5072.945
Fitch R. M. Polymer Colloids (1971). (10.1007/978-1-4684-1920-7)
GUAN, Z, POLYM PREPR AM CHEM 33: 329 (1992). / POLYM PREPR AM CHEM (1992)
GUAN, Z, POLYM PREPR AM CHEM 34: 447 (1993). / POLYM PREPR AM CHEM (1993)
GUAN, Z, POLYM PREPR AM CHEM 34: 614 (1993). / POLYM PREPR AM CHEM (1993)
GUAN, Z, HOMOGENEOUS FREE-RADICAL POLYMERIZATIONS IN SUPERCRITICAL CARBON-DIOXIDE .2. THERMAL-DECOMPOSITION OF 2,2'-AZOBIS(ISOBUTYRONITRILE), MACROMOLECULES 26: 2663 (1993). (10.1021/ma00063a003) / MACROMOLECULES (1993)
HOEFLING, T, JOURNAL OF SUPERCRITICAL FLUIDS 5: 237 (1992). (10.1016/0896-8446(92)90013-A) / JOURNAL OF SUPERCRITICAL FLUIDS (1992)
HOEFLING, T.A., EFFECT OF STRUCTURE ON THE CLOUD-POINT CURVES OF SILICONE-BASED AMPHIPHILES IN SUPERCRITICAL CARBON-DIOXIDE, JOURNAL OF SUPERCRITICAL FLUIDS 6: 165 (1993). (10.1016/0896-8446(93)90015-P) / JOURNAL OF SUPERCRITICAL FLUIDS (1993)
LEMERT, R.M., REVERSE MICELLES IN SUPERCRITICAL FLUIDS .3. AMINO-ACID SOLUBILIZATION IN ETHANE AND PROPANE, JOURNAL OF PHYSICAL CHEMISTRY 94: 6021 (1990). (10.1021/j100378a073) / JOURNAL OF PHYSICAL CHEMISTRY (1990)
LU, Y.Y., DISPERSION POLYMERIZATION OF STYRENE IN ETHANOL - MONOMER PARTITIONING BEHAVIOR AND LOCUS OF POLYMERIZATION, JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS 26: 1187 (1988). (10.1002/polb.1988.090260604) / JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS (1988)
Matijevic E. Surface and Colloid Science 15 (1993). (10.1007/978-1-4615-3002-2)
MAURY, E.E., POLYM PREPR AM CHEM 34: 664 (1993). / POLYM PREPR AM CHEM (1993)
MCFANN, G.J., PHASE-BEHAVIOR OF AOT MICROEMULSIONS IN COMPRESSIBLE LIQUIDS, JOURNAL OF PHYSICAL CHEMISTRY 95: 4889 (1991). (10.1021/j100165a052) / JOURNAL OF PHYSICAL CHEMISTRY (1991)
McHugh M. Supercritical Fluid Extraction 2 (1994).
Napper D. H. Polymeric Stabilization of Colloidal Dispersions (1983).
Odian G. Principles of Polymerization 3 (1981).
PECK, D.G., THEORY OF THE PRESSURE EFFECT ON THE CURVATURE AND PHASE-BEHAVIOR OF AOT PROPANE BRINE WATER-IN-OIL MICROEMULSIONS, JOURNAL OF PHYSICAL CHEMISTRY 95: 9549 (1991). (10.1021/j100176a092) / JOURNAL OF PHYSICAL CHEMISTRY (1991)
Piirma I. Polymeric Surfactants (1992).
SHEN, S, DISPERSION POLYMERIZATION OF METHYL-METHACRYLATE - MECHANISM OF PARTICLE FORMATION, JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 32: 1087 (1994). (10.1002/pola.1994.080320611) / JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY (1994)
TSENG, C.M., UNIFORM POLYMER PARTICLES BY DISPERSION POLYMERIZATION IN ALCOHOL, JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 24: 2995 (1986). (10.1002/pola.1986.080241126) / JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY (1986)

Dates

Type	When
Created	18 years, 10 months ago (Oct. 5, 2006, 8:01 p.m.)
Deposited	1 year, 7 months ago (Jan. 12, 2024, 4:54 p.m.)
Indexed	1 week, 3 days ago (Aug. 20, 2025, 9:12 a.m.)
Issued	31 years, 1 month ago (July 15, 1994)
Published	31 years, 1 month ago (July 15, 1994)
Published Print	31 years, 1 month ago (July 15, 1994)

Funders 0

None

BibTeX

@article{DeSimone_1994, title={Dispersion Polymerizations in Supercritical Carbon Dioxide}, volume={265}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.265.5170.356}, DOI={10.1126/science.265.5170.356}, number={5170}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={DeSimone, J. M. and Maury, E. E. and Menceloglu, Y. Z. and McClain, J. B. and Romack, T. J. and Combes, J. R.}, year={1994}, month=jul, pages={356–359} }

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