DOI: 10.1126/science.286.5444.1540. The Gelation of CO <sub>2</sub> : A Sustainable Route to the Creation of Microcellular Materials

The Gelation of CO 2 : A Sustainable Route to the Creation of Microcellular Materials

10.1126/science.286.5444.1540

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

Compounds with strong thermodynamic affinity for carbon dioxide (CO 2 ) have been designed and synthesized that dissolve in CO 2 , then associate to form gels. Upon removal of the CO 2 , these gels produced free-standing foams with cells with an average diameter smaller than 1 micrometer and a bulk density reduction of 97 percent relative to the parent material.

Bibliography

Shi, C., Huang, Z., Kilic, S., Xu, J., Enick, R. M., Beckman, E. J., Carr, A. J., Melendez, R. E., & Hamilton, A. D. (1999). The Gelation of CO 2 â¯: A Sustainable Route to the Creation of Microcellular Materials. Science, 286(5444), 1540â1543.

Authors 9

C. Shi (first)
Z. Huang (additional)
S. Kilic (additional)
J. Xu (additional)
R. M. Enick (additional)
E. J. Beckman (additional)
A. J. Carr (additional)
R. E. Melendez (additional)
A. D. Hamilton (additional)

References 28 Referenced 185

10.1126/science.257.5072.945
10.1021/ma960764s
; M. L. O'Neill et al. Macromolecules 30 5050 (1997). (10.1021/ma9616930)
10.1021/cr970037a
10.1021/ie980738d
; Industr. Eng. Chem. Res. 38 2833 (1999). (10.1021/ie9807396)
10.1021/cr970040u
Super M., Beckman E. J., Trends Polym. Sci. 5, 236 (1997); / Trends Polym. Sci. by Super M. (1997)
10.1016/0010-8545(95)01232-X
10.1021/la00011a014
D. Klempner and K. C. Frisch Polymeric Foams (Hanser New York 1991).
10.1002/pen.760341407
; Polym. Eng. Sci. 14 1148 (1994).
K. Hanabusa K Okui K. Karaki T. Koyama H. Shirai J. Chem. Soc. Chem. Commun. 1992 1371; (10.1039/c39920001371)
10.1073/pnas.90.1.163
10.1021/ma00120a036
10.1021/ma951001s
U. Maitra et al. Chem. Commun. 1999 595. (10.1039/a809821b)
J. R. Fredericks and A. D. Hamilton in Comprehensive Supramolecular Chemistry J. P. Sauvage and M. W. Hosseini Eds. (Pergamon Oxford 1996) vol. 9 pp. 565–594.
10.1021/ja00137a007
; A. T. Ung R. Bishop D. C. Craig I. G. Dance M. L. Scudder J. Chem. Soc. Chem. Commun. 1991 1012.
The bisurea gelling agents were prepared by esterification of N -butoxycarbonyl (BOC)-aspartic acid in dichloromethane with 1-[3-(dimethylamino)propyl]-3-ethylcarbondiimide hydrochloride (EDCI) 4-(dimethylamino)pyridine (DMAP) and 1 H 1 H 2 H 2 H -perfluorodecanol followed by deprotection with trifluoroacetic acid/CH 2 Cl 2 (50:50) and reaction with the appropriate mono- or bis-isocyanates in CH 2 Cl 2 with excess triethylamine. The resultant bisureas were filtered off and washed with CH 2 Cl 2 1% aqueous HCl water and more CH 2 Cl 2 . All compounds gave spectroscopic characteristics consistent with their structure and were shown to be >95% pure. For more details of the synthesis of fluorinated aspartate bisureas and ureas see Science Online (www.sciencemag.org/feature/data/1044209.shl).
Foam samples were fractured sputter-coated with gold then analyzed by SEM as described [
10.1002/pen.10640
]. Sizes given throughout this report are average diameters as generated from these analyses of SEM images.
Monomers (styrene N N -dimethyl amino ethyl methacrylate n -hexyl acrylate 1 H 1 H 2 H 2 H -perfluorodecyl acrylate; Aldrich) were purified using conventional procedures (washing to remove inhibitors drying vacuum distillation as appropriate). Copolymers were prepared via bulk polymerization at 65°C using azobisisobutyronitrile (AIBN) (0.2 mol % recrystallized from methanol). Copolymers were purified via dissolution in 1 1 2-trichloroethane or perfluoromethyl cyclohexane followed by precipitation into methanol. Copolymer content was quantified using 1 H nuclear magnetic resonance. The aspartate methacrylate monomer was prepared using the scheme shown in (13) and 2-isocyanato ethyl methacrylate (Aldrich). Styrene-fluorinated acrylate copolymers were sulfonated using an SO 3 /acetic anhydride complex (acetyl sulfate).
We are developing CO 2 -philic hydrocarbons to form the building blocks for the next generation of such agents (E. J. Beckman Design of CO 2 -Philic Hydrocarbons paper presented at the Engineering Foundation Conference on Supercritical Fluids in Materials Processing and Synthesis Davos Switzerland September–October 1999).
Supported by the U.S. Department of Energy (National Petroleum Technology Office contract DE-AC26-98BC15108) NSF (grants CTS-9870925 and CHE-9817240) Air Products & Chemicals and Cabot Oil & Gas.

Dates

Type	When
Created	23 years ago (July 27, 2002, 5:45 a.m.)
Deposited	1 year, 7 months ago (Jan. 13, 2024, 5:03 a.m.)
Indexed	2 months, 1 week ago (June 18, 2025, 1:02 p.m.)
Issued	25 years, 9 months ago (Nov. 19, 1999)
Published	25 years, 9 months ago (Nov. 19, 1999)
Published Print	25 years, 9 months ago (Nov. 19, 1999)

Funders 0

None

BibTeX

@article{Shi_1999, title={The Gelation of CO 2  : A Sustainable Route to the Creation of Microcellular Materials}, volume={286}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.286.5444.1540}, DOI={10.1126/science.286.5444.1540}, number={5444}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Shi, C. and Huang, Z. and Kilic, S. and Xu, J. and Enick, R. M. and Beckman, E. J. and Carr, A. J. and Melendez, R. E. and Hamilton, A. D.}, year={1999}, month=nov, pages={1540–1543} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        6,
        18
      ]
    ],
    "date-time": "2025-06-18T17:02:51Z",
    "timestamp": 1750266171786
  },
  "reference-count": 28,
  "publisher": "American Association for the Advancement of Science (AAAS)",
  "issue": "5444",
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        1999,
        11,
        19
      ]
    ]
  },
  "abstract": "<jats:p>\n            Compounds with strong thermodynamic affinity for carbon dioxide (CO\n            <jats:sub>2</jats:sub>\n            ) have been designed and synthesized that dissolve in CO\n            <jats:sub>2</jats:sub>\n            , then associate to form gels. Upon removal of the CO\n            <jats:sub>2</jats:sub>\n            , these gels produced free-standing foams with cells with an average diameter smaller than 1 micrometer and a bulk density reduction of 97 percent relative to the parent material.\n          </jats:p>",
  "DOI": "10.1126/science.286.5444.1540",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2002,
        7,
        27
      ]
    ],
    "date-time": "2002-07-27T09:45:50Z",
    "timestamp": 1027763150000
  },
  "page": "1540-1543",
  "source": "Crossref",
  "is-referenced-by-count": 185,
  "title": "The Gelation of CO\n            <sub>2</sub>\n            : A Sustainable Route to the Creation of Microcellular Materials",
  "prefix": "10.1126",
  "volume": "286",
  "author": [
    {
      "given": "C.",
      "family": "Shi",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA."
        }
      ]
    },
    {
      "given": "Z.",
      "family": "Huang",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA."
        }
      ]
    },
    {
      "given": "S.",
      "family": "Kilic",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA."
        }
      ]
    },
    {
      "given": "J.",
      "family": "Xu",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA."
        }
      ]
    },
    {
      "given": "R. M.",
      "family": "Enick",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA."
        }
      ]
    },
    {
      "given": "E. J.",
      "family": "Beckman",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA."
        }
      ]
    },
    {
      "given": "A. J.",
      "family": "Carr",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, Yale University, New Haven, CT 06520, USA."
        }
      ]
    },
    {
      "given": "R. E.",
      "family": "Melendez",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, Yale University, New Haven, CT 06520, USA."
        }
      ]
    },
    {
      "given": "A. D.",
      "family": "Hamilton",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, Yale University, New Haven, CT 06520, USA."
        }
      ]
    }
  ],
  "member": "221",
  "reference": [
    {
      "key": "e_1_3_1_2_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.257.5072.945"
    },
    {
      "key": "e_1_3_1_2_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ma960764s"
    },
    {
      "key": "e_1_3_1_2_4",
      "doi-asserted-by": "crossref",
      "unstructured": "; M. L. O'Neill et al. Macromolecules 30 5050 (1997).",
      "DOI": "10.1021/ma9616930"
    },
    {
      "key": "e_1_3_1_3_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr970037a"
    },
    {
      "key": "e_1_3_1_3_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ie980738d"
    },
    {
      "key": "e_1_3_1_3_4",
      "doi-asserted-by": "crossref",
      "unstructured": "; Industr. Eng. Chem. Res. 38 2833 (1999).",
      "DOI": "10.1021/ie9807396"
    },
    {
      "key": "e_1_3_1_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr970040u"
    },
    {
      "key": "e_1_3_1_5_2",
      "first-page": "236",
      "volume": "5",
      "author": "Super M.",
      "year": "1997",
      "unstructured": "Super M., Beckman E. J., Trends Polym. Sci. 5, 236 (1997);",
      "journal-title": "Trends Polym. Sci."
    },
    {
      "key": "e_1_3_1_5_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0010-8545(95)01232-X"
    },
    {
      "key": "e_1_3_1_6_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/la00011a014"
    },
    {
      "key": "e_1_3_1_7_2",
      "unstructured": "D. Klempner and K. C. Frisch Polymeric Foams (Hanser New York 1991)."
    },
    {
      "key": "e_1_3_1_8_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pen.760341407"
    },
    {
      "key": "e_1_3_1_8_3",
      "unstructured": "; Polym. Eng. Sci. 14 1148 (1994)."
    },
    {
      "key": "e_1_3_1_9_2",
      "doi-asserted-by": "crossref",
      "unstructured": "K. Hanabusa K Okui K. Karaki T. Koyama H. Shirai J. Chem. Soc. Chem. Commun. 1992 1371;",
      "DOI": "10.1039/c39920001371"
    },
    {
      "key": "e_1_3_1_9_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1073/pnas.90.1.163"
    },
    {
      "key": "e_1_3_1_10_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ma00120a036"
    },
    {
      "key": "e_1_3_1_10_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ma951001s"
    },
    {
      "key": "e_1_3_1_11_2",
      "doi-asserted-by": "crossref",
      "unstructured": "U. Maitra et al. Chem. Commun. 1999 595.",
      "DOI": "10.1039/a809821b"
    },
    {
      "key": "e_1_3_1_12_2",
      "unstructured": "J. R. Fredericks and A. D. Hamilton in Comprehensive Supramolecular Chemistry J. P. Sauvage and M. W. Hosseini Eds. (Pergamon Oxford 1996) vol. 9 pp. 565\u2013594."
    },
    {
      "key": "e_1_3_1_13_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00137a007"
    },
    {
      "key": "e_1_3_1_13_3",
      "unstructured": "; A. T. Ung R. Bishop D. C. Craig I. G. Dance M. L. Scudder J. Chem. Soc. Chem. Commun. 1991 1012."
    },
    {
      "key": "e_1_3_1_14_2",
      "unstructured": "The bisurea gelling agents were prepared by esterification of N -butoxycarbonyl (BOC)-aspartic acid in dichloromethane with 1-[3-(dimethylamino)propyl]-3-ethylcarbondiimide hydrochloride (EDCI) 4-(dimethylamino)pyridine (DMAP) and 1 H 1 H 2 H 2 H -perfluorodecanol followed by deprotection with trifluoroacetic acid/CH 2 Cl 2 (50:50) and reaction with the appropriate mono- or bis-isocyanates in CH 2 Cl 2 with excess triethylamine. The resultant bisureas were filtered off and washed with CH 2 Cl 2 1% aqueous HCl water and more CH 2 Cl 2 . All compounds gave spectroscopic characteristics consistent with their structure and were shown to be >95% pure. For more details of the synthesis of fluorinated aspartate bisureas and ureas see Science Online (www.sciencemag.org/feature/data/1044209.shl)."
    },
    {
      "key": "e_1_3_1_15_2",
      "unstructured": "Foam samples were fractured sputter-coated with gold then analyzed by SEM as described ["
    },
    {
      "key": "e_1_3_1_15_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pen.10640"
    },
    {
      "key": "e_1_3_1_15_4",
      "unstructured": "]. Sizes given throughout this report are average diameters as generated from these analyses of SEM images."
    },
    {
      "key": "e_1_3_1_16_2",
      "unstructured": "Monomers (styrene N N -dimethyl amino ethyl methacrylate n -hexyl acrylate 1 H 1 H 2 H 2 H -perfluorodecyl acrylate; Aldrich) were purified using conventional procedures (washing to remove inhibitors drying vacuum distillation as appropriate). Copolymers were prepared via bulk polymerization at 65\u00b0C using azobisisobutyronitrile (AIBN) (0.2 mol % recrystallized from methanol). Copolymers were purified via dissolution in 1 1 2-trichloroethane or perfluoromethyl cyclohexane followed by precipitation into methanol. Copolymer content was quantified using 1 H nuclear magnetic resonance. The aspartate methacrylate monomer was prepared using the scheme shown in (13) and 2-isocyanato ethyl methacrylate (Aldrich). Styrene-fluorinated acrylate copolymers were sulfonated using an SO 3 /acetic anhydride complex (acetyl sulfate)."
    },
    {
      "key": "e_1_3_1_17_2",
      "unstructured": "We are developing CO 2 -philic hydrocarbons to form the building blocks for the next generation of such agents (E. J. Beckman Design of CO 2 -Philic Hydrocarbons paper presented at the Engineering Foundation Conference on Supercritical Fluids in Materials Processing and Synthesis Davos Switzerland September\u2013October 1999)."
    },
    {
      "key": "e_1_3_1_18_2",
      "unstructured": "Supported by the U.S. Department of Energy (National Petroleum Technology Office contract DE-AC26-98BC15108) NSF (grants CTS-9870925 and CHE-9817240) Air Products & Chemicals and Cabot Oil & Gas."
    }
  ],
  "container-title": "Science",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://www.science.org/doi/pdf/10.1126/science.286.5444.1540",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        1,
        13
      ]
    ],
    "date-time": "2024-01-13T10:03:33Z",
    "timestamp": 1705140213000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://www.science.org/doi/10.1126/science.286.5444.1540"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1999,
        11,
        19
      ]
    ]
  },
  "references-count": 28,
  "journal-issue": {
    "issue": "5444",
    "published-print": {
      "date-parts": [
        [
          1999,
          11,
          19
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1126/science.286.5444.1540"
  ],
  "URL": "http://dx.doi.org/10.1126/science.286.5444.1540",
  "relation": {},
  "ISSN": [
    "0036-8075",
    "1095-9203"
  ],
  "subject": [],
  "container-title-short": "Science",
  "published": {
    "date-parts": [
      [
        1999,
        11,
        19
      ]
    ]
  }
}