DOI: 10.1126/science.272.5263.866. Polymers with Very Low Polydispersities from Atom Transfer Radical Polymerization

Polymers with Very Low Polydispersities from Atom Transfer Radical Polymerization

10.1126/science.272.5263.866

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

A radical polymerization process that yields well-defined polymers normally obtained only through anionic polymerizations is reported. Atom transfer radical polymerizations of styrene were conducted with several solubilizing ligands for the copper(I) halides: 4,4′-di- tert -butyl, 4,4′-di- n -heptyl, and 4,4′-di-(5-nonyl)-2,2′-dipyridyl. The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities (ratio of the weight-average to number-average molecular weights of 1.04 to 1.05). Similar results were obtained for the polymerization of acrylates.

Bibliography

Patten, T. E., Xia, J., Abernathy, T., & Matyjaszewski, K. (1996). Polymers with Very Low Polydispersities from Atom Transfer Radical Polymerization. Science, 272(5263), 866â868.

Authors 4

Timothy E. Patten (first)
Jianhui Xia (additional)
Teresa Abernathy (additional)
Krzysztof Matyjaszewski (additional)

References 16 Referenced 821

GAYNOR S.G., CONTROLLED RADICAL POLYMERIZATION BY DEGENERATIVE TRANSFER - EFFECT OF THE STRUCTURE OF THE TRANSFER AGENT, MACROMOLECULES 28, 8051 (1995). (10.1021/ma00128a012) / MACROMOLECULES / CONTROLLED RADICAL POLYMERIZATION BY DEGENERATIVE TRANSFER - EFFECT OF THE STRUCTURE OF THE TRANSFER AGENT by GAYNOR S.G. (1995)
GEORGES M.K., NARROW POLYDISPERSITY POLYSTYRENE BY A FREE-RADICAL POLYMERIZATION PROCESS - RATE ENHANCEMENT, MACROMOLECULES 27, 7228 (1994). (10.1021/ma00102a039) / MACROMOLECULES / NARROW POLYDISPERSITY POLYSTYRENE BY A FREE-RADICAL POLYMERIZATION PROCESS - RATE ENHANCEMENT by GEORGES M.K. (1994)
GRESZTA D, LIVING RADICAL POLYMERIZATION .1. POSSIBILITIES AND LIMITATIONS, MACROMOLECULES 27, 638 (1994). (10.1021/ma00081a002) / MACROMOLECULES / LIVING RADICAL POLYMERIZATION .1. POSSIBILITIES AND LIMITATIONS by GRESZTA D (1994)
HADDA T.B., POLYHEDRON 7, 575 (1988). (10.1016/S0277-5387(00)86335-4) / POLYHEDRON by HADDA T.B. (1988)
HARWOOD H.J., POLYM PREPR AM CHEM 35, 549 (1994). / POLYM PREPR AM CHEM by HARWOOD H.J. (1994)
KATO M, POLYMERIZATION OF METHYL-METHACRYLATE WITH THE CARBON-TETRACHLORIDE DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) METHYLALUMINUM BIS(2,6-DI-TERT-BUTYLPHENOXIDE) INITIATING SYSTEM - POSSIBILITY OF LIVING RADICAL POLYMERIZATION, MACROMOLECULES 28, 1721 (1995). (10.1021/ma00109a056) / MACROMOLECULES / POLYMERIZATION OF METHYL-METHACRYLATE WITH THE CARBON-TETRACHLORIDE DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) METHYLALUMINUM BIS(2,6-DI-TERT-BUTYLPHENOXIDE) INITIATING SYSTEM - POSSIBILITY OF LIVING RADICAL POLYMERIZATION by KATO M (1995)
LEHN J.M., ANGEW CHEM INT EDIT 32, 703 (1993). (10.1002/anie.199307031) / ANGEW CHEM INT EDIT by LEHN J.M. (1993)
MARDARE D, LIVING RADICAL POLYMERIZATION OF VINYL-ACETATE, MACROMOLECULES 27, 645 (1994). (10.1021/ma00081a003) / MACROMOLECULES / LIVING RADICAL POLYMERIZATION OF VINYL-ACETATE by MARDARE D (1994)
MATYJASZEWSKI K unpublished data.
RIZZARDO E, CHEM AUST 54, 32 (1987). / CHEM AUST by RIZZARDO E (1987)
SZWARC M, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 78, 2657 (1956). / JOURNAL OF THE AMERICAN CHEMICAL SOCIETY by SZWARC M (1956)
SZWARC M, LIVING POLYMERS, NATURE 178, 1168 (1956). (10.1038/1781168a0) / NATURE / LIVING POLYMERS by SZWARC M (1956)
WANG J.S., CONTROLLED LIVING RADICAL POLYMERIZATION - ATOM-TRANSFER RADICAL POLYMERIZATION IN THE PRESENCE OF TRANSITION-METAL COMPLEXES, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 117, 5614 (1995). (10.1021/ja00125a035) / JOURNAL OF THE AMERICAN CHEMICAL SOCIETY / CONTROLLED LIVING RADICAL POLYMERIZATION - ATOM-TRANSFER RADICAL POLYMERIZATION IN THE PRESENCE OF TRANSITION-METAL COMPLEXES by WANG J.S. (1995)
WANG J.S., CONTROLLED LIVING RADICAL POLYMERIZATION - HALOGEN ATOM-TRANSFER RADICAL POLYMERIZATION PROMOTED BY A CU(I)CU(II) REDOX PROCESS, MACROMOLECULES 28, 7901 (1995). (10.1021/ma00127a042) / MACROMOLECULES / CONTROLLED LIVING RADICAL POLYMERIZATION - HALOGEN ATOM-TRANSFER RADICAL POLYMERIZATION PROMOTED BY A CU(I)CU(II) REDOX PROCESS by WANG J.S. (1995)
WAYLAND B.B., LIVING RADICAL POLYMERIZATION OF ACRYLATES BY ORGANOCOBALT PORPHYRIN COMPLEXES, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 116, 7943 (1994). (10.1021/ja00096a080) / JOURNAL OF THE AMERICAN CHEMICAL SOCIETY / LIVING RADICAL POLYMERIZATION OF ACRYLATES BY ORGANOCOBALT PORPHYRIN COMPLEXES by WAYLAND B.B. (1994)
10.1126/science.251.4996.887

Dates

Type	When
Created	18 years, 9 months ago (Oct. 27, 2006, 2:30 p.m.)
Deposited	1 year, 7 months ago (Jan. 12, 2024, 4:51 p.m.)
Indexed	1 month, 3 weeks ago (July 1, 2025, 9:49 a.m.)
Issued	29 years, 3 months ago (May 10, 1996)
Published	29 years, 3 months ago (May 10, 1996)
Published Print	29 years, 3 months ago (May 10, 1996)

Funders 0

None

BibTeX

@article{Patten_1996, title={Polymers with Very Low Polydispersities from Atom Transfer Radical Polymerization}, volume={272}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.272.5263.866}, DOI={10.1126/science.272.5263.866}, number={5263}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Patten, Timothy E. and Xia, Jianhui and Abernathy, Teresa and Matyjaszewski, Krzysztof}, year={1996}, month=may, pages={866–868} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        7,
        1
      ]
    ],
    "date-time": "2025-07-01T13:49:05Z",
    "timestamp": 1751377745052
  },
  "reference-count": 16,
  "publisher": "American Association for the Advancement of Science (AAAS)",
  "issue": "5263",
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        1996,
        5,
        10
      ]
    ]
  },
  "abstract": "<jats:p>\n            A radical polymerization process that yields well-defined polymers normally obtained only through anionic polymerizations is reported. Atom transfer radical polymerizations of styrene were conducted with several solubilizing ligands for the copper(I) halides: 4,4\u2032-di-\n            <jats:italic>tert</jats:italic>\n            -butyl, 4,4\u2032-di-\n            <jats:italic>n</jats:italic>\n            -heptyl, and 4,4\u2032-di-(5-nonyl)-2,2\u2032-dipyridyl. The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities (ratio of the weight-average to number-average molecular weights of 1.04 to 1.05). Similar results were obtained for the polymerization of acrylates.\n          </jats:p>",
  "DOI": "10.1126/science.272.5263.866",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2006,
        10,
        27
      ]
    ],
    "date-time": "2006-10-27T18:30:41Z",
    "timestamp": 1161973841000
  },
  "page": "866-868",
  "source": "Crossref",
  "is-referenced-by-count": 821,
  "title": "Polymers with Very Low Polydispersities from Atom Transfer Radical Polymerization",
  "prefix": "10.1126",
  "volume": "272",
  "author": [
    {
      "given": "Timothy E.",
      "family": "Patten",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA."
        }
      ]
    },
    {
      "given": "Jianhui",
      "family": "Xia",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA."
        }
      ]
    },
    {
      "given": "Teresa",
      "family": "Abernathy",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA."
        }
      ]
    },
    {
      "given": "Krzysztof",
      "family": "Matyjaszewski",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA."
        }
      ]
    }
  ],
  "member": "221",
  "reference": [
    {
      "key": "e_1_2_1_2_2",
      "doi-asserted-by": "crossref",
      "first-page": "8051",
      "DOI": "10.1021/ma00128a012",
      "article-title": "CONTROLLED RADICAL POLYMERIZATION BY DEGENERATIVE TRANSFER - EFFECT OF THE STRUCTURE OF THE TRANSFER AGENT",
      "volume": "28",
      "author": "GAYNOR S.G.",
      "year": "1995",
      "unstructured": "GAYNOR S.G., CONTROLLED RADICAL POLYMERIZATION BY DEGENERATIVE TRANSFER - EFFECT OF THE STRUCTURE OF THE TRANSFER AGENT, MACROMOLECULES 28, 8051 (1995).",
      "journal-title": "MACROMOLECULES"
    },
    {
      "key": "e_1_2_1_3_2",
      "doi-asserted-by": "crossref",
      "first-page": "7228",
      "DOI": "10.1021/ma00102a039",
      "article-title": "NARROW POLYDISPERSITY POLYSTYRENE BY A FREE-RADICAL POLYMERIZATION PROCESS - RATE ENHANCEMENT",
      "volume": "27",
      "author": "GEORGES M.K.",
      "year": "1994",
      "unstructured": "GEORGES M.K., NARROW POLYDISPERSITY POLYSTYRENE BY A FREE-RADICAL POLYMERIZATION PROCESS - RATE ENHANCEMENT, MACROMOLECULES 27, 7228 (1994).",
      "journal-title": "MACROMOLECULES"
    },
    {
      "key": "e_1_2_1_4_2",
      "doi-asserted-by": "crossref",
      "first-page": "638",
      "DOI": "10.1021/ma00081a002",
      "article-title": "LIVING RADICAL POLYMERIZATION .1. POSSIBILITIES AND LIMITATIONS",
      "volume": "27",
      "author": "GRESZTA D",
      "year": "1994",
      "unstructured": "GRESZTA D, LIVING RADICAL POLYMERIZATION .1. POSSIBILITIES AND LIMITATIONS, MACROMOLECULES 27, 638 (1994).",
      "journal-title": "MACROMOLECULES"
    },
    {
      "key": "e_1_2_1_5_2",
      "doi-asserted-by": "crossref",
      "first-page": "575",
      "DOI": "10.1016/S0277-5387(00)86335-4",
      "volume": "7",
      "author": "HADDA T.B.",
      "year": "1988",
      "unstructured": "HADDA T.B., POLYHEDRON 7, 575 (1988).",
      "journal-title": "POLYHEDRON"
    },
    {
      "key": "e_1_2_1_6_2",
      "first-page": "549",
      "volume": "35",
      "author": "HARWOOD H.J.",
      "year": "1994",
      "unstructured": "HARWOOD H.J., POLYM PREPR AM CHEM 35, 549 (1994).",
      "journal-title": "POLYM PREPR AM CHEM"
    },
    {
      "key": "e_1_2_1_7_2",
      "doi-asserted-by": "crossref",
      "first-page": "1721",
      "DOI": "10.1021/ma00109a056",
      "article-title": "POLYMERIZATION OF METHYL-METHACRYLATE WITH THE CARBON-TETRACHLORIDE DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) METHYLALUMINUM BIS(2,6-DI-TERT-BUTYLPHENOXIDE) INITIATING SYSTEM - POSSIBILITY OF LIVING RADICAL POLYMERIZATION",
      "volume": "28",
      "author": "KATO M",
      "year": "1995",
      "unstructured": "KATO M, POLYMERIZATION OF METHYL-METHACRYLATE WITH THE CARBON-TETRACHLORIDE DICHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) METHYLALUMINUM BIS(2,6-DI-TERT-BUTYLPHENOXIDE) INITIATING SYSTEM - POSSIBILITY OF LIVING RADICAL POLYMERIZATION, MACROMOLECULES 28, 1721 (1995).",
      "journal-title": "MACROMOLECULES"
    },
    {
      "key": "e_1_2_1_8_2",
      "doi-asserted-by": "crossref",
      "first-page": "703",
      "DOI": "10.1002/anie.199307031",
      "volume": "32",
      "author": "LEHN J.M.",
      "year": "1993",
      "unstructured": "LEHN J.M., ANGEW CHEM INT EDIT 32, 703 (1993).",
      "journal-title": "ANGEW CHEM INT EDIT"
    },
    {
      "key": "e_1_2_1_9_2",
      "doi-asserted-by": "crossref",
      "first-page": "645",
      "DOI": "10.1021/ma00081a003",
      "article-title": "LIVING RADICAL POLYMERIZATION OF VINYL-ACETATE",
      "volume": "27",
      "author": "MARDARE D",
      "year": "1994",
      "unstructured": "MARDARE D, LIVING RADICAL POLYMERIZATION OF VINYL-ACETATE, MACROMOLECULES 27, 645 (1994).",
      "journal-title": "MACROMOLECULES"
    },
    {
      "key": "e_1_2_1_10_2",
      "unstructured": "MATYJASZEWSKI K unpublished data."
    },
    {
      "key": "e_1_2_1_11_2",
      "first-page": "32",
      "volume": "54",
      "author": "RIZZARDO E",
      "year": "1987",
      "unstructured": "RIZZARDO E, CHEM AUST 54, 32 (1987).",
      "journal-title": "CHEM AUST"
    },
    {
      "key": "e_1_2_1_12_2",
      "first-page": "2657",
      "volume": "78",
      "author": "SZWARC M",
      "year": "1956",
      "unstructured": "SZWARC M, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 78, 2657 (1956).",
      "journal-title": "JOURNAL OF THE AMERICAN CHEMICAL SOCIETY"
    },
    {
      "key": "e_1_2_1_13_2",
      "doi-asserted-by": "crossref",
      "first-page": "1168",
      "DOI": "10.1038/1781168a0",
      "article-title": "LIVING POLYMERS",
      "volume": "178",
      "author": "SZWARC M",
      "year": "1956",
      "unstructured": "SZWARC M, LIVING POLYMERS, NATURE 178, 1168 (1956).",
      "journal-title": "NATURE"
    },
    {
      "key": "e_1_2_1_14_2",
      "doi-asserted-by": "crossref",
      "first-page": "5614",
      "DOI": "10.1021/ja00125a035",
      "article-title": "CONTROLLED LIVING RADICAL POLYMERIZATION - ATOM-TRANSFER RADICAL POLYMERIZATION IN THE PRESENCE OF TRANSITION-METAL COMPLEXES",
      "volume": "117",
      "author": "WANG J.S.",
      "year": "1995",
      "unstructured": "WANG J.S., CONTROLLED LIVING RADICAL POLYMERIZATION - ATOM-TRANSFER RADICAL POLYMERIZATION IN THE PRESENCE OF TRANSITION-METAL COMPLEXES, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 117, 5614 (1995).",
      "journal-title": "JOURNAL OF THE AMERICAN CHEMICAL SOCIETY"
    },
    {
      "key": "e_1_2_1_15_2",
      "doi-asserted-by": "crossref",
      "first-page": "7901",
      "DOI": "10.1021/ma00127a042",
      "article-title": "CONTROLLED LIVING RADICAL POLYMERIZATION - HALOGEN ATOM-TRANSFER RADICAL POLYMERIZATION PROMOTED BY A CU(I)CU(II) REDOX PROCESS",
      "volume": "28",
      "author": "WANG J.S.",
      "year": "1995",
      "unstructured": "WANG J.S., CONTROLLED LIVING RADICAL POLYMERIZATION - HALOGEN ATOM-TRANSFER RADICAL POLYMERIZATION PROMOTED BY A CU(I)CU(II) REDOX PROCESS, MACROMOLECULES 28, 7901 (1995).",
      "journal-title": "MACROMOLECULES"
    },
    {
      "key": "e_1_2_1_16_2",
      "doi-asserted-by": "crossref",
      "first-page": "7943",
      "DOI": "10.1021/ja00096a080",
      "article-title": "LIVING RADICAL POLYMERIZATION OF ACRYLATES BY ORGANOCOBALT PORPHYRIN COMPLEXES",
      "volume": "116",
      "author": "WAYLAND B.B.",
      "year": "1994",
      "unstructured": "WAYLAND B.B., LIVING RADICAL POLYMERIZATION OF ACRYLATES BY ORGANOCOBALT PORPHYRIN COMPLEXES, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 116, 7943 (1994).",
      "journal-title": "JOURNAL OF THE AMERICAN CHEMICAL SOCIETY"
    },
    {
      "key": "e_1_2_1_17_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.251.4996.887"
    }
  ],
  "container-title": "Science",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://www.science.org/doi/pdf/10.1126/science.272.5263.866",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        1,
        12
      ]
    ],
    "date-time": "2024-01-12T21:51:59Z",
    "timestamp": 1705096319000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://www.science.org/doi/10.1126/science.272.5263.866"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1996,
        5,
        10
      ]
    ]
  },
  "references-count": 16,
  "journal-issue": {
    "issue": "5263",
    "published-print": {
      "date-parts": [
        [
          1996,
          5,
          10
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1126/science.272.5263.866"
  ],
  "URL": "http://dx.doi.org/10.1126/science.272.5263.866",
  "relation": {},
  "ISSN": [
    "0036-8075",
    "1095-9203"
  ],
  "subject": [],
  "container-title-short": "Science",
  "published": {
    "date-parts": [
      [
        1996,
        5,
        10
      ]
    ]
  }
}