DOI: 10.1002/macp.1982.021830811. Synthesis and free radical ring‐opening polymerization of 2‐methylene‐4‐phenyl‐1,3‐dioxolane

Synthesis and free radical ring‐opening polymerization of 2‐methylene‐4‐phenyl‐1,3‐dioxolane

10.1002/macp.1982.021830811

Crossref journal-article

Wiley

Die Makromolekulare Chemie (311)

Abstract

AbstractThe cyclic ketene acetal, 2‐methylene‐4‐phenyl‐1,3‐dioxolane (3), was shown to undergo free radical ring‐opening polymerization to produce the polyester, poly[γ‐(β‐phenyl)butyrolactone]. The monomer 3 was synthesized by an acetal exchange reaction of chloroacetaldehyde dimethyl acetal with styrene glycol in an 87% yield followed by dehydrochlorination of the resulting cis and trans‐2‐chloromethyl‐4‐phenyl‐1,3‐dioxolane (2) with potassium tert‐butoxide in tert‐butyl alcohol in a 70% yield. 3 was shown to undergo essentially quantitative free radical ring‐opening at all temperatures from 60–150°C and also nearly complete regioselective ring‐opening with cleavage to give the more highly stable secondary benzyl free radical. Even in free radical copolymerization with styrene, methyl methacrylate, vinyl acetate, or 4‐vinylpyridine, 3 gives essentially complete ring opening to introduce an ester groups into the backbone of the addition copolymer. The structures of the polymers were established by elemental analysis and 1H and 13C NMR spectroscopy.

Bibliography

Bailey, W. J., Wu, S., & Ni, Z. (1982). Synthesis and free radical ringâopening polymerization of 2âmethyleneâ4âphenylâ1,3âdioxolane. Die Makromolekulare Chemie, 183(8), 1913â1920. Portico.

Authors 3

William J. Bailey (first)
Shang‐Ren Wu (additional)
Zhende Ni (additional)

References 15 Referenced 119

10.1002/pol.1961.1204915209
10.1002/pol.1968.150060210
{'key': 'e_1_2_1_2_3', 'first-page': '1066', 'volume': '7', 'author': 'Linshansky I. S.', 'year': '1965', 'journal-title': 'Vysokomol. Soedin.'} / Vysokomol. Soedin. by Linshansky I. S. (1965)
10.1021/jo01339a068
10.1002/pol.1977.130151208
10.1002/pol.1975.130130401
10.1021/bk-1977-0059.ch004
10.1002/pol.1980.130180106
W. J.Bailey Z.Ni S.‐R.Wu J. Polym. Sci. Polym. Chem. Ed. in press
W. J.Bailey Z.Ni S.‐R.Wu Macromolecules in press
W. J.Bailey P. Y.Chen N.Yamazaki unpublished results
10.1021/ja01191a071
10.1016/0040-4020(78)89052-8
U. S. 3431281 (1969) Goodyear Tire and Rubber Co. inv.
{'key': 'e_1_2_1_11_3', 'first-page': '87789f', 'volume': '70', 'author': 'Sawaya A. R.', 'year': '1969', 'journal-title': 'Chem. Abstr.'} / Chem. Abstr. by Sawaya A. R. (1969)

Dates

Type	When
Created	22 years, 4 months ago (April 15, 2003, 7:41 p.m.)
Deposited	1 year, 9 months ago (Nov. 13, 2023, 12:58 p.m.)
Indexed	1 week ago (Aug. 20, 2025, 9:20 a.m.)
Issued	43 years ago (Aug. 10, 1982)
Published	43 years ago (Aug. 10, 1982)
Published Online	22 years, 5 months ago (March 12, 2003)
Published Print	43 years ago (Aug. 10, 1982)

Funders 0

None

BibTeX

@article{Bailey_1982, title={Synthesis and free radical ring‐opening polymerization of 2‐methylene‐4‐phenyl‐1,3‐dioxolane}, volume={183}, ISSN={0025-116X}, url={http://dx.doi.org/10.1002/macp.1982.021830811}, DOI={10.1002/macp.1982.021830811}, number={8}, journal={Die Makromolekulare Chemie}, publisher={Wiley}, author={Bailey, William J. and Wu, Shang‐Ren and Ni, Zhende}, year={1982}, month=aug, pages={1913–1920} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        8,
        20
      ]
    ],
    "date-time": "2025-08-20T13:20:17Z",
    "timestamp": 1755696017567
  },
  "reference-count": 15,
  "publisher": "Wiley",
  "issue": "8",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            2003,
            3,
            12
          ]
        ],
        "date-time": "2003-03-12T00:00:00Z",
        "timestamp": 1047427200000
      },
      "content-version": "vor",
      "delay-in-days": 7519,
      "URL": "http://onlinelibrary.wiley.com/termsAndConditions#vor"
    }
  ],
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        1982,
        8,
        10
      ]
    ]
  },
  "abstract": "<jats:title>Abstract</jats:title><jats:p>The cyclic ketene acetal, 2\u2010methylene\u20104\u2010phenyl\u20101,3\u2010dioxolane (<jats:bold>3</jats:bold>), was shown to undergo free radical ring\u2010opening polymerization to produce the polyester, poly[\u03b3\u2010(\u03b2\u2010phenyl)butyrolactone]. The monomer <jats:bold>3</jats:bold> was synthesized by an acetal exchange reaction of chloroacetaldehyde dimethyl acetal with styrene glycol in an 87% yield followed by dehydrochlorination of the resulting <jats:italic>cis</jats:italic> and <jats:italic>trans</jats:italic>\u20102\u2010chloromethyl\u20104\u2010phenyl\u20101,3\u2010dioxolane (<jats:bold>2</jats:bold>) with potassium <jats:italic>tert</jats:italic>\u2010butoxide in <jats:italic>tert</jats:italic>\u2010butyl alcohol in a 70% yield. <jats:bold>3</jats:bold> was shown to undergo essentially quantitative free radical ring\u2010opening at all temperatures from 60\u2013150\u00b0C and also nearly complete regioselective ring\u2010opening with cleavage to give the more highly stable secondary benzyl free radical. Even in free radical copolymerization with styrene, methyl methacrylate, vinyl acetate, or 4\u2010vinylpyridine, <jats:bold>3</jats:bold> gives essentially complete ring opening to introduce an ester groups into the backbone of the addition copolymer. The structures of the polymers were established by elemental analysis and <jats:sup>1</jats:sup>H and <jats:sup>13</jats:sup>C NMR spectroscopy.</jats:p>",
  "DOI": "10.1002/macp.1982.021830811",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2003,
        4,
        15
      ]
    ],
    "date-time": "2003-04-15T23:41:48Z",
    "timestamp": 1050450108000
  },
  "page": "1913-1920",
  "source": "Crossref",
  "is-referenced-by-count": 119,
  "title": "Synthesis and free radical ring\u2010opening polymerization of 2\u2010methylene\u20104\u2010phenyl\u20101,3\u2010dioxolane",
  "prefix": "10.1002",
  "volume": "183",
  "author": [
    {
      "given": "William J.",
      "family": "Bailey",
      "sequence": "first",
      "affiliation": []
    },
    {
      "given": "Shang\u2010Ren",
      "family": "Wu",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "Zhende",
      "family": "Ni",
      "sequence": "additional",
      "affiliation": []
    }
  ],
  "member": "311",
  "published-online": {
    "date-parts": [
      [
        2003,
        3,
        12
      ]
    ]
  },
  "reference": [
    {
      "key": "e_1_2_1_1_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1961.1204915209"
    },
    {
      "key": "e_1_2_1_2_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1968.150060210"
    },
    {
      "key": "e_1_2_1_2_3",
      "first-page": "1066",
      "volume": "7",
      "author": "Linshansky I. S.",
      "year": "1965",
      "journal-title": "Vysokomol. Soedin."
    },
    {
      "key": "e_1_2_1_2_4",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/jo01339a068"
    },
    {
      "key": "e_1_2_1_2_5",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1977.130151208"
    },
    {
      "key": "e_1_2_1_3_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1975.130130401"
    },
    {
      "key": "e_1_2_1_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/bk-1977-0059.ch004"
    },
    {
      "key": "e_1_2_1_5_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/pol.1980.130180106"
    },
    {
      "key": "e_1_2_1_6_2",
      "unstructured": "W. J.Bailey Z.Ni S.\u2010R.Wu J. Polym. Sci. Polym. Chem. Ed. in press"
    },
    {
      "key": "e_1_2_1_7_2",
      "unstructured": "W. J.Bailey Z.Ni S.\u2010R.Wu Macromolecules in press"
    },
    {
      "key": "e_1_2_1_8_2",
      "unstructured": "W. J.Bailey P. Y.Chen N.Yamazaki unpublished results"
    },
    {
      "key": "e_1_2_1_9_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja01191a071"
    },
    {
      "key": "e_1_2_1_10_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0040-4020(78)89052-8"
    },
    {
      "key": "e_1_2_1_11_2",
      "unstructured": "U. S. 3431281 (1969) Goodyear Tire and Rubber Co. inv."
    },
    {
      "key": "e_1_2_1_11_3",
      "first-page": "87789f",
      "volume": "70",
      "author": "Sawaya A. R.",
      "year": "1969",
      "journal-title": "Chem. Abstr."
    }
  ],
  "container-title": "Die Makromolekulare Chemie",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fmacp.1982.021830811",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/pdf/10.1002/macp.1982.021830811",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2023,
        11,
        13
      ]
    ],
    "date-time": "2023-11-13T17:58:12Z",
    "timestamp": 1699898292000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://onlinelibrary.wiley.com/doi/10.1002/macp.1982.021830811"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1982,
        8,
        10
      ]
    ]
  },
  "references-count": 15,
  "journal-issue": {
    "issue": "8",
    "published-print": {
      "date-parts": [
        [
          1982,
          8,
          10
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1002/macp.1982.021830811"
  ],
  "URL": "http://dx.doi.org/10.1002/macp.1982.021830811",
  "relation": {},
  "ISSN": [
    "0025-116X",
    "0025-116X"
  ],
  "subject": [],
  "container-title-short": "Makromol. Chem.",
  "published": {
    "date-parts": [
      [
        1982,
        8,
        10
      ]
    ]
  }
}