Aqueous cationic olefin polymerization using tris(pentafluorophenyl)gallium and aluminum

Robert Timothy Mathers, Stewart P. Lewis

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Tris(pentafluorophenyl)gallium (3) and aluminum (7) are active coinitiators for the production of medium-high molecular weight (MW) polymers of styrene and isobutene (IB) under aqueous reaction conditions. Strong Brønsted acids formed in situ by reaction of these coinitiators with background moisture present in the monomer droplet (5 and 8, respectively) are believed to be responsible for inducing cationic polymerization of these monomers. Of the two, 7 is the most active for IB polymerization in both aqueous media and anhydrous aliphatic solvents. These results are in contradistinction to tris(pentafluorophenyl)boron (2), which is incapable of polymerizing IB in aqueous or aliphatic media. The MWs of the polyisobutenes (PIBs) produced under aqueous conditions by either coinitiator greatly exceed those formed under similar reaction conditions by the strongly acidic chelating diborane (1,2-C 6F 4[B(C 6F 5) 2] 2, 1) or diborole (1,2-C 6F 4[9-BC 12F 8] 2, 6). Both 3 and 7 are readily synthesized from the corresponding Group 13 halide compounds in conjunction with bis(pentafluorophenyl)zinc (4). Aqueous polymerization of IB dissolved in aliphatic solvents with 3 or 7 can yield PIBs with relatively narrow polydispersities.

Original languageEnglish (US)
Pages (from-to)1325-1332
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume50
Issue number7
DOIs
StatePublished - Apr 1 2012

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Gallium
Alkenes
Aluminum
Olefins
Monomers
Polymerization
Cationic polymerization
Polydispersity
Chelation
Boron
Styrene
Zinc
Moisture
Molecular weight
Acids
Polymers
isobutylene

All Science Journal Classification (ASJC) codes

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

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title = "Aqueous cationic olefin polymerization using tris(pentafluorophenyl)gallium and aluminum",
abstract = "Tris(pentafluorophenyl)gallium (3) and aluminum (7) are active coinitiators for the production of medium-high molecular weight (MW) polymers of styrene and isobutene (IB) under aqueous reaction conditions. Strong Br{\o}nsted acids formed in situ by reaction of these coinitiators with background moisture present in the monomer droplet (5 and 8, respectively) are believed to be responsible for inducing cationic polymerization of these monomers. Of the two, 7 is the most active for IB polymerization in both aqueous media and anhydrous aliphatic solvents. These results are in contradistinction to tris(pentafluorophenyl)boron (2), which is incapable of polymerizing IB in aqueous or aliphatic media. The MWs of the polyisobutenes (PIBs) produced under aqueous conditions by either coinitiator greatly exceed those formed under similar reaction conditions by the strongly acidic chelating diborane (1,2-C 6F 4[B(C 6F 5) 2] 2, 1) or diborole (1,2-C 6F 4[9-BC 12F 8] 2, 6). Both 3 and 7 are readily synthesized from the corresponding Group 13 halide compounds in conjunction with bis(pentafluorophenyl)zinc (4). Aqueous polymerization of IB dissolved in aliphatic solvents with 3 or 7 can yield PIBs with relatively narrow polydispersities.",
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Aqueous cationic olefin polymerization using tris(pentafluorophenyl)gallium and aluminum. / Mathers, Robert Timothy; Lewis, Stewart P.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 50, No. 7, 01.04.2012, p. 1325-1332.

Research output: Contribution to journalArticle

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AB - Tris(pentafluorophenyl)gallium (3) and aluminum (7) are active coinitiators for the production of medium-high molecular weight (MW) polymers of styrene and isobutene (IB) under aqueous reaction conditions. Strong Brønsted acids formed in situ by reaction of these coinitiators with background moisture present in the monomer droplet (5 and 8, respectively) are believed to be responsible for inducing cationic polymerization of these monomers. Of the two, 7 is the most active for IB polymerization in both aqueous media and anhydrous aliphatic solvents. These results are in contradistinction to tris(pentafluorophenyl)boron (2), which is incapable of polymerizing IB in aqueous or aliphatic media. The MWs of the polyisobutenes (PIBs) produced under aqueous conditions by either coinitiator greatly exceed those formed under similar reaction conditions by the strongly acidic chelating diborane (1,2-C 6F 4[B(C 6F 5) 2] 2, 1) or diborole (1,2-C 6F 4[9-BC 12F 8] 2, 6). Both 3 and 7 are readily synthesized from the corresponding Group 13 halide compounds in conjunction with bis(pentafluorophenyl)zinc (4). Aqueous polymerization of IB dissolved in aliphatic solvents with 3 or 7 can yield PIBs with relatively narrow polydispersities.

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