One-pot synthesis of branched poly(styrene-divinylbenzene) suspension polymerized resins

S. Durie, K. Jerabek, C. Mason, D.C. Sherrington

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Spherical particulate polymer resins have become ubiquitous support materials in both solid phase synthesis and in the heterogenizing of homogeneous catalysts. In the former case lightly cross-linked so-called gel-type species are favored whereas in the latter so-called macroporous species are finding increasing utility. Despite the success of these materials, mass transfer limitations can lead to poor performance, and in this context there is still a need for improvement in the morphology of these species. One potential advancement would be resins with a highly branched backbone architecture since such a molecular level structure would in principle generate a large proportion of functional groups near chain ends or at least on mobile chains anchored to the main matrix by a single linkage. In addition a high level of chain ends relative to that in conventional resins might lead to novel solvation characteristics. We now report a facile one-pot suspension polymerization which allows synthesis of both branched gel-type and branched macroporous resins. The procedure is an adaptation of our earlier reported methodology for producing soluble branched vinyl polymers and involves use of controlled levels of a free radical chain transfer agent which functions in effect to limit chain growth and in combination with a cross-linking comonomer leads essentially to branched backbone architectures. The system styrene/divinylbenzene/dodecanethiol has been probed in detail, and a range of experimental conditions have been identified which lead to branched gel-type and branched macroporous resins. The structure of these has been evaluated from solvent swelling data, dry state surface area measurements, and inverse size exclusion chromatographic data.
LanguageEnglish
Pages9665-9672
Number of pages7
JournalMacromolecules
Volume35
Issue number26
DOIs
Publication statusPublished - 17 Dec 2002

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Styrene
Suspensions
Resins
divinyl benzene
Gels
Polymers
Solvation
Surface states
Free radicals
Functional groups
Free Radicals
Swelling
Mass transfer
Polymerization
Amberlite XAD-2 resin
Catalysts

Keywords

  • HYPERBRANCHED POLYMERS
  • COPOLYMERS

Cite this

Durie, S. ; Jerabek, K. ; Mason, C. ; Sherrington, D.C. / One-pot synthesis of branched poly(styrene-divinylbenzene) suspension polymerized resins. In: Macromolecules. 2002 ; Vol. 35, No. 26. pp. 9665-9672.
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Durie, S, Jerabek, K, Mason, C & Sherrington, DC 2002, 'One-pot synthesis of branched poly(styrene-divinylbenzene) suspension polymerized resins' Macromolecules, vol. 35, no. 26, pp. 9665-9672. https://doi.org/10.1021/ma0209794

One-pot synthesis of branched poly(styrene-divinylbenzene) suspension polymerized resins. / Durie, S.; Jerabek, K.; Mason, C.; Sherrington, D.C.

In: Macromolecules, Vol. 35, No. 26, 17.12.2002, p. 9665-9672.

Research output: Contribution to journalArticle

TY - JOUR

T1 - One-pot synthesis of branched poly(styrene-divinylbenzene) suspension polymerized resins

AU - Durie, S.

AU - Jerabek, K.

AU - Mason, C.

AU - Sherrington, D.C.

PY - 2002/12/17

Y1 - 2002/12/17

N2 - Spherical particulate polymer resins have become ubiquitous support materials in both solid phase synthesis and in the heterogenizing of homogeneous catalysts. In the former case lightly cross-linked so-called gel-type species are favored whereas in the latter so-called macroporous species are finding increasing utility. Despite the success of these materials, mass transfer limitations can lead to poor performance, and in this context there is still a need for improvement in the morphology of these species. One potential advancement would be resins with a highly branched backbone architecture since such a molecular level structure would in principle generate a large proportion of functional groups near chain ends or at least on mobile chains anchored to the main matrix by a single linkage. In addition a high level of chain ends relative to that in conventional resins might lead to novel solvation characteristics. We now report a facile one-pot suspension polymerization which allows synthesis of both branched gel-type and branched macroporous resins. The procedure is an adaptation of our earlier reported methodology for producing soluble branched vinyl polymers and involves use of controlled levels of a free radical chain transfer agent which functions in effect to limit chain growth and in combination with a cross-linking comonomer leads essentially to branched backbone architectures. The system styrene/divinylbenzene/dodecanethiol has been probed in detail, and a range of experimental conditions have been identified which lead to branched gel-type and branched macroporous resins. The structure of these has been evaluated from solvent swelling data, dry state surface area measurements, and inverse size exclusion chromatographic data.

AB - Spherical particulate polymer resins have become ubiquitous support materials in both solid phase synthesis and in the heterogenizing of homogeneous catalysts. In the former case lightly cross-linked so-called gel-type species are favored whereas in the latter so-called macroporous species are finding increasing utility. Despite the success of these materials, mass transfer limitations can lead to poor performance, and in this context there is still a need for improvement in the morphology of these species. One potential advancement would be resins with a highly branched backbone architecture since such a molecular level structure would in principle generate a large proportion of functional groups near chain ends or at least on mobile chains anchored to the main matrix by a single linkage. In addition a high level of chain ends relative to that in conventional resins might lead to novel solvation characteristics. We now report a facile one-pot suspension polymerization which allows synthesis of both branched gel-type and branched macroporous resins. The procedure is an adaptation of our earlier reported methodology for producing soluble branched vinyl polymers and involves use of controlled levels of a free radical chain transfer agent which functions in effect to limit chain growth and in combination with a cross-linking comonomer leads essentially to branched backbone architectures. The system styrene/divinylbenzene/dodecanethiol has been probed in detail, and a range of experimental conditions have been identified which lead to branched gel-type and branched macroporous resins. The structure of these has been evaluated from solvent swelling data, dry state surface area measurements, and inverse size exclusion chromatographic data.

KW - HYPERBRANCHED POLYMERS

KW - COPOLYMERS

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JF - Macromolecules

SN - 0024-9297

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ER -