"Click" synthesis of thermally stable au nanoparticles with highly grafted polymer shell and control of their behavior in polymer matrix

Jongmin Lim, Hyunseung Yang, Kwanyeol Paek, Chul Hee Cho, Seyong Kim, Joona Bang, Bumjoon J. Kim

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Thermally stable core-shell gold nanoparticles (Au NPs) with highly grafted polymer shells were synthesized by combining reversible addition-fragmentation transfer (RAFT) polymerization and click chemistry of copper-catalyzed azide-alkyne cycloaddition (CuAAC). First, alkyne-terminated poly(4-benzylchloride-b-styrene) (alkyne-PSCl-b-PS) was prepared from the alkyne-terminated RAFT agent. Then, an alkyne-PSCl-b-PS chain was coupled to azide-functionalized Au NPs via the CuAAC reaction. Careful characterization using FT-IR, UV-Vis, and TGA showed that PSCl-b-PS chains were successfully grafted onto the Au NP surface with high grafting density. Finally, azide groups were introduced to PSCl-b-PS chains on the Au NP surface to produce thermally stable Au NPs with crosslinkable polymer shell (Au-PSN3-b-PS 1). As the control sample, PS-b-PSN3-coated Au NPs (Au-PSN3-b-PS 2) were made by the conventional "grafting to" approach. The grafting density of polymer chains on Au-PSN3-b-PS 1 was found to be much higher than that on Au-PSN3-b-PS 2. To demonstrate the importance of having the highly packed polymer shell on the nanoparticles, Au-PSN 3-b-PS 1 particles were added into the PS and PS-b-poly(2- vinylpyridine) matrix, respectively. Consequently, it was found that Au-PSN 3-b-PS 1 nanoparticles were well dispersed in the PS matrix and PS-b-P2VP matrix without any aggregation even after annealing at 220 °C for 2 days. Our simple and powerful approach could be easily extended to design other core-shell inorganic nanoparticles.

Original languageEnglish
Pages (from-to)3464-3474
Number of pages11
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume49
Issue number16
DOIs
Publication statusPublished - 2011 Aug 15

Fingerprint

Alkynes
Polymer matrix
Polymers
Azides
Nanoparticles
Cycloaddition
Styrene
Agglomeration
Gold
Polymerization
Annealing
Copper

Keywords

  • block copolymers
  • click chemistry
  • grafting density
  • nanocomposites
  • nanoparticles
  • polymer coated Au nanoparticles
  • reversible addition fragmentation chain transfer (RAFT)

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

"Click" synthesis of thermally stable au nanoparticles with highly grafted polymer shell and control of their behavior in polymer matrix. / Lim, Jongmin; Yang, Hyunseung; Paek, Kwanyeol; Cho, Chul Hee; Kim, Seyong; Bang, Joona; Kim, Bumjoon J.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 49, No. 16, 15.08.2011, p. 3464-3474.

Research output: Contribution to journalArticle

Lim, Jongmin ; Yang, Hyunseung ; Paek, Kwanyeol ; Cho, Chul Hee ; Kim, Seyong ; Bang, Joona ; Kim, Bumjoon J. / "Click" synthesis of thermally stable au nanoparticles with highly grafted polymer shell and control of their behavior in polymer matrix. In: Journal of Polymer Science, Part A: Polymer Chemistry. 2011 ; Vol. 49, No. 16. pp. 3464-3474.
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AU - Cho, Chul Hee

AU - Kim, Seyong

AU - Bang, Joona

AU - Kim, Bumjoon J.

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AB - Thermally stable core-shell gold nanoparticles (Au NPs) with highly grafted polymer shells were synthesized by combining reversible addition-fragmentation transfer (RAFT) polymerization and click chemistry of copper-catalyzed azide-alkyne cycloaddition (CuAAC). First, alkyne-terminated poly(4-benzylchloride-b-styrene) (alkyne-PSCl-b-PS) was prepared from the alkyne-terminated RAFT agent. Then, an alkyne-PSCl-b-PS chain was coupled to azide-functionalized Au NPs via the CuAAC reaction. Careful characterization using FT-IR, UV-Vis, and TGA showed that PSCl-b-PS chains were successfully grafted onto the Au NP surface with high grafting density. Finally, azide groups were introduced to PSCl-b-PS chains on the Au NP surface to produce thermally stable Au NPs with crosslinkable polymer shell (Au-PSN3-b-PS 1). As the control sample, PS-b-PSN3-coated Au NPs (Au-PSN3-b-PS 2) were made by the conventional "grafting to" approach. The grafting density of polymer chains on Au-PSN3-b-PS 1 was found to be much higher than that on Au-PSN3-b-PS 2. To demonstrate the importance of having the highly packed polymer shell on the nanoparticles, Au-PSN 3-b-PS 1 particles were added into the PS and PS-b-poly(2- vinylpyridine) matrix, respectively. Consequently, it was found that Au-PSN 3-b-PS 1 nanoparticles were well dispersed in the PS matrix and PS-b-P2VP matrix without any aggregation even after annealing at 220 °C for 2 days. Our simple and powerful approach could be easily extended to design other core-shell inorganic nanoparticles.

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KW - nanocomposites

KW - nanoparticles

KW - polymer coated Au nanoparticles

KW - reversible addition fragmentation chain transfer (RAFT)

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