Skip to main content
Journal cover image

Diblock copolymers, micelles, and shell-crosslinked nanoparticles containing poly(4-fluorostyrene): Tools for detailed analyses of nanostructured materials

Publication ,  Journal Article
Becker, ML; Remsen, EE; Wooley, KL
Published in: Journal of Polymer Science, Part A: Polymer Chemistry
December 1, 2001

Amphiphilic core-shell nanostructures containing 19F stable isotopic labels located regioselectively within the core domain were prepared by a combination of atom transfer radical polymerization (ATRP), supramolecular assembly, and condensation-based crosslinking. Homopolymers and diblock copolymers containing 4-fluorostyrene and methyl acrylate were prepared by ATRP, hydrolyzed, assembled into micelles, and converted into shell-crosslinked nanoparticles (SCKs) by covalent stabilization of the acrylic acid residues in the shell. The ATRP-based polymerizations, producing the homopolymers and diblock copolymers, were initiated by (1-bromoethyl)benzene in the presence of CuBr metal and employed N,N,N′,N″,N″-pentamethyldiethylenetriamine as the coordinating ligand for controlled polymerizations at 75-90°C for 1-3 h. Number-average molecular weights ranged from 2000 to 60,000 Da, and molecular weight distributions, generally less than 1.1 and 1.2, were achieved for the homopolymers and diblock copolymers, respectively. Methyl acrylate conversions as high as 70% were possible, without observable chain-chain coupling reactions or molecular weight distribution broadening, when bromoalkyl-terminated poly(4-fluorostyrene) was used as the macroinitiator. Poly(4-fluorostyrene), incorporated as the second segment in the diblock copolymer synthesis, was initiated from a bromoalkyl-terminated poly(methyl acrylate) macroinitiator. After hydrolysis of the poly(methyl acrylate) block segments, micelles were formed from the resulting amphiphilic block copolymers in aqueous solutions and were then stabilized by covalent intramicellar crosslinking throughout the poly(acrylic acid) shells to yield SCKs. The SCK nanostructures on solid substrates were visualized by atomic force microscopy and transmission electron microscopy. Dynamic light scattering was used to probe the effects of crosslinking on the resulting hydrodynamic diameters of nanoparticles in aqueous and buffered solutions. The presence of fluorine atoms in the diblock copolymers and resulting SCK nanostructures allowed for characterization by 19F NMR in addition to 1H NMR, 13C NMR, and IR spectroscopy.

Duke Scholars

Altmetric Attention Stats
Dimensions Citation Stats

Published In

Journal of Polymer Science, Part A: Polymer Chemistry

DOI

ISSN

0887-624X

Publication Date

December 1, 2001

Volume

39

Issue

23

Start / End Page

4152 / 4166

Related Subject Headings

  • Polymers
  • 3406 Physical chemistry
  • 3403 Macromolecular and materials chemistry
  • 0912 Materials Engineering
  • 0306 Physical Chemistry (incl. Structural)
  • 0303 Macromolecular and Materials Chemistry
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Becker, M. L., Remsen, E. E., & Wooley, K. L. (2001). Diblock copolymers, micelles, and shell-crosslinked nanoparticles containing poly(4-fluorostyrene): Tools for detailed analyses of nanostructured materials. Journal of Polymer Science, Part A: Polymer Chemistry, 39(23), 4152–4166. https://doi.org/10.1002/pola.10070
Becker, M. L., E. E. Remsen, and K. L. Wooley. “Diblock copolymers, micelles, and shell-crosslinked nanoparticles containing poly(4-fluorostyrene): Tools for detailed analyses of nanostructured materials.” Journal of Polymer Science, Part A: Polymer Chemistry 39, no. 23 (December 1, 2001): 4152–66. https://doi.org/10.1002/pola.10070.
Becker ML, Remsen EE, Wooley KL. Diblock copolymers, micelles, and shell-crosslinked nanoparticles containing poly(4-fluorostyrene): Tools for detailed analyses of nanostructured materials. Journal of Polymer Science, Part A: Polymer Chemistry. 2001 Dec 1;39(23):4152–66.
Becker, M. L., et al. “Diblock copolymers, micelles, and shell-crosslinked nanoparticles containing poly(4-fluorostyrene): Tools for detailed analyses of nanostructured materials.” Journal of Polymer Science, Part A: Polymer Chemistry, vol. 39, no. 23, Dec. 2001, pp. 4152–66. Scopus, doi:10.1002/pola.10070.
Becker ML, Remsen EE, Wooley KL. Diblock copolymers, micelles, and shell-crosslinked nanoparticles containing poly(4-fluorostyrene): Tools for detailed analyses of nanostructured materials. Journal of Polymer Science, Part A: Polymer Chemistry. 2001 Dec 1;39(23):4152–4166.
Journal cover image

Published In

Journal of Polymer Science, Part A: Polymer Chemistry

DOI

ISSN

0887-624X

Publication Date

December 1, 2001

Volume

39

Issue

23

Start / End Page

4152 / 4166

Related Subject Headings

  • Polymers
  • 3406 Physical chemistry
  • 3403 Macromolecular and materials chemistry
  • 0912 Materials Engineering
  • 0306 Physical Chemistry (incl. Structural)
  • 0303 Macromolecular and Materials Chemistry