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Surface-initiated polymerization with poly(n-hexylisocyanate) to covalently functionalize silica nanoparticles

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Abstract

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium(IV) catalysis, to grow poly(n-hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles were “seeded” with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, surface tethered catalyst provided the sites for n-hexyl isocyanate monomer insertion to “build up” the surface-grown polymer layers from the “bottom-up”. A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance spectroscopy (NMR), gas chromatography-mass spectrometry (GC-MS), gel permeation chromatography (GPC), and thermogravimetric analyses.

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Authors and Affiliations

  1. Wellman Center for Photomedicine, Massachusetts General Hospital, Boston, MA, 02114, USA

    Fatma Vatansever & Michael R. Hamblin

  2. Department of Dermatology, Harvard Medical School, Boston, MA, 02115, USA

    Fatma Vatansever & Michael R. Hamblin

  3. Harvard-MIT Division of Health Sciences and Technology, Boston, MA, 02139, USA

    Michael R. Hamblin

Authors
  1. Fatma Vatansever
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  2. Michael R. Hamblin
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Correspondence to Fatma Vatansever or Michael R. Hamblin.

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Vatansever, F., Hamblin, M.R. Surface-initiated polymerization with poly(n-hexylisocyanate) to covalently functionalize silica nanoparticles. Macromol. Res. 25, 97–107 (2017). https://doi.org/10.1007/s13233-017-5009-9

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  • DOI: https://doi.org/10.1007/s13233-017-5009-9

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