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

Fatma Vatansever; Michael R. Hamblin

Macromolecular Research, Vol.25, No.2, 97-107, February, 2017

DOI10.1007/s13233-017-5009-9 Export Citation

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

Fatma Vatansever^{1, 2, †}, and Michael R. Hamblin^{1, 2, †}

¹Wellman Center for Photomedicine, Massachusetts General Hospital, Boston, MA 02114, USA
²Department of Dermatology, Harvard Medical School, Boston, MA 02115, USA

E-mail:,

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.

Keywords:polymeric nanocomposites;inorganic-organic interfacing;controlled polymerization;surface initiated polymerization;nanoparticle surface modification;titanium catalyst;n-hexyl isocyanate polymerization

[References]

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[Referenced By]

[1] Manca M, Cannavale A, De Marco L, Arico AS, Cingolani R, Gigli G, Langmuir, 25(11), 6357 (2009)

[2] Bravo J, Zhai L, Wu ZZ, Cohen RE, Rubner MF, Langmuir, 23(13), 7293 (2007)

[3] Chen JF, Ding HM, Wang JX, Shao L, Biomaterials, 25, 723 (2004)

[4] Burns A, Ow H, Wiesner U, Chem. Soc. Rev., 35, 1028 (2006)

[5] Yang HH, Zhang SQ, Chen XL, Zhuang ZX, Xu JG, Wang XR, Anal. Chem., 76, 1316 (2004)

[6] Katz E, Willner I, Angew. Chem.-Int. Edit., 43, 6042 (2004)

[7] Radhakrishnan B, Ranjan R, Brittain WJSM, Soft Matter, 2, 386 (2006)

[8] Zou H, Wu SS, Shen J, Chem. Rev., 108(9), 3893 (2008)

[9] Chen Z, Cui ZM, Cao CY, He WD, Jiang L, Song WG, Langmuir, 28(37), 13452 (2012)

[10] Edmondson S, Osborne VL, Huck WT, Chem. Soc. Rev., 33, 14 (2004)

[11] Pruker O, Ruhe J, Mater. Res. Soc. Symp. Proc., 304, 1675 (1993)

[12] Patten TE, Novak BM, Macromolecules, 26, 436

[13] Cook R, Johnson RD, Wade CG, O’Leary DJ, Munoz B, Green MM, Macromolecules, 34, 3454 (1990)

[14] Dubin PL, Principi JM, Macromolecules, 22, 1891 (1989)

[15] Hegedus LS, Transition Metals in the Synthesis of Complex Organic Molecules, University Science Books, New York, 1994.

[16] Shmueli U, Traub W, Rosenheck K, J. Polym. Sci. B: Polym. Phys., 7, 515 (1969)

[17] Lifson S, Felder C, Green MM, Macromolecules, 25, 4142 (1992)

[18] Bianco E, Ciferri A, Conio G, Krigbaum WR, Polymer, 28, 813 (1987)

[19] Itou T, Teramoto A, Macromolecules, 21, 2225 (1988)

[20] Green MM, Andreola C, Munuz B, Rridy MP, Zero K, J. Am. Chem. Soc., 110, 4063 (1988)

[21] Green MM, Khatri C, Peterson NC, J. Am. Chem. Soc., 115, 4941 (1993)

[22] Belyakova LD, Dzhigit OM, Kiselev AV, R. J., Phys. Chem. Engl. Trans., 33, 551 (1959).

[23] Boehm HP, Angew. Chem.-Int. Edit., 5, 533 (1966)

[24] Hair ML, Infrared Spectroscopy in Surface Chemistry, Dekker, New York, 1967.

[25] Liu CH, Maciel GE, J. Am. Chem. Soc., 118(21), 5103 (1996)

[26] Chuang IS, Maciel GE, J. Am. Chem. Soc., 118(2), 401 (1996)

[27] Vrij A, Philipse AP, J. Colloid Interface Sci., 128, 121 (1989)

[28] Stober W, Fink A, Bohn E, J. Colloid Interface Sci., 26, 62 (1968)

[29] Vansant EF, Voort P, Vrancken KC, Characterization and Chemical Modification of the Silica Surface, Elsevier, New York, 1994.

[30] Iler RK, The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties, and Biochemistry, Wiley, New York, 1979.

[31] Wong J, Angell CA, Glass Structure by Spectroscopy, Marcell Dekker, New York, 1976.

[32] Porous Silicon, World Scientific, Singapore, 1994.

[33] Corey EJ, Venkateswarlu A, J. Am. Chem. Soc., 94, 6190 (1972)

[34] Corey EJ, Snider BB, J. Am. Chem. Soc., 94, 2549 (1972)

[35] Nakamura E, Kuwajima I, J. Am. Chem. Soc., 97, 3257 (1975)

[36] Webster OW, Science, 251, 887 (1991)

[37] Quirk RP, Lee B, Polym. Int., 27, 359 (1992)

[38] Khadem J, Veloso AA, Tolentino F, Hasan T, Hamblin MR, Invest Ophthalmol Vis Sci., 40, 3132 (1999)