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Inorganic–organic hybrid copolymers are promising materials where the size of the inorganic/organic domains, the phase continuity and the interface between the domains play an important role in their behavior. Two types of hybrid copolymers composed of 3-butynoate-substituted zirconium-oxoclusters covalently bonded to a (3-mercaptopropyl)trimethoxysilane or a vinyltrimethoxysilane matrix are investigated in bulk. Their properties are directly correlated with the degree of condensation of the silanes and the alkyne-3-mercaptopropyl or alkyne-vinyl interface. Both copolymers show storage moduli and glass-transition temperatures (TgG″) above 130 MPa and 230°C. However, the more impressive results are achieved with the (3-mercaptopropyl)trimethoxysilane copolymer where a TgG″ of about 300°C holds over six dynamical mechanical spectroscopy analyses. In addition to their excellent thermo-mechanical proprieties, the copolymers show unreacted 3-mercaptopropyl or vinyl groups which could be employed either in direct usage of the materials or for post-functional modifications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

A new zirconium nano building block (ZrNBB) was prepared by the reaction of Zirconium tetrapropoxide with 3-butynoic acid in an alkoxide/acid at a 1 : 3 or 1 : 6 molar ratio. The complex was characterized by FTIR, 1H-NMR and 13C-NMR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, energy-dispersive X-ray analysis, and elementary analysis. A spontaneous alkyne-to-allene isomerization process was observed for ZrNBB. A bulk sample was also prepared and analyzed via dynamical mechanical spectroscopy in compression mode. The zirconium complex was then embedded in a polymeric matrix by radical copolymerization with vinyl trimethoxysilane. The inorganic–organic hybrid material was chemically and thermally stable. The shear storage modulus and loss modulus were measured to determine the mechanical properties of the material. The preliminary results are presented. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

This article describes the preparation and characterization of hybrid materials obtained from the polymerization of vinyl-substituted zirconium oxo-clusters [Zr6O4(OH)4(OOCCH2CHCH2)12(n-PrOH)]2·4(CH2CHCH2COOH) (Zr12) and 2-hydroxyethyl methacrylate (HEMA). The zirconium oxo-clusters serve as cross-linking agents, forming a 3D network by means of the copolymerization of their vinylic ligands with HEMA. To optimize the conditions for cross-linking, the polymerization was monitored with a differential scanning calorimeter. The resulting hybrid materials were also characterized using thermo-mechanical techniques. There was evidence not only of a greater rigidity above Tg, but also of a better thermal stability for several hybrid formulations than for simple poly-2-hydroxyethyl methacrylate. After immersion in water, the hybrids containing 20 or 60% w/w zirconium oxo-clusters also showed a stable behavior with an equilibrium swelling at about 27 and 18% w/w of water, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41568.