Abstract
A series of hybrid networks based on polyhedral oligomeric silsesquioxane (POSS) were prepared by thiol-epoxy click reaction using commercially available octakis-glycidyl-POSS (G-POSS), trimethylolpropane triglycidyl ether, and trimethylolpropane tris(3-mercaptopropionate) as monomers. The click reaction was simply catalyzed by lithium hydroxide which proceeded readily at ambient conditions in very good yields. The incorporation of G-POSS into the network was clearly determined by transmission electron microscopy, FTIR, and 1H-NMR spectroscopy techniques performed with a model study using 1-butane thiol and G-POSS molecules. The homogeneous distribution of G-POSS up to 5 wt% in the hybrid network was apparently confirmed by morphological investigations. By increasing G-POSS content higher than 5 wt%, the heterogeneous dispersion of G-POSS was determined from the tensile strength measurements. The significant decrease in tensile strength was possible due to the agglomeration of G-POSS. On the other hand, thermal properties of hybrid networks were compared together by thermogravimetric analyses, where all samples exhibited one-step degradation in the range of 220–500 °C. The thermal decomposition of hybrid network led to complete degradation of the organic part and favored the formation of stable carbonaceous and inorganic residues as char. Thus, the char yields of hybrid networks were increased to 6.2, 7.8, 10.1, 12.7, and 15.1% by G-POSS loadings from 0 to 15 wt%. This improvement was also a proof of the incorporation of G-POSS into the hybrid networks that resulted in high heat-resistant POSS-based hybrid networks compared to a sample without G-POSS.
Similar content being viewed by others
References
Dawson R, Cooper AI, Adams DJ (2012) Nanoporous organic polymer networks. Prog Polym Sci 37:530–563
Liu S, Dicker KT, Jia X (2015) Modular and orthogonal synthesis of hybrid polymers and networks. Chem Commun 51:5218–5237
Kuo SW, Chang FC (2011) POSS related polymer nanocomposites. Prog Polym Sci 36:1649–1696
Doganci E, Tasdelen MA, Yilmaz F (2015) Synthesis of miktoarm star-shaped polymers with poss core via a combination of CuAAC click chemistry, atrp, and rop techniques. Macromol Chem Phys 216:1823–1830
Sencevik RG, Tasdelen MA (2014) Poly(methyl methacrylate)/POSS hybrid networks by type II photoinitiated free radical polymerization. Polym Composite 35:1614–1620
Dizman C, Uyar T, Tasdelen MA, Yagci Y (2013) Synthesis and characterization of polysulfone/POSS hybrid networks by photoinduced crosslinking polymerization. Macromol Mater Eng 298:1117–1123
Arslan I, Tasdelen MA (2016) POSS-based hybrid thermosets via photoinduced copper-catalyzed azide-alkyne cycloaddition click chemistry. Des Monomers Polym 19:155–160
Hou G, Li N, Han H, Huo L, Gao J (2015) Hybrid cationic ring-opening polymerization of epoxy resin/glycidyloxypropyl-polyhedral oligomeric silsesquioxane nanocomposites and dynamic mechanical properties. Iran Polym J 24:299–307
Kolb HC, Finn MG, Sharpless KB (2001) Click chemistry: diverse chemical function from a few good reactions. Angew Chem Int Ed 40:2004–2021
Tasdelen MA, Yagci Y (2013) Light-induced click reactions. Angew Chem Int Ed 52:5930–5938
Tasdelen MA, Kiskan B, Yagci Y (2016) Externally stimulated click reactions for macromolecular syntheses. Prog Polym Sci 52:19–78
Rostovtsev VV, Green LG, Fokin VV, Sharpless KB (2002) A stepwise Huisgen cycloaddition process: copper(i)-catalyzed regioselective “ligation” of azides and terminal alkynes. Angew Chem Int Ed 41:2596–2599
Tornøe CW, Christensen C, Meldal M (2002) Peptidotriazoles on solid phase: [1–3]-triazoles by regiospecific copper(I)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides. J Org Chem 67:3057–3064
Tasdelen MA (2011) Diels-alder “click” reactions: recent applications in polymer and material science. Polym Chem 2:2133–2145
Lowe AB (2010) Thiol-ene “click” reactions and recent applications in polymer and materials synthesis. Polym Chem 1:17–36
Yagci Y, Tasdelen MA, Jockusch S (2014) Reduction of Cu (II) by photochemically generated phosphonyl radicals to generate Cu (I) as catalyst for atom transfer radical polymerization and azide-alkyne cycloaddition click reactions. Polymer 55:3468–3474
Tinmaz HB, Arslan I, Tasdelen MA (2015) Star polymers by photoinduced copper-catalyzed azide–alkyne cycloaddition click chemistry. J Polym Sci A Polym Chem 53:1687–1695
Demirci G, Tasdelen MA (2015) Synthesis and characterization of graft copolymers by photoinduced cuaac click chemistry. Eur Polym J 66:282–289
Jiang L, Peng Z, Guo A, Ye L, Feng ZG (2015) A one-step synthesis of polyrotaxane via in situ michael addition reaction. Iran Polym J 24:679–685
Stuparu MC, Khan A (2016) Thiol-epoxy “click” chemistry: application in preparation and postpolymerization modification of polymers. J Polym Sci A Polym Chem 54:3057–3070
De S, Khan A (2012) Efficient synthesis of multifunctional polymers via thiol-epoxy “click” chemistry. Chem Commun 48:3130–3132
Binder S, Gadwal I, Bielmann A, Khan A (2014) Thiol-epoxy polymerization via an AB monomer: synthetic access to high molecular weight poly(beta-hydroxythio-ether)s. J Polym Sci A Polym Chem 52:2040–2046
Brandle A, Khan A (2012) Thiol-epoxy ‘click’ polymerization: efficient construction of reactive and functional polymers. Polym Chem 3:3224–3227
Gadwal I, Khan A (2013) Protecting-group-free synthesis of chain-end multifunctional polymers by combining atrp with thiol-epoxy ‘click’ chemistry. Polym Chem 4:2440–2444
Acebo C, Fernandez-Francos X, Ramis X, Serra A (2016) Multifunctional allyl-terminated hyperbranched poly(ethyleneimine) as component of new thiol-ene/thiol-epoxy materials. React Funct Polym 99:17–25
Cengiz N, Rao JY, Sanyal A, Khan A (2013) Designing functionalizable hydrogels through thiol-epoxy coupling chemistry. Chem Commun 49:11191–11193
Fernandez-Francos X, Konuray AO, Belmonte A, De la Flor S, Serra A, Ramis X (2016) Sequential curing of off-stoichiometric thiol-epoxy thermosets with a custom-tailored structure. Polym Chem 7:2280–2290
Guzman D, Ramis X, Fernandez-Francos X, Serra A (2015) Preparation of click thiol-ene/thiol-epoxy thermosets by controlled photo/thermal dual curing sequence. RSC Adv 5:101623–101633
Guzman D, Ramis X, Fernandez-Francos X, Serra A (2014) New catalysts for diglycidyl ether of bisphenol a curing based on thiol-epoxy click reaction. Eur Polym J 59:377–386
Guzman D, Ramis X, Fernandez-Francos X, Serra A (2015) Enhancement in the glass transition temperature in latent thiol-epoxy click cured thermosets. Polymers 7:680–694
Acebo C, Fernandez-Francos X, Ramis X, Serra A (2016) Thiol-yne/thiol-epoxy hybrid crosslinked materials based on propargyl modified hyperbranched poly(ethyleneimine) and diglycidylether of bisphenol a resins. RSC Adv 6:61576–61584
Kickelbick G (2003) Concepts for the incorporation of inorganic building blocks into organic polymers on a nanoscale. Prog Polym Sci 28:83–114
Binder WH, Sachsenhofer R (2007) ‘Click’ chemistry in polymer and materials science. Macromol Rapid Commun 28:15–54
Hoyle CE, Bowman CN (2010) Thiol-ene click chemistry. Angew Chem Int Ed 49:1540–1573
Sumerlin BS, Vogt AP (2010) Macromolecular engineering through click chemistry and other efficient transformations. Macromolecules 43:1–13
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Bekin Acar, S., Ozcelik, M., Uyar, T. et al. Polyhedral oligomeric silsesquioxane-based hybrid networks obtained via thiol-epoxy click chemistry. Iran Polym J 26, 405–411 (2017). https://doi.org/10.1007/s13726-017-0529-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13726-017-0529-x