POSS-based hybrid thermosets via photoinduced copper-catalyzed azide–alkyne cycloaddition click chemistry

Abstract

An efficient approach for the preparation of inorganic/organic hybrid thermosets via photoinduced copper-catalyzed azide-alkyne cycloaddition click chemistry is established. Highly cross-linked thermoset polymers have been practically obtained by this technique using multifunctional compounds, tri-alkyne (1,1,1-tris[4-(2-propynyloxy) phenyl]-ethane) with octakis-azido-POSS or tri-azide (3,3′-((2-((3-azido-2-hydroxypropoxy)methyl)-2-ethylpropane-1,3-diyl)bis(oxy))bis(1-azidopropan-2-ol)) in the presence of Cu(II)Br 2 /N,N,N′,N″,N‴-pentamethyldiethylenetriamine/2-dimethoxy-2-phenyl acetophenone. The homogeneously distributed POSS nanoparticles are clearly detected in the TEM micrographs; whereas the TGA analysis shows that the obtained hybrid thermosets are thermally stable up to 360 °C and begin to lose weight at higher temperatures with a char yield of 23-50% at 800 °C.

Soybean oil based thermoset networks via photoinduced CuAAC click chemistry

“…According to Bowman and coworkers, the kinetics of photoinduced CuAAC were extremely influenced by the resin viscosity and copper concentration . In recent years, this versatile route has been utilized to synthesize a wide range of complex macromolecular architectures such as telechelic, star and network polymers, block and graft copolymers, surface modification and bioconjugation . Although thermoset networks from renewable resources such as soybean, linseed, corn and canola oils were prepared either by CuAAC using CuSO 4 /sodium ascorbate as catalyst or by thermally initiated copper‐free azide − alkyne cycloaddition reactions, a long reaction time was required to get good yields .…”

Aliphatic Polyester/polyhedral Oligomeric Silsesquioxanes Hybrid Networks via Copper‐free 1,3‐dipolar Cycloaddition Click Reaction

“…The FTIR and 13 C‐NMR spectroscopies were utilized to enlighten the structures of the PCA while showing signals at around 1710 and 2120 cm −1 in FTIR spectrum, and 151.6 and 74.5 ppm in 13 C‐NMR spectrum assignable to the CO and CC groups, respectively. On the other hand, the octakis‐azido POSS was successfully prepared by ring‐opening reaction of octakis‐glycidyl‐POSS with sodium azide according to the literature . The appearance of asymmetric stretching band of azide at 2080 cm −1 as well as disappearance of asymmetric stretching band of glycidyl at 910 cm −1 confirmed the successful transformation of glycidyl groups of POSS to azide functionalities (Fig.…”

“…Octakis‐glycidyl‐POSS (EP0409, Hybrid Plastic), and octaisobutyl POSS (MS0825, Hybrid Plastic), 98.0%, Aldrich), 2‐propanol (%98, Acros), acetic acid (%99, Glacidal, Merck), and sodium azide (NaN 3 , 99%, Merck) were used as received. Octakis azido‐POSS (POSS‐N 3 as viscous liquid) was prepared according to the literature . The poly(1,4‐cyclohexanedimethylene acetylene dicarboxylate) (PCA) was synthesized according to our published procedure .…”

Synthesis and characterization of POSS hybrid organogels using Menschutkin quaternization chemistry

“…Usually, monofunctional POSS structures are used for side chain or end chain functionalization of organic compounds. On the other hand, multifunctional POSS molecules are employed as gelators to produce thermoset polymers or as cores to obtain star polymeric structures . Several POSS cored star polymers have been synthesized via copper mediated click chemistry and controlled radical polymerization techniques .…”