A library of monoalkenylsilsesquioxanes as potential comonomers for synthesis of hybrid materials

Abstract

In this paper we demonstrate a facile and efficient synthesis of monoalkenylsubstituted POSS compounds, i.e., R 7 (Si 8 O 12 )alkenyl and R 7 (Si 8 O 12 )(OSiMe 2 )-alkenyl with a functional alkenyl group of chain length (from vinyl to dec-9-enyl, with or without additional -OSiMe 2 -spacer between the silsesquioxane core and alkenyl moiety) and with five types of inert groups (Et, iBu, iOc, Cy, Ph) at the POSS core. These compounds constitute a library of monosubstituted POSS systems, including thorough spectroscopic and thermal characteristics. These findings could be especially useful for material chemists applying the compounds as modifiers or comonomers for copolymerization reaction, e.g., with olefins. Graphical AbstractJournal of Thermal Analysis and Calorimetry (2018) 132:1545-1555 https://doi.org/10.1007/s10973-018-7121-2( 0123456789().,-volV) (0123456789().,-volV)

Polysiloxanes Grafted with Mono(alkenyl)Silsesquioxanes—Particular Concept for Their Connection

“…In our previous studies, we reported on an efficient synthetic protocol for the preparation of a library of mono(alkenyl)silsesquioxanes varying in the length of the alkenyl chain and also in the inert substituents (R = Et, iBu, Cy, iOc, Ph) at the silsesquioxane core [101]. These studies revealed the dependence of the thermal stability of this series of compounds on the type of inert (R) and alkenyl group at SQs as well as the presence of the -OSi(Me 2 )spacer.…”

“…In this paper, our goal was to synthesize a series of hybrid materials based on selected PDMHS-Poly(dimethylsiloxane-co-methylhydrosiloxane)-PS1 (with 4.3 mmol/g Si-H content) and PS2 (with 1.1 mmol/g Si-H content) grafted with mono(alkenyl)substituted T 8 SQs as pendant groups. Basing on the scientific literature and our experience, we selected two types of mono(alkenyl)substituted T 8 SQs possessing two distinct inert substituents, i.e., iBu and Ph that exhibit different solubility as well as thermal stability [101]. It is well known that the type of inert and functional groups determine the physical and chemical properties of silsesquioxane [56,60,87] and as a consequence, may influence the properties of polysiloxanes modified with these compounds.…”

“…Polysiloxanes: Cross-linker 101 (PS1, 4.3 mmol/g Si-H content) and 120 (PS2, 1.1 mmol/g Si-H content) from Evonik (Darmstadt, Germany). ((IPr*)Pt(dvds)) (IPr* = 1,3-bis{2,6-bis(diphenylmethyl)-4-methylphenyl}-imidazol-2-ylidene) and Mono(alkenyl)functionalized silsesquioxanes were synthesized according to the literature [101,102]. Toluene, tetrahydrofuran (THF), chloroform-d, molecular sieves type 4 Å from Chempur (Piekarý Sląskie, Poland).…”

Preparation of Tri(alkenyl)functional Open-Cage Silsesquioxanes as Specific Polymer Modifiers

“…Silica gel-MN-Kieselgel 60 from Fluka Chemie AG, Buchs, Switzerland. Chloro(hex-5-enyl)silane and chloro(dec-9-enyl)silane were obtained via the procedure described earlier [48]. SQ-iBu-OH was prepared prior to use, i.e., dissolved in DCM, precipitated in MeOH, and then dried under vacuum.…”

“…The exemplary procedure is presented for SQ-iBu-Vi. Trisilanol SQ-iBu-OH (0.31 g, 0.39 mmol), anhydrous THF (4 mL), and chloro(dimethyl)vinylsilane (0.17 mL, 1.21 mmol) were introduced into a two-neck round-bottom flask that was equipped with a magnetic stirrer and placed in an ice-water bath (the respective chloro(dimethyl)(hex-3-enyl)silane and chloro(dimethyl)(dec-5-enyl)silane were prepared according to the literature procedure [48]). This was followed by adding Et 3 N (0.17 mL, 1.23 mmol) to the reaction mixture.…”