Novel Silsesquioxane-Derived Boronate Esters—Synthesis and Thermal Properties

The functionalization of mono- and octahydrospherosilicate with vinylboranes and allylboranes via hydrosilylation reaction in the presence of a Karstedt’s platinum (0) catalyst is presented. This is the catalytic route to obtain a new class of silsesquioxanes containing boron atoms in their structure in high yields (>90%) and with satisfactory selectivity. The obtained compounds were fully characterized by spectroscopic (1H, 13C, 29Si NMR) and spectrometric methods (MALDI-TOF-MS), as well as thermal analysis (TGA). The obtained compounds were subjected to thermal tests, characterizing the processes of melting, thermal evaporation, sublimation and thermal decomposition.

Selective hydrosilylation of allyl chloride with trichlorosilane

The transition-metal-catalysed hydrosilylation reaction of alkenes is one of the most important catalytic reactions in the silicon industry. In this field, intensive studies have been thus far performed in the development of base-metal catalysts due to increased emphasis on environmental sustainability. However, one big drawback remains to be overcome in this field: the limited functional group compatibility of the currently available Pt hydrosilylation catalysts in the silicon industry. This is a serious issue in the production of trichloro(3-chloropropyl)silane, which is industrially synthesized on the order of several thousand tons per year as a key intermediate to access various silane coupling agents. In the present study, an efficient hydrosilylation reaction of allyl chloride with trichlorosilane is achieved using the Rh(I) catalyst [RhCl(dppbzF)]2 (dppbzF = 1,2-bis(diphenylphosphino)-3,4,5,6-tetrafluorobenzene) to selectively form trichloro(3-chloropropyl)silane. The catalyst enables drastically improved efficiency (turnover number, TON, 140,000) and selectivity (>99%) to be achieved compared to conventional Pt catalysts.

Functionalization of polyhydromethylsiloxane with nitrogen-containing organic compounds

Linear polyhydromethylsiloxane (PHMS) was functionalized with nitrogen-containing organic compounds: N-allylaniline (Naa), N-allylcyclohexylamine (Nach), N-allylpiperidine (Nap) and 4-vinylpyridine (4VP) via hydrosilylation reaction in the presence of Pt0 complex (Karstedt’s catalyst) under mild conditions. Reaction course was followed by FTIR spectroscopy and final hydrosilylation products were characterized by FTIR, 1H, 29Si NMR and 29Si MAS-NMR spectroscopies as well as by elemental analysis. Results showed that functionalization of PHMS with N-allyl amines took place but in none of the systems it was complete. Hydrosilylation of Naa, Nach and Nap with PHMS led both, to the β and α addition products. 29Si NMR spectroscopy showed unequivocally that the reaction of PHMS with 4VP did not occur and the only reactions in the systems were hydrolysis of Si–H groups of PHMS followed by condensation of the silanol groups resulting in cross-linking of the polymer. All the functionalized polymers studied in the work contained reactive amine moieties prone to further modifications, therefore exhibit a great potential for various applications.

Novel Approaches to Chemically Cross-Linked Phosphazene Structures: Hydrosilylation vs Piers–Rubinsztajn Reaction

Finding new ways for the preparation of cross-linked structures is a significant problem in terms of materials for biomedical application, lithium batteries electrolytes, and etc. Within this work we have studied the possibility to utilize hydrosilylation and Piers-Rubinsztajn reactions to obtain cross-linked model phosphazene compounds, containing eugenoxy and guaiacoxy groups. It was shown that Piers-Rubinsztajn reaction cannot be efficiently used to prepare tailored polymer-matrix, due to the catalyst deactivation by nitrogen atoms of phosphazene units. A number of cross-linked phosphazene-based materials was obtained with the use of hydrosilylation reaction and their properties were studied by NMR spectroscopy, FTIR, DSC, and TGA. This work showed a perspective for the use of eugenoxy functional groups for the preparation of three-dimensional hybrid phosphazene/siloxane-based materials for various applications.

Transparent cyclo-linear polyphenylsiloxane elastomer integrating high refractive index, thermal stability and flexibility.

A new type of cyclo-linear structured high phenyl content siloxane elastomer (Ph-CLS-E) is prepared through “one-pot” hydrosilylation reaction that take advantage of the reactivity differences of the cyclic, linear precursors...