Synthesis of new functional siloxane derivatives of limonene. Part I: Combination of hydrosilylation and hydrothiolation reactions

Terpene- and terpenoid-based polymeric resins for stereolithography 3D printing

“…[19][20][21][22] This class of monomer is widely available, and may be found in essential oils, tree sap and materials, citrus fruit, and even as by-products from other manufacturing processes, such as the paper industry's Kraft process, or simply through the processing of citrus fruits and other renewable resources. [23][24][25][26] The inherent double bonds present in mono-, di-, tri-, and other polyterpenes make them excellent candidates for the creation of sustainably-sourced photo-crosslinkable resins, yet to date only a few studies have investigated their application beyond utilizing appended (meth)acrylate or epoxide functionalities for (controlled) radical polymerisation 27,[28][29][30] modified polysaccharides, 31 polycarbonates, 32 and even polysilanes, 33 with processing still being limited in such studies. Herein, we report our study of the application of five terpenes: limonene, terpinene, geraniol, nerol and linalool ( Fig.…”

The selective hydrosilylation of norbornadiene-2,5 by monohydrosiloxanes

“…A catalyst can exert a strong effect on the selectivity of the hydrosilylation reaction. For example, in the hydrosilylation reaction the Pt-containing systems tolerate any hydrosilane (e.g., HSiCl n Me 3Àn (n ¼ 1-3), HSi(OR) 3 , and H n SiR 4Àn (n ¼ 1-3)), while Pd-catalysts are mostly applicable to HSiCl n R 3Àn (n ¼ 2, 3) and Rh-compounds display a good tolerance to HSiR 3 (R alkyl or aryl). 31,32 In this work the catalysts based on Rh-, Pd-, and Pt-complexes were compared for the hydrosilylation of NBD using PMDS or HMTS (Scheme 2).…”

“…The hydrosilylation of alkenes and dienes is a powerful synthetic tool for the production of various organosilicon compounds [1][2][3] and modication of the properties of the material. 4,5 Among the low-molecular-weight organosilicon compounds, alkenylsilanes are the most commonly used building blocks in organic synthesis owing to their versatile reactivity.…”

Synthesis and properties of prepolymers and their siloxane analogues by thiol‐ene polyaddition of limonene with dithiols

“…The difference in the chemical activity of unsaturated bonds of limonene – endocyclic and exocyclic – allows its regioselective modification by hydride addition reactions, in particular hydrosilylation and hydrothiolation. If only the isoprene bond is subject to hydrosilylation, thiol‐ene addition can occur in both directions to give both complete and partial modification products . In this case, monomers with various functionalities can be obtained regioselectively from limonene by means of hydrothiolation.…”

“…We have recently reported a successful process of limonene hydrosilylation by low molecular weight hydridosiloxanes at the isoprene bond to give new organosilicon precursors capable of further transformations by hydrothiolation of the remaining cyclohexene bond in the limonene moiety. We assume that combining hydride addition reactions at various stages of reactions will expand the options to synthesize silicones using limonene as a renewable comonomer, which will open up new prospects in the creation of polymers with a special combination of properties.…”