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

Abstract

This work presents a synthesis of monomers from a natural compound (limonene) and dimethylsiloxanes with various chain lengths by hydrosilylation. Based on these monomers, prepolymers with various lengths of the siloxane and methylene parts,as well as their analogues without siloxane moieties, were obtained by thiol-ene polyaddition with ethanedithiol, butanedithiol and hexanedithiol. Their physicochemical characteristics, namely the thermal stability, phase behaviour and intrinsic viscosity of the polymers obtained, were compared as a function of the length of the methylene spacer and the siloxane part in the polymer chain.

Ring-Opening Polymerization (ROP) and Catalytic Rearrangement as a Way to Obtain Siloxane Mono- and Telechelics, as Well as Well-Organized Branching Centers: History and Prospects

“…The methacrylate-terminated PDMS macromonomers synthesiz in this study have been successfully used to form films by UV-induced crosslinking, a studies of the properties of crosslinked films are the subject of future publications. In the work of Drozdov F. V. [144], the preparation of limonene functional PDMS the mechanism of cationic ROP from D4 and difunctional siloxane derivative of limone in the presence of Purolite ST-175 catalyst was considered (Figure 27). In this work, a ser of prepolymers based on difunctional siloxane derivatives of limonene and dithiols w different methylene spacer lengths was obtained by a photoinitiated thiol polyadditi In the work of Drozdov F.V.…”

“…In this work, a ser of prepolymers based on difunctional siloxane derivatives of limonene and dithiols w different methylene spacer lengths was obtained by a photoinitiated thiol polyadditi In the work of Drozdov F.V. [144], the preparation of limonene functional PDMS by the mechanism of cationic ROP from D4 and difunctional siloxane derivative of limonene in the presence of Purolite ST-175 catalyst was considered (Figure 27). In this work, a series of prepolymers based on difunctional siloxane derivatives of limonene and dithiols with different methylene spacer lengths was obtained by a photoinitiated thiol polyaddition reaction.…”

The Use of the Thiol-Ene Addition Click Reaction in the Chemistry of Organosilicon Compounds: An Alternative or a Supplement to the Classical Hydrosilylation?

“… Strategies for the synthesis of functional limonene derivatives by hydrosilylation and hydrothiolation ( a ) [ 46 ]; synthesis of limonene-based copolymers by thiol-ene polyaddition ( b ) [ 127 ]. Adopted from Refs.…”

“…Firstly, this approach was demonstrated in this example and then in the synthesis of copolymers (see Figure 29 b). It is possible to perform the first Hs reaction to obtain AA type monomers, and then perform their polyaddition with dithiols by the second Ht at the final stage [ 127 ]. Another approach was also shown: based on limonene, a dicarboxylic derivative is first obtained by the Ht reaction and then used in a polycondensation reaction with the corresponding diamine, which leads to the formation of polyamides [ 128 ].…”

“…Fast photoinitiated hydrothiolation, in contrast to hydrosilylation, allows functional siloxanes to be used as precursors to obtain objects with complex structure based on silicone elastomers in 3D printing (see Figure 37 ) [ 139 ], imprint lithography [ 140 ], and photolithography [ 127 ].…”