Coupling agents with 2,4,6,8-tetramethylcyclotetrasiloxane core - synthesis and application in styrene-butadiene rubber production

A facile one-pot procedure for the functionalization of 2,4,6,8-tetramethylcyclotetrasiloxane DH4 to branched organosilicon compounds DSP3 or DS3P bearing various, but clearly defined, numbers of silyl groups with an affinity to silica (S) and organic groups (alkyl, alkenyl, perfluoroaryl, epoxy, ether and ester) capable of bonding with polymers (P) has been demonstrated. Sequential hydrosilylation of allyltrimethoxysilane in the first step and olefin or alkyne in the second (and reverse order of reagents) has been applied in the presence of Karstedt's catalyst, which is commercially available and commonly used in industry. The developed procedure permitted the synthesis of 13 new, branched organosilicon compounds DSP3 and DS3P with excellent yields and precise distribution of functional groups. All products were easily isolated by simple filtration followed by drying under reduced pressure and fully characterized by spectroscopic methods (H-1, C-13, Si-29 NMR, IR) and mass spectrometry (ESI or MALDI). The obtained compounds, because of the presence of two different functional groups with an affinity to inorganic filler and polymer matrix, are regarded as versatile silica modifiers, silane coupling agents for various applications, and starting materials in the preparation of polymer networks and vapor-deposited coatings. The vulcanizates prepared using cyclosiloxane-functionalized rubber showed enhanced rolling resistance and wet skid resistance, proving the compound's potential in producing novel Green Tire treads.

Automated summary

A simple one-step reaction was demonstrated for the functionalization of 2,4,6,8-tetramethylcyclotetrasiloxane DH4, resulting in branched organosilicon compounds DSP3 or DS3P with affinity to silica and various organic groups capable of bonding with polymers. The synthesis of 13 new compounds with excellent yields and precise functional group distribution was achieved using sequential hydrosilylation and Karstedt's catalyst. The obtained compounds are versatile silica modifiers, silane coupling agents, and starting materials for polymer networks and vapor-deposited coatings.