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New modified off-stoichiometry thiol–enes polymers, called OSTE-MS polymers, were developed by introducing mercaptosilane into the polymer mixture. This modification made it possible to introduce silane groups into the polymer frame, due to which the polymer gained the ability to bond with silicon wafers without modification of the wafer surface by any adhesive. The optimal composition for creating 3D polymer structures on a chip was selected, which consists of a volume ratio of 6:6:1 of allyl monomer, mercapto monomer, and mercaptosilane, respectively. The hardness, shift force, tensile strength, Young’s modulus, optical transparency, glass transition temperature, thermal stability, and chemical resistance of the OSTE-MS polymer, and the viscosity for the prepolymer mixture were studied. On the basis of the OSTE-MS polymer, 3D polymer structures of the well type and microfluidic system on the silicon chips were obtained.

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