α-cyanoacryloyloxyethyloxypropyl-functionalized polysiloxanes were prepared using a condensation reaction between the adduct of anthracene/α-cyanoacryloyl chloride and hydroxyethyloxypropyl-modified polydimethylsiloxanes, followed by a retro-Diels-Alder reaction to deprotect the anthracene. Structures of the obtained polymers and their intermediates were characterized using 1 H NMR, 13 C NMR, and FT-IR spectroscopies. Under mild conditions such as at room temperature with a relative humidity of 60%, the α-cyanoacryloyloxyethyloxypropyl-functionalized polysiloxanes could be completely cured within 3 minutes. With a small amount of N,Ndimethyl-p-toluidine as the initiator, the curing time could be further shortened to 3-5 seconds. Various factors affected on the cross-linking density and the average molecular weight between two adjacent cross-linking points were investigated. The results indicated that with the introduction of the α-cyanoacryloyloxyethyloxypropyl group, α-cyanoacryloyloxyethyloxypropylfunctionalized PDMS exhibited much better thermal stabilities than that of pure poly(ethyl α-cyanoacrylate). Besides, the introduction of an αcyanoacryloyloxyethyloxypropyl group in the PDMS molecule also eliminated the crystallization behavior and glass transition temperature of PDMS. The results of the water contact angle test showed the interfacial characteristics of the prepared material changed significantly relative to pure PDMS. With the increase in the content of the functional group, the water contact angle of the material showed an overall increasing trend.

MT‐type polysiloxanes containing active vinyl group were prepared under acid conditions initiated from divinyltetramethyldisiloxane and methyltrimethoxysilane by one‐pot method, co‐hydrolysis method, and reaction‐rectification coupling method, respectively. The influence of different methods on molecular weight, molecular weight distribution, and ratios of each kind of segment in the MT‐type polysiloxane containing active vinyl group were discussed in detail. The results indicated that with the reaction‐rectification coupling method, the residual hydroxyl segment in the prepared MT‐type polysiloxane could be lower than 0.5 wt%. For MT‐type polysiloxanes with high hydroxyl group content, the hydroxyl content could be reduced when treated with hexamethyldisilazane, trimethylchlorosilane, zinc naphthalate, or tetramethylammonium hydroxide under suitable conditions. Hexamethyldisilazane was the most convenient and effective regents among these four compounds, the residual hydroxyl content contained in the prepared MT‐type polysiloxanes could be reduced from 13.4 to 0.9 wt% when MT‐type polysiloxane sample was treated with hexamethyldisilazane.