The design and application of polysulfone–polysiloxanes block copolymers remains as a big challenge mainly owing to limited synthetic methods of sulfone prepolymers. In this contribution, vinyl-terminated poly(siloxane sulfone) (PSS) was applied as the hard segment to obtain novel polysulfone-polysiloxane multi-block copolymers by hydrosilylation with hydride-terminated polysiloxane (PDMS-H) for the first time. The new vinyl-functionalized sulfone prepolymers were prepared by ring-opening polymerization of benzylsulfonyl macroheterocyclosiloxane (BSM) using divinyltetramethyldisiloxane as end-capping reagent and KOH as a catalyst, which differs from the traditional condensation methods. Based on the polysulfone prepolymers, a better control of the molecular weight of the obtained polymers was achieved, affording relatively low PDI. Their morphological properties were investigated by atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS), which revealed a mild microphase separation in the copolymers. Their surface and fluorescence properties can be effectively tuned by changing the PSS content. Besides, the obtained copolymers exhibited high hydrolytic and thermal-oxidative stability, and underwent a controlled and effective degradation into the starting benzylsulfonyl macroheterocyclosiloxane with a high conversion of 85% in the presence of KHSO₄ at room temperature. This strategy may provide new ideas for the design and application of new polysulfone–polysiloxanes block copolymers.

聚砜-聚硅氧烷嵌段共聚物的设计和应用仍然是一个巨大的挑战，这主要是由于砜预聚物的合成方法有限。在这一贡献中，乙烯基封端的聚（硅氧烷砜）（PSS）被用作硬链段，以首次通过与氢化物封端的聚硅氧烷（PDMS-H）进行氢化硅烷化反应获得新型的聚砜-聚硅氧烷多嵌段共聚物。新型乙烯基官能化砜预聚物是通过使用二乙烯基四甲基二硅氧烷作为封端剂和KOH作为催化剂，通过苄基磺酰基大杂环硅氧烷（BSM）的开环聚合反应制备的，这不同于传统的缩合方法。基于聚砜预聚物，可以更好地控制所得聚合物的分子量，从而提供相对较低的PDI。通过原子力显微镜（AFM）和小角X射线散射（SAXS）研究了它们的形态特性，揭示了共聚物中微相的分离。通过改变PSS含量可以有效地调节其表面和荧光性质。此外，所获得的共聚物表现出高的水解和热氧化稳定性，并且在KHSO存在下可控地有效降解为起始苄基磺酰基大杂环硅氧烷，其高转化率为85％。₄在室温下。该策略可能为新型聚砜-聚硅氧烷嵌段共聚物的设计和应用提供新思路。