Thiol–ene (TE)‐based polymer particles are traditionally prepared via emulsion polymerization in water (using surfactants, stabilizers, and cosolvents). Here, a green and simple alternative is presented with excellent control over particle size, while avoiding the addition of stabilizers. Glycerol is applied as a dispersing medium for the preparation of off‐stoichiometric TE microparticles, where sizes in the range of 40–400 µm are obtained solely by changing the mixing speed of the emulsions prior to crosslinking. Control over surface chemistry is achieved by surface functionalization of excess thiol groups via photochemical thiol–ene chemistry resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization is used for the first time to introduce a thicker polymer layer on the particle surface. The application potential of the system is demonstrated by using functional particles as adsorbent for metal ions and as a support for immobilized enzymes.

中文翻译：

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甘油中硫醇-烯颗粒的简单制备和硫醇-烯化学（TEC）和表面链转移自由基聚合（SCT-FRP）的表面功能化

传统上，基于硫醇（TE）的聚合物颗粒是通过在水中乳液聚合（使用表面活性剂，稳定剂和助溶剂）制备的。在此，提出了一种绿色且简单的替代方法，可以很好地控制粒度，同时避免添加稳定剂。甘油用作制备非化学计量TE微粒的分散介质，仅通过改变交联前乳液的混合速度即可获得40-400 µm的粒径。对表面化学的控制是通过过量的硫醇基团通过光化学硫醇-烯化学的表面官能化来实现的，从而产生功能性单层。另外，第一次使用表面链转移自由基聚合在颗粒表面上引入较厚的聚合物层。