AI 中文总结
研究建立弹性介导的PIPS机制（DiPolES），通过在弹性网络内可控聚合弥合液态PIPS限制。利用该方法制备含可调PMMA微粒的弹性体复合材料，可推广且高产率生产。揭示颗粒形成过程，发现应变可直接制椭圆形颗粒。
AI 中文摘要
聚合诱导相分离（PIPS）通过将化学转化与热力学相分离相结合，为生成结构化聚合物材料提供了一条有力途径。液态系统中的PIPS是分散聚合的基础，是微粒生产的一项关键技术，但受到溶剂相容性和形态范围有限的限制。本文建立了一种弹性介导的PIPS机制，通过在可变形的弹性网络内进行可控聚合来弥合这两个限制。这种方法称为弹性体溶剂中的分散聚合（DiPolES），是分散聚合的固态类似物，其中弹性网络同时充当溶剂和物理稳定剂。使用光引发转移终止剂介导的聚甲基丙烯酸甲酯（MMA）在聚二甲基硅氧烷（PDMS）弹性体溶剂中的聚合，DiPolES能够稳健地制备包含尺寸可调（0.85至3μm）和形状（球形和椭圆形）均匀PMMA微粒的弹性体复合材料。该策略可推广到PDMS/MMA系统之外，适用于多种单体，如丙烯腈和2-乙烯基吡啶，这些单体可从弹性体溶剂中萃取，从而实现微粒的高产率生产。实时成像和成分分析表明，颗粒形成在低单体转化率下通过快速成核进行，随后生长并伴随着周围网络的空化。单体负载量控制颗粒尺寸，而溶剂弹性调节从孤立的均匀球体到异质簇的转变。有趣的是，在DiPolES过程中施加单轴应变能够在无需任何后处理的情况下生产椭圆形颗粒。
英文摘要
Polymerization-induced phase separation (PIPS) provides a powerful route to generate structured polymeric materials by coupling chemical conversion with thermodynamic demixing. PIPS in liquid-state systems underlies dispersion polymerization, serving as a cornerstone technique for microparticle production, yet is constrained by solvent compatibility and limited range of morphologies. Here, we establish an elastically mediated PIPS regime that bridges these two limits by conducting controlled polymerization within a deformable elastomeric network. This approach, termed Dispersion Polymerization in an Elastomeric Solvent (DiPolES), serves as a solid-state analogue of dispersion polymerization in which an elastomeric network simultaneously serves as solvent and physical stabilizer. Using photoiniferter-mediated polymerization of methyl methacrylate (MMA) within poly(dimethyl siloxane) (PDMS) elastomeric solvent, DiPolES enables robust fabrication of elastomeric composites containing uniform PMMA microparticles with tunable size (0.85 to 3 μm) and shape (spheroidal and ellipsoidal). The strategy is generalizable beyond the PDMS/MMA system and is applicable to diverse monomers, such as acrylonitrile and 2-vinyl pyridine, which can be extracted from the elastomeric solvent, enabling high-yield production of microparticles. Real-time imaging and compositional analysis reveal that particle formation proceeds through rapid nucleation at low monomer conversion, followed by growth accompanied by cavitation of the surrounding network. Monomer loading governs the particle size, while solvent elasticity modulates the transition from isolated uniform spheroids to heterogeneous clusters. Interestingly, applying uniaxial strain during DiPolES enables production of ellipsoidal particles without any post-processing.
Comments26 pages, 5 figures
