Beccard Malte Sebastian, Nüesch Frank A, Raman Venkatesan Thulasinath, Opris Dorina M
Functional Polymers, Empa, Swiss Federal Laboratories for Materials Science and Technology (EMPA) 8600 Dübendorf Switzerland
Eidgenössische Technische Hochschule Zürich (ETHZ) 8092 Zurich Switzerland.
Polym Chem. 2024 Nov 27;16(2):204-216. doi: 10.1039/d4py00964a. eCollection 2025 Jan 2.
Silicone elastomers are widely used in various applications, each demanding different properties and functionalities. To be used in such a broad spectrum, silicones with easily tunable or switchable properties are needed. We showed this is achievable with novel metallo-supramolecular polysiloxanes. Poly(dimethylsiloxane--3-aminopropylmethylsiloxane) was reacted with an epoxy-modified spiropyran (SP) in the presence of ZnCl as a catalyst. We have found that the ZnCl allows the formation of metallo-supramolecular polymers with tuneable mechanical propertiers. The influence of the amount of ZnCl used on the thermal and mechanical properties of the synthesized materials was investigated by DSC, tensile test, and DMA. The ability of SP to act not only as a physical cross-linker, but also as a molecular switch was investigated by UV-Vis spectroscopy and dielectric permittivity measurements. It was found that depending on the amount of ZnCl used, the dielectric permittivity can either increase or decrease after exposure to UV or visible light, respectively. Additionally, the developed materials can be reprocessed similarly to thermoplastic elastomers. Furthermore, their solubility can be manipulated from insoluble in practically any solvent to highly soluble by simply adding ZnCl.
有机硅弹性体广泛应用于各种领域,每个领域都需要不同的性能和功能。为了在如此广泛的领域中使用,需要具有易于调节或切换性能的有机硅。我们证明了新型金属超分子聚硅氧烷可以实现这一点。聚(二甲基硅氧烷-3-氨丙基甲基硅氧烷)在氯化锌作为催化剂的存在下与环氧改性螺吡喃(SP)反应。我们发现氯化锌能够形成具有可调节机械性能的金属超分子聚合物。通过差示扫描量热法(DSC)、拉伸试验和动态热机械分析(DMA)研究了所用氯化锌的量对合成材料的热性能和机械性能的影响。通过紫外-可见光谱和介电常数测量研究了SP不仅作为物理交联剂,而且作为分子开关的能力。结果发现,根据所用氯化锌的量,在分别暴露于紫外线或可见光后,介电常数可以增加或降低。此外,所开发的材料可以像热塑性弹性体一样进行再加工。此外,通过简单地添加氯化锌,它们的溶解性可以从几乎不溶于任何溶剂变为高度可溶。