Petróczy Anna, Szanka István, Wacha András, Varga Zoltán, Thomann Yi, Thomann Ralf, Mülhaupt Rolf, Bereczki Laura, Hegyesi Nóra, Iván Béla
Polymer Chemistry and Physics Research Group, Institute of Materials and Environmental Chemistry, HUN-REN Research Centre for Natural Sciences, Magyar tudósok körútja 2, H-1117 Budapest, Hungary.
George Hevesy PhD School of Chemistry, Institute of Chemistry, Faculty of Science, Eötvös Loránd University, Pázmány Péter Sétány 2, H-1117 Budapest, Hungary.
Gels. 2025 Apr 24;11(5):318. doi: 10.3390/gels11050318.
Polymer conetworks, which consist of two or more covalently crosslinked polymer chains, not only combine the individual characteristics of their components, but possess various unique structural features and properties as well. In this study, we report on the successful synthesis of a library of polystyrene--poly(dimethylsiloxane) (PSt--PDMS) ("" stands for "") and polystyrene--poly(dimethylsiloxane)/divinylbenzene (PSt--PDMS/DVB) polymer conetworks. These conetworks were prepared via free radical copolymerization of styrene (St) with methacryloxypropyl-telechelic poly(dimethylsiloxane) (MA-PDMS-MA) as macromolecular crosslinker in the absence and presence of DVB with 36:1 and 5:1 St/DVB ratios (/), the latter leading to hypercrosslinked conetworks. Macroscopically homogeneous, transparent conetworks with high gel fractions were obtained over a wide range of PDMS contents from 30 to 80 /%. The composition of the conetworks determined by elemental analysis was found to be in good agreement with that obtained from the H NMR spectra of the extraction residues, as a new method which can be widely used to easily determine the composition of multicomponent networks and gels. DSC, SAXS, and AFM measurements clearly indicate bicontinuous disordered nanophase separated morphology for all the investigated conetworks with domain sizes in the range of 3-30 nm, even for the hypercrosslinked PSt--PDMS/DVB conetworks with extremely high crosslinking density. The cocontinuous morphology is also proved by selective, composition-dependent uniform swelling in hexane for the PDMS and in 1-nitropropane for the PSt domains. The Korsmeyer-Peppas type evaluation of the swelling data indicates hindered Fickian diffusion of both solvents in the conetwork organogels. The unique nanophasic bicontinuous morphology and the selective swelling behavior of the PSt--PDMS and PSt--PDMS/DVB conetworks and their gels offer a range of various potential applications.
聚合物互穿网络由两条或更多条共价交联的聚合物链组成，它不仅结合了各组分的个体特性，还具备各种独特的结构特征和性能。在本研究中，我们报道了聚苯乙烯-聚（二甲基硅氧烷）（PSt-PDMS）（“--”表示“至”）和聚苯乙烯-聚（二甲基硅氧烷）/二乙烯基苯（PSt-PDMS/DVB）聚合物互穿网络库的成功合成。这些互穿网络是通过苯乙烯（St）与作为大分子交联剂的甲基丙烯酰氧基丙基-遥爪聚（二甲基硅氧烷）（MA-PDMS-MA）在不存在和存在二乙烯基苯（DVB）的情况下进行自由基共聚制备的，St/DVB比例分别为36:1和5:1（质量比），后者导致超交联互穿网络。在30%至80%（质量分数）的广泛PDMS含量范围内，获得了宏观均匀、透明且凝胶分数高的互穿网络。通过元素分析确定的互穿网络组成与从萃取残渣的1H NMR光谱获得的结果高度一致，这是一种可广泛用于轻松确定多组分网络和凝胶组成的新方法。差示扫描量热法（DSC）、小角X射线散射（SAXS）和原子力显微镜（AFM）测量清楚地表明，所有研究的互穿网络都具有双连续无序的纳米相分离形态，其域尺寸在3至30纳米范围内，即使是具有极高交联密度的超交联PSt-PDMS/DVB互穿网络也是如此。PDMS在己烷中以及PSt域在1-硝基丙烷中的选择性、依赖组成的均匀溶胀也证明了这种共连续形态。对溶胀数据的Korsmeyer-Peppas类型评估表明，两种溶剂在互穿网络有机凝胶中的扩散均受到阻碍，呈现菲克扩散受阻的情况。PSt-PDMS和PSt-PDMS/DVB互穿网络及其凝胶独特的纳米相双连续形态和选择性溶胀行为提供了一系列潜在的应用。
