Diez Sergej, Hoefling Alexander, Theato Patrick, Pauer Werner
Technical and Macromolecular Chemistry, University of Hamburg, Hamburg D-20146, Germany.
Polymers (Basel). 2017 Feb 15;9(2):59. doi: 10.3390/polym9020059.
Recently, new methods have been developed for the utilization of elemental sulfur as a feedstock for novel polymeric materials. One promising method is the inverse vulcanization, which is used to prepare polymeric structures derived from sulfur and divinyl comonomers. However, the mechanical and electrical properties of the products are virtually unexplored. Hence, in the present study, we synthesized a 200 g scale of amorphous, hydrophobic as well as translucent, hyperbranched polymeric sulfur networks that provide a high thermal resistance (>220 °C). The polymeric material properties of these sulfur copolymers can be controlled significantly by varying the monomers as well as the feed content. The investigated comonomers are divinylbenzene (DVB) and 1,3-diisopropenylbenzene (DIB). Plastomers with low elastic content and high shape retention containing 12.5%⁻30% DVB as well as low viscose waxy plastomers with a high flow behavior containing a high DVB content of 30%⁻35% were obtained. Copolymers with 15%⁻30% DIB act, on the one hand, as thermoplastics and, on the other hand, as vitreous thermosets with a DIB of 30%⁻35%. Results of the thermogravimetric analysis (TGA), the dynamic scanning calorimetry (DSC) and mechanical characterization, such as stress⁻strain experiments and dynamic mechanical thermal analysis, are discussed with the outcome that they support the assumption of a polymeric cross-linked network structure in the form of hyper-branched polymers.
最近，已开发出利用元素硫作为新型聚合物材料原料的新方法。一种有前景的方法是反向硫化，用于制备由硫和二乙烯基共聚单体衍生的聚合物结构。然而，这些产品的机械和电学性能几乎未被探索。因此，在本研究中，我们合成了200克规模的无定形、疏水且半透明的超支化聚合物硫网络，其具有高耐热性（>220°C）。通过改变单体以及进料含量，可以显著控制这些硫共聚物的聚合物材料性能。所研究的共聚单体是二乙烯基苯（DVB）和1,3 - 二异丙烯基苯（DIB）。获得了弹性含量低且形状保持率高的塑性体，其中含有12.5% - 30%的DVB，以及具有高流动行为的低粘度蜡状塑性体，其DVB含量高达30% - 35%。含有15% - 30% DIB的共聚物一方面表现为热塑性塑料，另一方面，当DIB含量为30% - 35%时表现为玻璃态热固性材料。讨论了热重分析（TGA）、动态扫描量热法（DSC）和机械表征（如应力 - 应变实验和动态机械热分析）的结果，结果支持了超支化聚合物形式的聚合物交联网络结构的假设。
