Sulfenyl Chlorides: An Alternative Monomer Feedstock from Elemental Sulfur for Polymer Synthesis
Sulfenyl Chlorides: An Alternative Monomer Feedstock from Elemental Sulfur for Polymer Synthesis
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DOI：
10.1021/jacs.2c10317
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发表时间：
2022-12-07
影响因子：
15
通讯作者：
Pyun, Jeffrey
中科院分区：
文献类型：
--
作者：
Kang, Kyung-Seok;Olikagu, Chisom;Pyun, Jeffrey
报道了使用一氯化硫（S2 Cl 2）作为聚合物材料的替代原料的聚合方法。S2 Cl 2是一种源自元素硫（S8）的廉价石化产品，但与S8相比，作为聚合反应的反应性单体具有许多优点。这种新的工艺，称为磺酰氯反相硫化，利用高反应性和可溶解性的S2 Cl 2与广泛的烯丙基单体制备可溶性，高摩尔质量的线性聚合物，嵌段共聚物，和交联热固性材料具有更大的合成精度比使用经典的反相硫化。这种逐步增长加成聚合还允许制备一类新的无硫醇、廉价、高度光学透明的热固性材料（在1310 nm处α = 0.045 cm-1），其相对于商品光学聚合物表现出最好的光学透明度和低双折射率，同时在可见光和近红外光谱中具有较高的折射率（n > 1.6）。同时也展示了大尺寸光学元件的制作。
A polymerization methodology is reported using sulfur mono chloride (S2Cl2) as an alternative feedstock for polymeric materials. S2Cl2 is an inexpensive petrochemical derived from elemental sulfur (S8) but has numerous advantages as a reactive monomer for polymerization vs S8. This new process, termed sulfenyl chloride inverse vulcanization, exploits the high reactivity and miscibility of S2Cl2 with a broad range of allylic monomers to prepare soluble, high molar-mass linear polymers, segmented block copolymers, and crosslinked thermosets with greater synthetic precision than achieved using classical inverse vulcanization. This step-growth addition polymerization also allows for preparation of a new class of thiol-free, inexpensive, highly optically transparent thermosets (alpha = 0.045 cm-1 at 1310 nm), which exhibit among the best optical transparency and low birefringence relative to commodity optical polymers, while possessing a higher refractive index (n > 1.6) in the visible and near-infrared spectra. The fabrication of large-sized optical components is also demonstrated.