Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003, United States.
ACS Macro Lett. 2022 Nov 15;11(11):1245-1251. doi: 10.1021/acsmacrolett.2c00548. Epub 2022 Oct 13.
Methyl-, vinyl-, and hydride-terminated polymers of the heterocyclic monomer, 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane (-ME) were prepared by sulfuric acid-catalyzed, ring-opening equilibration with the end-capping agents hexamethyldisiloxane (MM), divinyltetramethyldisiloxane (MM), and tetramethyldisiloxane (MM), respectively. The molecular weights of the polymers were controlled by adjusting the ratio of monomer to end-capping agent. All of these polymers are oils and exhibit molecular weight-dependent viscosities that are qualitatively similar to those of polydimethylsiloxane (PDMS)-based analogs prepared by the same reaction using octamethylcyclotetrasiloxane (D) instead of -ME. Vinyl end-capped polymers with a range of molecular weights were cross-linked by platinum-catalyzed hydrosilylation with tetramethylcyclotetrasiloxane (D) to prepare a series of transparent solid elastomers with moduli that increase with decreasing molecular weight. These studies suggest that reactive polymers prepared from -ME may be useful resins in two-part curable elastomer formulations. Several experiments, as well as the over 60-year-old initial synthesis of this polymer, suggest that the recyclability of these resins and elastomers may be practical.
通过硫酸催化,分别用端封试剂六甲基二硅氧烷(MM)、二乙烯基四甲基二硅氧烷(MM)和四甲基二硅氧烷(MM)与杂环单体 2,2,5,5-四甲基-2,5-二硅氧杂环戊烷(-ME)进行开环平衡反应,制备了 -ME 的甲基、乙烯基和氢封端聚合物。通过调节单体与端封试剂的比例控制聚合物的分子量。所有这些聚合物都是油状的,表现出分子量依赖性粘度,与使用八甲基环四硅氧烷(D)代替 -ME 通过相同反应制备的基于聚二甲基硅氧烷(PDMS)的类似物的粘度定性相似。通过铂催化的氢化硅烷化反应,用四甲基环四硅氧烷(D)交联具有一系列分子量的乙烯基封端聚合物,制备了一系列具有模量随分子量降低而增加的透明固体弹性体。这些研究表明,由 -ME 制备的反应性聚合物可能是双组分可固化弹性体配方中的有用树脂。一些实验以及该聚合物超过 60 年的初始合成表明,这些树脂和弹性体的可回收性可能是实际的。