Department of Chemistry , Massachusetts Institute of Technology , Cambridge , Massachusetts 02139 , United States.
J Am Chem Soc. 2019 Aug 14;141(32):12498-12501. doi: 10.1021/jacs.9b06009. Epub 2019 Jul 31.
The postpolymerization modification of polymers produced by living polymerization is an attractive method to create precision nanomaterials. We describe the living cationic ring-opening polymerization of a 2-alkylthio-2-oxazoline to furnish a polythiocarbamate. The polythiocarbamate is activated toward substitution by - and -nucleophiles via oxidation of the S to an SO. Mild substitution conditions provide broad functional group tolerance, constituting a versatile postpolymerization modification platform with access to a diversity of polyureas and polythiocarbamates. We further demonstrate the utility of this strategy by synthesizing and functionalizing block copolymers.
通过活性聚合制备的聚合物的后聚合修饰是一种制备精确纳米材料的有吸引力的方法。我们描述了通过 2-烷硫基-2-恶唑啉的活性阳离子开环聚合来制备聚硫代碳酸酯。该聚硫代碳酸酯通过将 S 氧化为 SO 而被 - 和 - 亲核试剂取代所激活。温和的取代条件提供了广泛的官能团耐受性，构成了一种多功能的后聚合修饰平台，可获得各种聚脲和聚硫代碳酸酯。我们通过合成和功能化嵌段共聚物进一步证明了该策略的实用性。
