Functional polypropylenes (FPs) are regarded as versatile building blocks for next-generation materials; however, their development has been stymied due to current synthetic limitations. Here, we report a diverse range of functionalized polypropylenes prepared via a two-step copolymerization−postmodification strategy. Solution-phase copolymerization of propylene and 11-bromo-1-undecene using C₂, C₁, and C_s-symmetric catalysts-afforded poly(propylene)-co-(11-bromo-1-undecene), with tunable comonomer incorporation levels, up to 15.5 mol %, with a range of tacticities (iso-, syndio-, and atactic) and a wide molecular weight span (4−212 kg mol⁻¹). The latent electrophilic reactivity of the pendent bromide has been utilized in one of three general synthetic routes, enabling the incorporation of an array of polar substituents through the formation of a series of covalent connections (C−O, C−N, C−S, C−P, and C−C). The resulting FPs display distinctly altered bulk and surface properties, compared to polypropylene: improved thermal stability and adhesion to metal, altered wettability, and latent reactivity. This strategy allows access to FPs with both high molecular weight and chosen tacticity, taking advantage of well-developed metallocene catalysts and classical organic substitution chemistry.

中文翻译：

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功能化聚丙烯：共聚和后改性平台


功能性聚丙烯 （FP） 被认为是下一代材料的多功能基础材料;然而，由于目前的合成限制，它们的发展受到了阻碍。在这里，我们报道了通过两步共聚-后修饰策略制备的各种官能化聚丙烯。丙烯和 11-溴-1-十一烯的液相共聚，使用 C₂、C₁ 和 C_{s 对称}催化剂-提供聚（丙烯）-co-（11-溴-1-十一烯），具有可调的共聚单体掺入水平，高达 15.5 mol %，具有一系列策略（iso-、syndio 和无规）和宽分子量范围 （4-212 kg ^mol-1).悬垂溴化物的潜在亲电反应性已用于三种一般合成路线之一，能够通过形成一系列共价连接（C-O、C-N、C-S、C-P 和 C-C）来掺入一系列极性取代基。与聚丙烯相比，所得 FP 显示出明显改变的体积和表面特性：更高的热稳定性和对金属的粘附性、改变的润湿性和潜伏反应性。该策略允许获得具有高分子量和所选策略的 FP，利用成熟的茂金属催化剂和经典的有机取代化学。