Navarro Rodrigo, Perrino Mónica Pérez, García Carolina, Elvira Carlos, Gallardo Alberto, Reinecke Helmut
Instituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Calle Juan de la Cierva 3, 28863 Madrid, Spain.
Polymers (Basel). 2016 Apr 19;8(4):152. doi: 10.3390/polym8040152.
Several synthetic strategies based on the use of substituted aromatic and hetero-aromatic thiols for the covalent binding of modifier compounds to PVC are described. A variety of aliphatic alcohols and amines are linked to the aromatic or heteroaromatic rings via highly active functionalities as the isocyanate, acidchloride, or chlorosulfonyl group, and the three chlorine atoms of trichlorotriazine. The first three pathways lead to protected aromatic disulfides obtaining the substituted aromatic thiols by reduction as a final step of an unprecedented synthetic route. The second approach, in a novel, extremely efficient, and scalable process, uses the particular selectivity of trichlorotriazine to connect aliphatic amines, alcohols, and thiols to the ring and creates the thiol via nucleophilic substitution of a heteroaromatic halogen by thiourea and subsequent hydrolysis. Most of the modifier compounds were linked to the polymer chains with high degrees of anchorage. The presented approaches are highly versatile as different activations of aromatic and heteroaromatic rings are used. Therefore, many types of tailored functional nucleophiles may be anchored to PVC providing non-migrating materials with a broad range of applications and properties.
描述了几种基于使用取代的芳族和杂芳族硫醇将改性剂化合物共价结合到聚氯乙烯（PVC）上的合成策略。多种脂肪族醇和胺通过高活性官能团（如异氰酸酯、酰氯或氯磺酰基以及三氯三嗪的三个氯原子）连接到芳族或杂芳族环上。前三种途径导致得到受保护的芳族二硫化物，通过还原得到取代的芳族硫醇，这是一条前所未有的合成路线的最后一步。第二种方法采用一种新颖、极其高效且可扩展的工艺，利用三氯三嗪的特殊选择性将脂肪族胺、醇和硫醇连接到环上，并通过硫脲对杂芳族卤素的亲核取代以及随后的水解来生成硫醇。大多数改性剂化合物以高度的锚固作用连接到聚合物链上。由于使用了芳族和杂芳族环的不同活化方式，所提出的方法具有高度的通用性。因此，许多类型的定制功能亲核试剂可以锚固到PVC上，从而提供具有广泛应用和性能的非迁移材料。
