Combination of Ring-Opening Polymerization and “Click Chemistry”:  Toward Functionalization and Grafting of Poly(ε-caprolactone)

Abstract

Raphae 1l Riva, Ste ´phanie Schmeits, Christine Je ´ro ˆme, Robert Je ´ro ˆme,* and

Synthesis of new substituted lactones by "click" chemistry

“…We previously reported on the successful cycloaddition of duly substituted low molecular weight or polymeric alkynes onto the pendant azide groups of PCL and poly(3,6-dimethyl-1,4-dioxane-2,5-dione) (poly(lactide) or PLA). 3,25,26 This reaction was complete within short reaction times (< 2h). Moreover, when the reaction was carried out at 35°C in an organic medium (THF or DMF), no degradation of the polyester chains was observed, even in case of the hydrolytically unstable PLA.…”

“…"Click" chemistry was used to convert the bromide group of 5-bromooxepan-2-one 6 into a bromoisobutyrate, known as an initiator of ATRP. 26 For this purpose, 5-azidooxepan-2-one 10 was reacted with prop-2-yn-1-yl 2-bromo-2-methylpropanoate 20 and [1-(7-oxooxepan-4-yl)-1H-1,2,3-triazol-4-yl]methyl 2-bromo-2-methylpropanoate 21 was formed in high yield (Scheme 4). Synthesis of aliphatic polyesters with pendant acrylates is highly desirable for making them cross-linkable and appropriate precursors of biodegradable networks.…”

“…Synthesis of aliphatic polyesters with pendant acrylates is highly desirable for making them cross-linkable and appropriate precursors of biodegradable networks. 5,26 Moreover, strategies for the production of nanoparticles 28 and macrocyclic polyesters 29 rely on the intramolecular crosslinking of pendant acrylates. Until now, acrylates substituted aliphatic polyesters were synthesized by ring-opening polymerization of 7-oxooxepan-4-yl acrylate 22 and 1-(2-oxooxepan-3-yl)ethyl acrylate 23, respectively.…”

Synthesis and Properties of Thermo-sensitive Amphiphilic Pluronic-b-poly((ε-caprolactone)-co-(6-(benzyl-oxycarbonylmethyl)-ε-caprolactone))

“…通 过对己内酯进行官能化改性, 改善其结晶性和疏水性, 赋予聚己内酯进一步参与反应的能力, 是拓展己内酯应 用的一种行之有效的方法. Jérôme 等 [13] 先后采用 4-溴-己内酯开环聚合得到溴修饰的聚己内酯, 采用 2-氯-己 内酯开环聚合得到悬挂有氯原子的聚己内酯, 再进一步 利用叠氮化钠亲核取代得到 2-叠氮基-聚己内酯 [14] . [18] 的前期研究中, 合成了主 链带有羧基的 PEG-PCL 聚合物, 并探索了羧基官能团 对于聚合物胶束形成机理和 pH 敏感性的影响.…”

“…如图 3 所示, 与 PFPC 9k 1 (Entry 0)相比, 随着 BCL 含量的增加, PCL 酯羰基吸收峰逐渐从结晶区的 1727.0 [19] . [14] . 此外, 可以发现随着 BCL 的加入, 共聚物的玻璃化转变温度也从-64.80 ℃ (PFPC 9k 1, Entry 0)升高到-55.26 ℃ (PFPB 9k 4, Entry 3), 这同样是由引入的侧乙酸苄酯基造成的 [24] .…”