Fluorinated polyesters have demonstrated significant research value and application prospects, while their traditional synthetic strategies were restrained by harsh reaction conditions, low monomer activity, and limited polymer topology. Herein, we exploited reversible addition–fragmentation chain transfer (RAFT) step-growth polymerization to prepare fluorinated polyesters with tailor-made chemical compositions and correlated their thermal and surface properties with chemical structures. A model polymerization was first performed using the fluorinated bifunctional chain transfer agent (CTA) BDMAT_8F and N,N′-(1,4-phenylene)dimaleimide as the monomers, and the polymerization kinetics was monitored through nuclear magnetic resonance (NMR) spectroscopy and size exclusion chromatography (SEC), which suggested a step-growth polymerization mechanism. With this method, fluorinated polyesters with different chemical structures were synthesized by varying the molecular structures of the bifunctional CTA and the bismaleimide monomer. The chemical structure and molecular weight of the synthesized fluorinated polyesters were characterized by ¹H NMR, ¹⁹F NMR, and SEC, the thermal properties were characterized by thermogravimetric analyses and differential scanning calorimetry, and the surface properties were characterized by water contact angle (WCA) measurements. The glass transition temperature (T_g) of these fluorinated polyesters was correlated with their chemical structures, where a rigid backbone favored a high T_g, while a flexible pendant group decreased the T_g. However, neither the backbone rigidity nor the fluorine content had an obvious effect on the WCA of the fluorinated polyesters. Instead, the pendant group showed a significant influence on their WCA. The unique advantage of RAFT step-growth polymerization for preparing fluorinated polyesters was demonstrated by the preparation of a novel fluorinated polyester brush by grafting copolymerization of acryloylmorpholine through RAFT radical polymerization from an as-synthesized fluorinated polyester. Both the thermal and surface properties of this fluorinated polyester brush were strongly correlated with the properties of the poly(acryloylmorpholine) sidechains. This method has provided a new platform for the preparation of fluorinated polyesters and will provide new insight for tailoring the properties of polyesters.

中文翻译：

---

可逆加成断裂链转移逐步增长聚合制备氟化聚酯

氟化聚酯已表现出重要的研究价值和应用前景，但其传统的合成策略受到反应条件苛刻、单体活性低和聚合物拓扑结构有限的限制。在此，我们利用可逆加成-断裂链转移（RAFT）逐步增长聚合来制备具有定制化学成分的氟化聚酯，并将其热性能和表面性能与化学结构相关联。首先使用氟化双功能链转移剂（CTA）BDMAT _8F和N , N '-(1,4-亚苯基)二马来酰亚胺作为单体进行模型聚合，并通过核磁共振（NMR）光谱监测聚合动力学和尺寸排阻色谱（SEC），这表明了逐步增长的聚合机制。利用该方法，通过改变双官能CTA和双马来酰亚胺单体的分子结构，合成了具有不同化学结构的氟化聚酯。^通过1 H NMR、¹⁹ F NMR和SEC表征合成的氟化聚酯的化学结构和分子量，通过热重分析和差示扫描量热法表征热性能，通过水接触角（WCA）表征表面性能。 ） 测量。这些氟化聚酯的玻璃化转变温度（T _g）与其化学结构相关，其中刚性主链有利于高T _g，而柔性侧基则降低T _g。然而，主链刚性和氟含量对氟化聚酯的WCA没有明显影响。相反，吊坠组对 WCA 表现出显着影响。通过将合成的氟化聚酯通过RAFT自由基聚合接枝共聚丙烯酰吗啉制备了新型氟化聚酯刷，证明了RAFT逐步增长聚合制备氟化聚酯的独特优势。这种氟化聚酯刷的热性能和表面性能与聚（丙烯酰吗啉）侧链的性能密切相关。该方法为氟化聚酯的制备提供了新的平台，并将为定制聚酯的性能提供新的见解。