Synthesis of hyperbranched polyesters via the ring-opening alternating copolymerisation of epoxides with a cyclic anhydride having a carboxyl group
Synthesis of hyperbranched polyesters via the ring-opening alternating copolymerisation of epoxides with a cyclic anhydride having a carboxyl group
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环氧化物与具有羧基的环状酸酐开环交替共聚合成超支化聚酯
DOI：
10.1039/d2py00571a
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发表时间：
2022
影响因子：
4.6
通讯作者：
Satoh Toshifumi
中科院分区：
文献类型：
--
作者：
Suzuki Ryota;Xia Xiaochao;Gao Tianle;Yamamoto Takuya;Tajima Kenji;Isono Takuya;Satoh Toshifumi
超支化聚酯（HBPE）是一种广泛应用的新型材料。然而，已知的HBPE合成方法缺乏通用性。在此，我们报告了一种新的合成方法HBPE通过开环交替共聚（ROAC）使用环氧化合物和偏苯三酸酐（TA）作为潜在的双官能和三官能单体，分别。TA和过量环氧化物的新戊酸铯催化的ROAC在醇引发剂的存在下在80 °C下本体进行。所获得的产物，连同它们的线性对应物（即，聚（邻苯二甲酰亚胺-交替-环氧化物）通过NMR、粘度和光散射表征。结果支持了超支化聚（TA-alt-epoxide）的成功合成。通过应用一系列醇引发剂，如典型的二醇和官能醇（例如，作为一元醇或二醇的聚（乙二醇）和作为另一元醇的叠氮基-/烯烃官能化醇），产生基于HBPE的嵌段共聚物和官能化HBPE。发现各种环氧化物，如单取代和二取代的环氧烷、缩水甘油醚和缩水甘油胺，可应用于本发明的聚合体系中，其成功地产生了具有不同性质的HBPE，这取决于聚合物的所得主链结构。
Hyperbranched polyesters (HBPEs) are well-known interesting materials used in many fields. However, the known synthetic approaches for HBPEs lack versatility. Herein, we report a novel synthetic approach for an HBPE via ring-opening alternating copolymerisation (ROAC) using epoxides and trimellitic anhydride (TA) as the latent difunctional and trifunctional monomers, respectively. Caesium pivalate-catalysed ROACs of TA and excess epoxides were performed in the presence of an alcohol initiator at 80 °C in bulk. The obtained products, together with their linear counterparts (i.e., poly(phthalic anhydride-alt-epoxide)s), were characterised by NMR, viscometry, and light scattering. The results supported the successful synthesis of hyperbranched poly(TA-alt-epoxide)s. The versatility of the present HBPE synthesis was demonstrated by applying a range of alcohol initiators, such as typical diol and functional alcohols (e.g., poly(ethylene glycol) as a mono-alcohol or diol, and azido-/alkene-functionalised alcohols as another mono-alcohol), leading to HBPE-based block copolymers and functional HBPEs. Various epoxides, such as mono- and disubstituted alkylene oxides, glycidyl ether, and glycidyl amine, were found to be applicable in the present polymerisation system, which successfully produced HBPEs with different properties depending on the resulting backbone structure of the polymer.