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Bioinspired All‐Polyester Diblock Copolymers Made from Poly(pentadecalactone) and Poly(3‐hydroxycinnamate): Synthesis and Polymer Film Properties
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-05-05 , DOI: 10.1002/macp.202000045 Julia S Saar 1 , Yue Shi 1 , Karen Lienkamp 1
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-05-05 , DOI: 10.1002/macp.202000045 Julia S Saar 1 , Yue Shi 1 , Karen Lienkamp 1
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A bioinspired diblock copolymer is synthesized from pentadecalactone and 3‐hydroxy cinnamic acid. Poly(pentadecalactone) (PPDL) with a molar mass of up to 43 000 g mol−1 is obtained by ring‐opening polymerization initiated by propargyl alcohol. Poly(3‐hydroxycinnamate) (P3HCA) is obtained by polycondensation and end‐functionalized with 3‐azido propanol. The two functionalized homopolymers are connected via 1,3‐dipolar Huisgen addition to yield the block copolymer PPDL‐triazole‐P3HCA. The structure of the block copolymer is confirmed by proton NMR, FTIR spectroscopy and GPC. By analyzing the morphology of polymer films made from the homopolymers, from a 1:1 homopolymer blend, and from the PPDL‐triazole‐P3HCA block copolymer, clearly distinct micro‐ and nanostructures are revealed. Quantitative nanomechanical measurements reveal that the block copolymer PPDL‐triazole‐P3HCA has a DMT modulus of 22.3 ± 2.7 MPa, which is lower than that of the PPDL homopolymer (801 ± 42 MPa), yet significantly higher than that of the P3HCA homopolymer (1.77 ± 0.63 MPa). Thermal analytics show that the melting point of PPDL‐triazole‐P3HCA is similar to PPDL (89–90 °C), while it has a glass transition temperature similar to P3HCA (123–124 °C). Thus, the semicrystalline, potentially degradable all‐polyester block copolymer PPDL‐triazole‐P3HCA combines the thermal properties of either homopolymer, and has an intermediate elastic modulus.
中文翻译：
由聚（十五内酯）和聚（3-羟基肉桂酸酯）制成的仿生全聚酯二嵌段共聚物：合成和聚合物薄膜性能
一种仿生二嵌段共聚物是由十五内酯和 3-羟基肉桂酸合成的。摩尔质量高达 43 000 g mol -1的聚十五内酯（PPDL）是通过炔丙醇引发的开环聚合获得的。聚（3-羟基肉桂酸酯）（P3HCA）通过缩聚获得，并用 3-叠氮基丙醇进行末端官能化。两种官能化均聚物通过 1,3-偶极惠斯根加成反应生成嵌段共聚物 PPDL-三唑-P3HCA。通过质子NMR、FTIR光谱和GPC证实了嵌段共聚物的结构。通过分析由均聚物、1:1 均聚物共混物和 PPDL-三唑-P3HCA 嵌段共聚物制成的聚合物薄膜的形态，揭示了明显不同的微米和纳米结构。定量纳米力学测量表明，嵌段共聚物 PPDL-三唑-P3HCA 的 DMT 模量为 22.3 ± 2.7 MPa，低于 PPDL 均聚物 (801 ± 42 MPa)，但显着高于 P3HCA 均聚物 (1.77 ±0.63兆帕）。热分析表明，PPDL-三唑-P3HCA的熔点与PPDL相似（89-90°C），而其玻璃化转变温度与P3HCA相似（123-124°C）。因此，半结晶、可降解的全聚酯嵌段共聚物 PPDL-三唑-P3HCA 结合了任一均聚物的热性能，并具有中间弹性模量。
更新日期：2020-05-05
中文翻译：
由聚（十五内酯）和聚（3-羟基肉桂酸酯）制成的仿生全聚酯二嵌段共聚物：合成和聚合物薄膜性能
一种仿生二嵌段共聚物是由十五内酯和 3-羟基肉桂酸合成的。摩尔质量高达 43 000 g mol -1的聚十五内酯（PPDL）是通过炔丙醇引发的开环聚合获得的。聚（3-羟基肉桂酸酯）（P3HCA）通过缩聚获得，并用 3-叠氮基丙醇进行末端官能化。两种官能化均聚物通过 1,3-偶极惠斯根加成反应生成嵌段共聚物 PPDL-三唑-P3HCA。通过质子NMR、FTIR光谱和GPC证实了嵌段共聚物的结构。通过分析由均聚物、1:1 均聚物共混物和 PPDL-三唑-P3HCA 嵌段共聚物制成的聚合物薄膜的形态，揭示了明显不同的微米和纳米结构。定量纳米力学测量表明，嵌段共聚物 PPDL-三唑-P3HCA 的 DMT 模量为 22.3 ± 2.7 MPa，低于 PPDL 均聚物 (801 ± 42 MPa)，但显着高于 P3HCA 均聚物 (1.77 ±0.63兆帕）。热分析表明，PPDL-三唑-P3HCA的熔点与PPDL相似（89-90°C），而其玻璃化转变温度与P3HCA相似（123-124°C）。因此，半结晶、可降解的全聚酯嵌段共聚物 PPDL-三唑-P3HCA 结合了任一均聚物的热性能，并具有中间弹性模量。
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