Bioinspired All‐Polyester Diblock Copolymers Made from Poly(pentadecalactone) and Poly(2‐(2‐hydroxyethoxy)benzoate): Synthesis and Polymer Film Properties,Macromolecular Chemistry and Physics

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Bioinspired All‐Polyester Diblock Copolymers Made from Poly(pentadecalactone) and Poly(2‐(2‐hydroxyethoxy)benzoate): Synthesis and Polymer Film Properties
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-05-19 , DOI: 10.1002/macp.202000118
Julia S Saar ₁ , Karen Lienkamp ₁

Affiliation

The bioinspired diblock copolymers poly(pentadecalactone)‐block‐poly(2‐(2‐hydroxyethoxy)benzoate) (PPDL‐block‐P2HEB) are synthesized from pentadecalactone and dihydro‐5H‐1,4‐benzodioxepin‐5‐one (2,3‐DHB). No transesterification between the blocks is observed. In a sequential approach, PPDL obtained by ring‐opening polymerization (ROP) is used to initiate 2,3‐DHB. Here, the molar mass M_n of the P2HEB block is limited. In a modular approach, end‐functionalized PPDL and P2HEB are obtained separately by ROP with functional initiators, and connected by 1,3‐dipolar Huisgen reaction (“click‐chemistry”). Block copolymer compositions from 85:15 mass percent to 28:72 mass percent (PPDL:P2HEB) are synthesized, with M_n of from about 30 000–50 000 g mol⁻¹. The structure of the block copolymer is confirmed by proton NMR, Fourier‐transform infrared spectroscopy, and gel permeation chromatography. Morphological studies by atomic force microscopy (AFM) further confirms the block copolymer structure, while quantitative nanomechanical AFM measurements reveal that the Derjaguin–Muller–Toporov moduli of the block copolymers range between 17.2 ± 1.8 and 62.3 ± 5.7 MPa, i.e., between the values of the parent P2HEB and PPDL homopolymers (7.6 ± 1.4 and 801 ± 42 MPa, respectively). Differential scanning calorimetry shows that the thermal properties of the homopolymers are retained by each of the copolymer blocks (melting temperature 90 °C, glass transition temperature 36 °C).

中文翻译：

由聚（十五内酯）和聚（2-（2-羟基乙氧基）苯甲酸酯）制成的仿生全聚酯二嵌段共聚物：合成和聚合物薄膜性能

仿生二嵌段共聚物聚（十五内酯）-嵌段-聚（2-（2-羟基乙氧基）苯甲酸酯）（PPDL-嵌段-P2HEB）由十五内酯和二氢-5H-1,4-苯并二氧杂环己烷-5-酮（2， 3-DHB）。没有观察到嵌段之间的酯交换反应。在顺序方法中，通过开环聚合 (ROP) 获得的 PPDL 用于引发 2,3-DHB。这里， P2HEB嵌段的摩尔质量M _{n是有限的。}在模块化方法中，末端功能化的 PPDL 和 P2HEB 分别通过 ROP 和功能引发剂获得，并通过 1,3-偶极 Huisgen 反应（“点击化学”）连接。合成了85:15质量百分比至28:72质量百分比(PPDL:P2HEB)的嵌段共聚物组合物，M _n为约30000-50000gmol ^-1。通过质子核磁共振、傅里叶变换红外光谱和凝胶渗透色谱证实了嵌段共聚物的结构。原子力显微镜 (AFM) 的形态研究进一步证实了嵌段共聚物的结构，而定量纳米机械 AFM 测量表明，嵌段共聚物的 Derjaguin-Muller-Toporov 模量范围在 17.2 ± 1.8 和 62.3 ± 5.7 MPa 之间，即在这些值之间母体 P2HEB 和 PPDL 均聚物（分别为 7.6 ± 1.4 和 801 ± 42 MPa）。差示扫描量热法表明，每个共聚物嵌段都保留了均聚物的热性能（熔融温度 90 °C，玻璃化转变温度 36 °C）。

更新日期：2020-05-19

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