Double neighbouring group participation for ultrafast exchange in phthalate monoester networks,Polymer Chemistry

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Double neighbouring group participation for ultrafast exchange in phthalate monoester networks
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-07-16 , DOI: 10.1039/d0py00681e
Maarten Delahaye _{1,

2,

3,

4,

5} , Flaminia Tanini _{1,

2,

3,

4,

5} , Joshua O. Holloway _{1,

2,

3,

4,

5} , Johan M. Winne _{3,

4,

5,

6,

7} , Filip E. Du Prez _{1,

2,

3,

4,

5}

Affiliation

Phthalate monoesters (PMEs) were recently introduced as a simple dynamic covalent bond for implementation in covalent adaptable networks (CANs), which undergo rapid transesterifications in the absence of catalysts, due to the neighbouring group participation (NGP) of a carboxylic acid moiety. In this work, it is shown that the PME transesterification can be very significantly accelerated by the presence of another neighbouring group on the reactive alcohol moieties. The kinetic effects are demonstrated using a short model study of PMEs with different substituents at the β-carbon position, showing a remarkable acceleration for alcohols containing tertiary amines on the β-carbon. Following the model study, materials were synthesised by a (partial) replacement of the conventionally used diol with a β-amino-diol, leading to the formation of networks with an increased T_g and Young's-modulus, which is rationalised as a result of the formation of an ionic network (COO⁻ and NHR₃⁺). Stress relaxation experiments show a decrease in relaxation times by a factor of 500, compared to similar networks derived from non-amine-substituted hydroxyl monomers. This ultrafast relaxation, enabled by a double NGP, resulted in CANs that show potential to be processed through extrusion while maintaining their overall network connectivity.

中文翻译：

邻国双倍参与，可实现邻苯二甲酸单酯网络的超快速交换

邻苯二甲酸单酯（PME）最近作为一种简单的动态共价键引入，用于在共价适应性网络（CAN）中实施，由于羧酸部分的相邻基团参与（NGP），该共价适应性网络在不存在催化剂的情况下进行了快速酯交换反应。在这项工作中，表明通过在反应性醇部分上存在另一个相邻基团，可以非常显着地促进PME酯交换反应。通过对在β-碳位置具有不同取代基的PME进行的简短模型研究，证明了动力学效果，对于在β-碳上包含叔胺的醇而言，显示出显着的加速作用。在进行模型研究之后，通过用β-氨基-二醇（部分）替代常规使用的二醇来合成材料，Ť_克该合理化作为离子网络的形成的结果和Young's模量，（COO ^-和NHR ₃⁺）。与衍生自非胺取代的羟基单体的类似网络相比，应力松弛实验显示松弛时间减少了500倍。双NGP可以实现这种超快的放松，从而使CAN表现出潜力，可以在保持总体网络连接性的同时通过挤压进行处理。

更新日期：2020-08-18

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