Tuning of the Topochemical Polymerization of Diacetylenes Based on an Odd/Even Effect of the Peripheral Alkyl Chain: Thermochromic Reversibility in a Thin Film and a Single-Component Ink for a Fountain Pen.
Tuning of the Topochemical Polymerization of Diacetylenes Based on an Odd/Even Effect of the Peripheral Alkyl Chain: Thermochromic Reversibility in a Thin Film and a Single-Component Ink for a Fountain Pen.
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DOI：
10.1021/acsami.8b05896
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发表时间：
2018-06
影响因子：
9.5
通讯作者：
M. Kim;Satheshkumar Angupillai;K. Min;Manivannan Ramalingam;Y. Son
中科院分区：
文献类型：
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作者：
M. Kim;Satheshkumar Angupillai;K. Min;Manivannan Ramalingam;Y. Son
双炔类的拓扑化学聚合与其烷基链的长度密切相关。DA单体具有两种类型的烷基链侧基：内部烷基链和外部烷基链，即外围烷基链。本文中，我们设计并合成了一系列具有不同外周烷基链的双酰胺键的DA单体（n = 6-9; DA 1-DA 4）。这些DA单体的外周烷基链长度表现出奇/偶的拓扑化学聚合的效果。只有当n为奇数时，才能实现DA的聚合，而当n为偶数时，则不会发生聚合。奇/偶效应的拓扑化学聚合进行了研究，使用从头算密度泛函理论计算。利用紫外-可见吸收光谱研究了聚二乙炔（PDA）在20 ~ 60 °C温度范围内的热致变色可逆性。MPDDA 2被用作钢笔中的单组分墨水溶液，其可以在常规纸上转化成热致变色字母。此外，包括PDA嵌入的聚环氧乙烷膜以监测热致变色可逆性，并且发现其在20 ° C至100 °C之间表现出优异的热致变色可逆性和稳定性，能够储存数月而不变形。最后，通过减色（蓝色和黄色）混合方法容易地获得绿色图案化聚合物膜，并且在20 ° C和100 °C之间的温度下表现出高热致变色可逆性。
The topochemical polymerization of diacetylenes (DAs) is closely related to the length of their alkyl chain. DA monomers have two types of alkyl chain side groups: the inner alkyl chain and the outer alkyl chain, that is, the peripheral alkyl chain. Herein, we designed and synthesized a series of DA monomers that possess bis-amide linkages with different peripheral alkyl chains ( n = 6-9; DA1-DA4). The peripheral alkyl chain length of these DA monomers exhibits an odd/even effect on topochemical polymerization. The polymerization of DAs was achieved only when n is an odd number, whereas no polymerization occurred when n is an even number. The odd/even effect on the topochemical polymerization was also investigated using ab initio density functional theory calculations. The thermochromic reversibility of polydiacetylenes (PDAs) was investigated using UV-vis absorption spectroscopy at temperatures ranging from 20 to 60 °C. Monomer DA2 was used as a single-component ink solution in a fountain pen that can be transformed into thermochromic letters on conventional paper. Furthermore, a PDA-embedded polyethylene oxide film was included to monitor the thermochromic reversibility and was found to exhibit excellent thermochromic reversibility between 20 and 100 °C and stability, enabling storage for a few months without deformation. Finally, a green-colored patterned polymer film is readily obtained by a subtractive color (blue and yellow) mixing method and exhibits high thermochromic reversibility at temperatures between 20 and 100 °C.