2016MacromoleculesRequires access

Low Temperature Thermochromic Polydiacetylenes: Design, Colorimetric Properties, and Nanofiber Formation

In‐Sung Park, Hye Jin Park, Woomin Jeong, Jihye Nam, Youngjong Kang, Kayeong Shin, Hoeil Chung, Jong‐Man Kim

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Abstract

Owing to their stimulus responsive color changing properties, polydiacetylenes (PDAs) have been extensively investigated as colorimetric sensors. Thermochromic properties of PDAs have been the central focus of a number of investigations that were aimed not only at gaining a fundamental understanding of the physical basis of the color change but also at developing practical applications as temperature sensors. The thermochromic transition temperature of a PDA polymer is closely related to the melting point of the corresponding diacetylene (DA) monomer. In addition, the majority of PDAs described to date undergo a blue-to-red color change above room temperature because PDAs are generally derived from DA monomers that have melting points above room temperature. In the current study, we developed a series of low temperature colorimetric PDAs that were designed based on the reasoning that removal of the sources for strong headgroup interactions would lower the melting points of the corresponding DA monomers. This strategy was used to design and fabrication of PDA sensors that display color transitions in the range of 5–30 °C. Moreover, the thermochromic transition temperatures of the PDAs were found to decrease by ca. 10 °C when the alkyl chain length in the DA monomer is truncated by two methylene units. The results of FTIR and Raman spectroscopic analyses suggest that the PDA alkyl chain adopts an all-trans conformation in the blue-phase and some gauche forms exist in the alkyl chain in the red-phase PDA. Finally, the new PDAs are stable up to 300 °C, and their processable nature enables them to be fabricated in nanofiber forms by employing an anodized aluminum oxide (AAO) membrane as a template.

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What this paper is about

Owing to their stimulus responsive color changing properties, polydiacetylenes (PDAs) have been extensively investigated as colorimetric sensors. Thermochromic properties of PDAs have been the central focus of a number of investigations that were aimed not only at gaining a fundamental understanding of the physical basis of the color change but also at developing practical applications as temperature sensors. The thermochromic transition temperature of a PDA polymer is closely related to the melting point of the corresponding diacetylene (DA) monomer. In addition, the majority of PDAs described to date undergo a blue-to-red color change above room temperature because PDAs are generally derived from DA monomers that have melting points above room temperature. In the current study, we developed a series of low temperature colorimetric PDAs that were designed based on the reasoning that removal of the sources for strong headgroup interactions would lower the melting points of the corresponding DA monomers. This strategy was used to design and fabrication of PDA sensors that display color transitions in the range of 5–30 °C. Moreover, the thermochromic transition temperatures of the PDAs were found to decrease by ca. 10 °C when the alkyl chain length in the DA monomer is truncated by two methylene units. The results of FTIR and Raman spectroscopic analyses suggest that the PDA alkyl chain adopts an all-trans conformation in the blue-phase and some gauche forms exist in the alkyl chain in the red-phase PDA. Finally, the new PDAs are stable up to 300 °C, and their processable nature enables them to be fabricated in nanofiber forms by employing an anodized aluminum oxide (AAO) membrane as a template.

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Available abstract

Owing to their stimulus responsive color changing properties, polydiacetylenes (PDAs) have been extensively investigated as colorimetric sensors. Thermochromic properties of PDAs have been the central focus of a number of investigations that were aimed not only at gaining a fundamental understanding of the physical basis of the color change but also at developing practical applications as temperature sensors. The thermochromic transition temperature of a PDA polymer is closely related to the melting point of the corresponding diacetylene (DA) monomer. In addition, the majority of PDAs described to date undergo a blue-to-red color change above room temperature because PDAs are generally derived from DA monomers that have melting points above room temperature. In the current study, we developed a series of low temperature colorimetric PDAs that were designed based on the reasoning that removal of the sources for strong headgroup interactions would lower the melting points of the corresponding DA monomers. This strategy was used to design and fabrication of PDA sensors that display color transitions in the range of 5–30 °C. Moreover, the thermochromic transition temperatures of the PDAs were found to decrease by ca. 10 °C when the alkyl chain length in the DA monomer is truncated by two methylene units. The results of FTIR and Raman spectroscopic analyses suggest that the PDA alkyl chain adopts an all-trans conformation in the blue-phase and some gauche forms exist in the alkyl chain in the red-phase PDA. Finally, the new PDAs are stable up to 300 °C, and their processable nature enables them to be fabricated in nanofiber forms by employing an anodized aluminum oxide (AAO) membrane as a template.

Key concepts: Diacetylene, Thermochromism, Polydiacetylenes, Alkyl, Monomer, Polymer, Phase transition, Raman spectroscopy

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