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Synthesis of novel cyclosiloxane monomers containing push-pull moieties and their anionic ring opening polymerization

机译：含有推拉部分的新型环硅氧烷单体的合成及其阴离子开环聚合

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摘要

The synthesis of three novel tetracyclosiloxane monomers modified either with a nitroaniline (NA) or with a Disperse Red 1 (DR1) push-pull group and their ring opening polymerization reaction in the presence of tetramethylammonium hydroxide are presented. The prepared monomers and polymers were characterized by different spectral methods and gel permeation chromatography. For the crystalline monomers, the structures were further proven by single crystal X-ray diffraction. Dynamic scanning calorimetry shows that the polymers that carry NA groups have a glass transition temperature (T-g) well below room temperature (RT), while the one that carries DR1 groups melts at 55 degrees C. The transition temperatures have a strong effect on permittivity as indicated by broadband impedance spectroscopy measurements conducted at different temperatures and frequencies. The polymers modified with NA groups have a high permittivity (maximum value of 17.3) at RT, suggesting the polar groups to be mobile and orientation polarization to be effective. However, the polar groups of the polymer modified with DR1 are frozen and thus cannot contribute to the permittivity via orientation polarization. Consequently, the permittivity is only 8.8 at RT, but increases to 22 above the melting temperature, where the dipoles are mobile. Because of the high dielectric permittivity and rather low T-g, the polymers modified with NA are attractive as active dielectric materials in actuators, capacitors, and stretchable electronics, whereas the polymer modified with DR1 may be of interest in nonlinear optical devices.
机译：提出了三种新型四环硅氧烷单体的合成，其用硝基苯胺（Na）或分散的红色1（DR1）推拉组和它们的环开口聚合反应在氢氧化四甲基铵存在下。通过不同的光谱方法和凝胶渗透色谱法表征制备的单体和聚合物。对于结晶单体，通过单晶X射线衍射进一步证明该结构。动态扫描量热法表明，携带NA基团的聚合物具有良好的室温（RT）玻璃化转变温度（Tg），而携带DR1组的玻璃化转变温度（Tg）在55℃下熔化。过渡温度对介电常数有很强的效果由在不同温度和频率下进行的宽带阻抗光谱测量。用Na基团改性的聚合物在室温下具有高介电常数（最大值为17.3），表明极性基团是流动的和取向极化的有效性。然而，用DR1改性的聚合物的极性基团被冷冻，因此不能通过取向极化有助于介电常数。因此，介电常数在室温下仅为8.8，但在熔化温度上方增加至22，其中偶极子是移动的。由于高介电介电常数和相当低的T-G，用NA改性的聚合物是在致动器，电容器和可伸展电子器件中的有源介电材料的吸引力，而用DR1改性的聚合物可能是非线性光学器件的感兴趣。

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  • 来源
    《RSC Advances》 |2018年第14期|共10页
  • 作者

    Perju Elena; Cuervo-Reyes Eduardo; Shova Sergiu; Opris Dorina M.;

  • 作者单位

    Swiss Fed Labs Mat Sci &

    Technol Empa Lab Funct Polymers Ueberlandstr 129 CH-8600 Dubendorf Switzerland;

    Swiss Fed Labs Mat Sci &

    Technol Empa Lab Energy Convers Ueberlandstr 129 CH-8600 Dubendorf Switzerland;

    Romanian Acad Petru Poni Inst Macromol Chem Aleea Gr Chica Voda 41A Iasi 700487 Romania;

    Swiss Fed Labs Mat Sci &

    Technol Empa Lab Funct Polymers Ueberlandstr 129 CH-8600 Dubendorf Switzerland;

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  • 正文语种 eng
  • 中图分类 化学;
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