Grigoryeva Olga, Fainleib Alexander, Starostenko Olga, Shulzhenko Diana, Rios de Anda Agustin, Gouanve Fabrice, Espuche Eliane, Grande Daniel
Institute of Macromolecular Chemistry, National Academy of Sciences of Ukraine, 48, Kharkivske Shose, 02155 Kyiv, Ukraine.
Université Paris Est Creteil, CNRS, Institut de Chimie et des Matériaux Paris-Est, UMR 7182, 2 rue Henri Dunant, 94320 Thiais, France.
Polymers (Basel). 2023 Dec 9;15(24):4654. doi: 10.3390/polym15244654.
Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12-15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, (DSC data), and the temperature of α relaxation, (DMTA data), by 45-55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/-phenylaminopropyl (PAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, ', at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99-3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO, He), and diffusion coefficients (CO) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5-4 times (CO), respectively, and the diffusion coefficient of CO increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (PAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of -NH and -NH- groups with -O-C≡N groups from CER.
合成并表征了填充三种不同反应性氨基官能化多面体低聚倍半硅氧烷（POSS）的氰酸酯树脂（CER）纳米复合材料。化学接枝到CER网络中的少量（0.1 wt.%）氨基POSS的添加，使CER基体的热稳定性提高了12 - 15℃，这取决于氨基POSS的类型。有证据表明，随着纳米填料的加入，CER基体的玻璃化转变温度（DSC数据）和α松弛温度（DMTA数据）显著提高了45 - 55℃。在研究的温度范围内，CER/POSS薄膜的储能模量高于纯CER薄膜。有证据表明，CER/氨丙基异丁基（APIB）-POSS、CER/-苯氨基丙基（PAP）-POSS和CER/氨乙基氨丙基异丁基（AEAPIB）-POSS纳米复合材料诱导了更均匀的α松弛现象，具有更高的α值和增强的纳米复合材料弹性行为。在25℃时，储能模量的值，'，从纯CER基体的2.72 GPa增加到含氨基官能化POSS纳米颗粒的纳米复合材料的2.99 - 3.24 GPa。此外，由于所研究的纳米复合材料的自由体积增加，这对其气体传输性能非常重要，CER/氨基-POSS纳米复合材料具有比纯CER更高的比表面积、气体渗透率（CO、He）和扩散系数（CO）值。与纯CER网络相比，CER/氨基-POSS纳米复合材料的渗透率分别提高了约2倍（He）和3.5 - 4倍（CO），CO的扩散系数增加了约两倍。氨基官能化POSS改善CER/氨基-POSS纳米复合材料热性能和传输性能的效率，按含一个伯氨基（APIB-POSS）<八个仲氨基（PAP-POSS）<一个仲氨基和一个伯氨基（AEAPIB-POSS）的反应性POSS顺序增加。APIB-POSS的作用最不明显，因为它只能通过一个-NH基团的反应与CER网络形成共价键，而AEAPIB-POSS的作用最显著，因为它可以通过-NH和-NH-基团与CER中的-O-C≡N基团反应轻松地掺入CER网络中。
