Kinetics analysis and physical properties of photocured silicate-based thiol-ene nanocomposites: The effects of vinyl POSS ene on the polymerization kinetics and physical properties of thiol-triallyl ether networks
Kinetics analysis and physical properties of photocured silicate-based thiol-ene nanocomposites: The effects of vinyl POSS ene on the polymerization kinetics and physical properties of thiol-triallyl ether networks
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DOI：
10.1007/s11998-008-9092-x
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发表时间：
2008-09-01
影响因子：
2.3
通讯作者：
Nazarenko, Sergei
中科院分区：
文献类型：
--
作者：
Clark, Tolecia S.;Hoyle, Charles E.;Nazarenko, Sergei
相对于增加聚低聚倍半硅氧烷（POSS）浓度测量三硫醇-TAE（三烯丙基醚）体系的动力学和热/物理性质，以了解POSS纳米颗粒的存在如何影响低负载下的网络形成。通过热引发的自由基反应合成了具有乙烯基和羧酸酯侧基的乙烯基POSS单体（vPOSS-Bu-4），以改善无机粒子与三硫醇和三烯丙基醚共聚单体的相容性。化学改性的vPOSS-Bu-4颗粒通过硫醇-烯自由基光聚合以0、1和5烯摩尔%的摩尔浓度并入三硫醇-TAE聚合物网络中。使用实时FTIR和photo-DSC分析聚合速率。随着vPOSS-Bu-4浓度的增加，聚合速率没有显着变化。通过差示扫描量热法（DSC）和热重分析（TGA）对膜进行的热分析表明，随着POSS浓度的增加，热稳定性提高而不影响T（g）。此外，耐刮擦性增加和火焰蔓延降低显着增加POSS浓度的浓度高达5摩尔% vPOSS-Bu-4。
The kinetics and thermal/physical properties of the trithiol-TAE (triallyl ether) system were measured with respect to increasing polyoligomeric silsesquioxane (POSS) concentrations in order to understand how the presence of POSS nanoparticles affects network formation at low loadings. Vinyl POSS monomer (vPOSS-Bu-4) with both vinyl and carboxylate pendant groups was synthesized via a thermally initiated, free-radical reaction to improve the compatibility of the inorganic particles with the trithiol and triallyl ether comomoners. Chemically modified vPOSS-Bu-4 particles were incorporated into the trithiol-TAE polymer networks by a thiol-ene free-radical photopolymerization at molar concentrations of 0, 1, and 5 ene mol%. The polymerization rates were analyzed using real-time FTIR and photo-DSC. The polymerization rates showed no significant changes with increasing vPOSS-Bu-4 concentration. Thermal analyses of the films by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) demonstrated that thermal stability improves without affecting T (g) as the POSS concentration increased. Additionally, scratch resistance increased and flame spread decreased markedly with increasing POSS concentration for concentrations up to 5 mol% vPOSS-Bu-4.