无酯硫醇-X树脂：具有增强机械性能和耐溶剂性的新材料。
Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance.
作者信息
Podgórski Maciej, Becka Eftalda, Chatani Shunsuke, Claudino Mauro, Bowman Christopher N
机构信息
Department of Chemical and Biological Engineering, University of Colorado, UCB 596, Boulder, Colorado 80309, United States ; Faculty of Chemistry, Department of Polymer Chemistry, Maria Curie-Sklodowska University, pl. Marii Curie-Skłodowskiej 5, 20-031 Lublin, Poland.
Department of Chemical and Biological Engineering, University of Colorado, UCB 596, Boulder, Colorado 80309, United States.
出版信息
Polym Chem. 2015;6(12):2234-2240. doi: 10.1039/C4PY01552E.
A series of thiol-Michael and radical thiol-ene network polymers were successfully prepared from ester-free as well as ester-containing monomer formulations. Polymerization reaction rates, dynamic mechanical analysis, and solvent resistance experiments were performed and compared between compositions with varied ester loading. The incorporation of ester-free alkyl thiol, vinyl sulfone and allylic monomers significantly improved the mechanical properties when compared with commercial, mercaptopropionate-based thiol-ene or thiol-Michael networks. For polymers with no hydrolytically degradable esters, glass transition temperatures (T's) as high as 100 °C were achieved. Importantly, solvent resistance tests demonstrated enhanced stability of ester-free formulations over PETMP-based polymers, especially in concentrated basic solutions. Kinetic analysis showed that glassy step-growth polymers are readily formed at ambient conditions with conversions reaching 80% and higher.
通过不含酯以及含酯的单体配方成功制备了一系列硫醇-迈克尔和自由基硫醇-烯网络聚合物。进行了聚合反应速率、动态力学分析和耐溶剂性实验，并对不同酯含量的组合物进行了比较。与市售的基于巯基丙酸酯的硫醇-烯或硫醇-迈克尔网络相比，不含酯的烷基硫醇、乙烯基砜和烯丙基单体的加入显著改善了机械性能。对于没有可水解降解酯的聚合物，实现了高达100°C的玻璃化转变温度（Tg）。重要的是，耐溶剂性测试表明，不含酯的配方比基于PETMP的聚合物具有更高的稳定性，尤其是在浓碱性溶液中。动力学分析表明，玻璃态逐步增长聚合物在环境条件下很容易形成，转化率可达80%及更高。
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