Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance.
Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance.
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DOI：
10.1039/c4py01552e
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发表时间：
2015
影响因子：
4.6
通讯作者：
Bowman CN
中科院分区：
文献类型：
--
作者：
Podgórski M;Becka E;Chatani S;Claudino M;Bowman CN
从无酯和含酯的单体配方中成功地合成了一系列硫醇-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成进行了比较。与商用的基于硫代丙酸的硫醇或硫醇-迈克尔网络相比，无酯的烷基硫醇、乙烯基砜和烯丙基单体的加入显著提高了力学性能。对于不含水解酯的聚合物，其玻璃化转变温度(Tg‘s)高达100°C。重要的是，耐溶剂性测试表明，与以PETMP为基础的聚合物相比，无酯配方的稳定性更高，特别是在浓缩碱性溶液中。动力学分析表明，在常温下很容易形成玻璃态的阶梯状聚合物，转化率可达80%以上。
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 (Tg'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.