Carioscia Jacquelyn A, Stansbury Jeffrey W, Bowman Christopher N
University of Colorado, Boulder, Department of Chemical and Biological Engineering, Boulder CO 80309-0424.
Polymer (Guildf). 2007 Mar 8;48(6):1526-1532. doi: 10.1016/j.polymer.2007.01.044.
The development of thiol-ene/thiol-epoxy hybrid networks offers the advantage of tailorable polymerization kinetics while producing a highly crosslinked, high T(g) polymer that has significantly reduced shrinkage stress. Stoichiometric mixtures of pentaerythritol tetra(3-mercaptopropionate) (PETMP)/triallyl-1,3,5-triazine-2,4,6-trione (TATATO) (thiol-ene, mixture 1) and PETMP/bisphenol a diglycidyl ether (BADGE) (thiol-epoxy, mixture 2) were prepared and hybrid mixtures of 75/25, 50/50, 25/75, and 10/90 w/w of mixtures 1 and 2 were polymerized using a combination of both radical and anionic initiation. The light exposure timing and the relative initiation conditions of the two types were used to control the order and relative rates of the radical and anionic polymerizations. The 50/50 w/w thiol-ene/thiol-epoxy hybrid material exhibited a final stress of only 0.2 MPa, which is 90 % lower than the stress developed in a control dimethacrylate resin. Kinetic analysis indicates composition affects network development in thiol-ene/thiol-epoxy hybrid networks and produces materials with robust mechanical properties.
硫醇-烯/硫醇-环氧杂化网络的发展具有可定制聚合动力学的优势，同时能生成高度交联、高玻璃化转变温度（T(g)）且收缩应力显著降低的聚合物。制备了季戊四醇四(3-巯基丙酸酯)(PETMP)/三烯丙基-1,3,5-三嗪-2,4,6-三酮(TATATO)(硫醇-烯，混合物1)和PETMP/双酚A二缩水甘油醚(BADGE)(硫醇-环氧，混合物2)的化学计量混合物，并使用自由基引发和阴离子引发相结合的方法使混合物1和混合物2按75/25、50/50、25/75和10/90 w/w的比例混合进行聚合。利用两种引发类型的光照时间和相对引发条件来控制自由基聚合和阴离子聚合的顺序及相对速率。50/50 w/w的硫醇-烯/硫醇-环氧杂化材料的最终应力仅为0.2 MPa，比对照二甲基丙烯酸酯树脂产生的应力低90%。动力学分析表明，组成会影响硫醇-烯/硫醇-环氧杂化网络中的网络形成，并产生具有强大机械性能的材料。
