Reaction Kinetics and Reduced Shrinkage Stress of Thiol-Yne-Methacrylate and Thiol-Yne-Acrylate Ternary Systems.
Reaction Kinetics and Reduced Shrinkage Stress of Thiol-Yne-Methacrylate and Thiol-Yne-Acrylate Ternary Systems.
复制标题
DOI：
10.1021/ma2018809
复制
发表时间：
2011-12-13
期刊：
影响因子：
5.5
通讯作者：
Bowman CN
中科院分区：
文献类型：
--
作者：
Ye S;Cramer NB;Smith IR;Voigt KR;Bowman CN
研究了硫醇-炔-甲基丙烯酸酯和硫醇-炔-丙烯酸酯三元体系的聚合动力学和材料性能，并与类似的纯硫醇-炔和（甲基）丙烯酸酯体系进行了比较。硫醇-炔-甲基丙烯酸酯和硫醇-炔-丙烯酸酯体系都被证明可以降低聚合诱导的收缩应力，同时实现高玻璃化转变温度（Tg）和模量。与纯硫醇-炔体系相比，具有70重量%甲基丙烯酸酯的制剂将Tg从51 ± 2 °C增加到75 ± 1 °C，并且将模量从1800 ± 100 MPa增加到3200 ± 400 MPa（增加44%）。另外，收缩应力为1.2 ± 0.2MPa，这低于纯甲基丙烯酸酯、二元硫醇-炔和硫醇-烯-甲基丙烯酸酯对照体系的收缩应力，所述对照体系均> 2 MPa。有趣的是，随着甲基丙烯酸酯或丙烯酸酯浓度的增加，观察到收缩应力值的降低和随后的增加。在50wt%甲基丙烯酸酯和70wt%丙烯酸酯体系中观察到最小收缩应力值（1.0 ± 0.2MPa）。这种可调的行为是由甲基丙烯酸酯或丙烯酸酯均聚与链转移到硫醇和伴随的硫醇-炔逐步增长聚合的竞争性反应动力学引起的。网络的交联密度和相对于总体积收缩率的凝胶化之前发生的体积收缩量被确定为控制三元体系的最终收缩应力的两个关键因素。
Thiol-yne-methacrylate and thiol-yne-acrylate ternary systems were investigated for polymerization kinetics and material properties and compared to the analogous pure thiol-yne and (meth)acrylate systems. Both thiol-yne-methacrylate and thiol-yne-acrylate systems were demonstrated to reduce polymerization induced shrinkage stress while simultaneously achieving high glass transition temperatures (Tg) and modulius. Formulations with 70 wt% methacrylate increased the Tg from 51 ± 2 to 75 ± 1 °C and the modulus from 1800 ± 100 to 3200 ± 400 MPa (44% increase) over the pure thiol-yne system. Additionally, the shrinkage stress was 1.2 ± 0.2 MPa, which is lower than that of the pure methacrylate, binary thiol-yne and thiol-ene-methacrylate control systems which are all > 2 MPa. Interestingly, with increasing methacrylate or acrylate concentration, a decrease and subsequent increase in the shrinkage stress values were observed. A minimum shrinkage stress value (1.0 ± 0.2 MPa) was observed in the 50 wt% methacrylate and 70 wt% acrylate systems. This tunable behavior results from the competitive reaction kinetics of the methacrylate or acrylate homopolymerization versus chain transfer to thiol and the accompanying thiol-yne step-growth polymerization. The crosslinking density of the networks and the amount of volumetric shrinkage that occurs prior to gelation relative to the total volumetric shrinkage were determined as two key factors that control the final shrinkage stress of the ternary systems.
登录
查看更多内容
影响因子：
5.5
作者：
Senyurt, Askim F.;Wei, Huanyu;Gould, Trenton E.
通讯作者：
Gould, Trenton E.
影响因子：
2.3
作者：
Dodiuk-Kenig, H;Lizenboim, K;Kenig, S
通讯作者：
Kenig, S
影响因子：
5.5
作者：
Fairbanks, Benjamin D.;Sims, Evan A.;Bowman, Christopher N.
通讯作者：
Bowman, Christopher N.
影响因子：
5.5
作者：
Chan, Justin W.;Shin, Jungwhan;Lowe, Andrew B.
通讯作者：
Lowe, Andrew B.
影响因子：
29.4
作者：
Fairbanks, Benjamin D;Schwartz, Michael P;Halevi, Alexandra E;Nuttelman, Charles R;Bowman, Christopher N;Anseth, Kristi S
通讯作者：
Anseth, Kristi S