Comparing solution and melt-state association of hydrogen bonds in supramolecular polymers
Comparing solution and melt-state association of hydrogen bonds in supramolecular polymers
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DOI：
10.1039/c3py00362k
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发表时间：
2013-01-01
影响因子：
4.6
通讯作者：
Binder, Wolfgang H.
中科院分区：
文献类型：
--
作者：
Herbst, Florian;Binder, Wolfgang H.
通过原子转移自由基聚合（ATRP）和叠氮/炔“点击”反应合成了具有不同氢键基序（胸腺嘧啶（THY）和2，6-二氨基三嗪（DAT））的单、双功能聚丙烯酸正丁酯（PnBA），研究了氢键基序在溶液（甲苯-d（8））和熔融状态下的缔合作用.合成了THY和DAT功能化的PnBA（3a，4a，B，5a和6a，B），其分子量从4000到25000 g mol（-1），NMR和MALDI-MS方法证明它们具有完全的端基转化。通过核磁共振滴定实验研究了溶液中端基的缔合，并与通过频率依赖性流变学实验研究的熔融状态下的缔合进行了比较。THY和DAT官能化的PnBA（3a、4a、B、5a和6a、B）在溶液中的缔合与在熔融状态下的缔合相比是显著不同的。而在解决方案中的关联遵循以下关联强度顺序：DAT-DAT < THY-THY
Mono- and bifunctional poly(n-butyl acrylate)s (PnBAs) bearing different hydrogen bonding motifs (thymine (THY) or 2,6-diaminotriazine (DAT)) were prepared by a combination of atom transfer radical polymerization (ATRP) and azide/alkyne "click"-reaction to investigate the association of hydrogen bonding motifs in solution (toluene-d(8)) and in the melt state. THY and DAT functionalized PnBAs (3a, 4a, b, 5a and 6a,b) with molecular weights of similar to 4000 up to similar to 25 000 g mol(-1) were synthesized and they exhibit complete end group transformation as proven by NMR and MALDI-MS methods. The association of end groups in solution was studied by NMR-titration experiments and compared to the association in the melt state, investigated via frequency dependent rheology experiments. Association of THY and DAT functionalized PnBAs (3a, 4a, b, 5a and 6a, b) in solution is strikingly different when compared to the association in the melt state. Whereas association in solution follows this order in association strength: DAT-DAT < THY-THY