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Synthesis and rheological behavior of poly(1,2-butylene oxide) based supramolecular architectures

机译：基于聚（1,2-丁基氧化物）的超分子施工的合成与流变行为

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In this work we present the synthesis of poly(1,2-butylene oxide) (PBO) functionalized with the complementary hydrogen bond forming groups 2,4-diaminotriazine (DAT) and thymine. PBO is a rubbery polymer. Due to its semi-polar nature PBO is expected to suppresses non-directed cluster formation of the supramolecular groups but not influence their directed interactions. For the synthesis of backbone functionalized polymers we developed a procedure which allowed randomly copolymerizing BO with 1,2-epoxy-7-octene using anionic ring opening polymerization with potassium tert -butanolate as initiator. The vinyl groups were converted to OH-groups by oxidation. In addition, PBO with one alcoholic end group was obtained by homopolymerization of BO. For the variant with OH-groups at both chain ends a procedure was developed which was based on the cleavage of the tert -butyl initiator group. In all the polymers the alcohol groups were basically quantitatively transformed into NH _(2) -groups. DAT and thymine functionalities were attached to the NH _(2) -groups again in almost quantitative conversion. All reaction steps were monitored by ~(1) H-NMR using pyridine-d _(5) as solvent. This method allowed determining the conversions of the different synthesis steps with high precision. The materials were examined in linear rheology in order to study the effect of the hydrogen-bonds on the dynamics of the resulting supramolecular structures. The results corroborate the exclusive existence of directed interactions between the supramolecular groups.
机译：在这项工作中，我们介绍了用互补氢键形成组2,4-二氨基嗪（DAT）和胸腺嘧啶官能团官能化的聚（1,2--丁基氧化物）（PBO）。 PBO是橡胶状的聚合物。由于其半极性性质，预计PBO将抑制超分子组的非定向簇形成，但不会影响其定向的相互作用。对于骨架官能化聚合物的合成，我们开发了一种方法，其使用使用叔丁醇酸钾作为引发剂的阴离子开口聚合随机将BO与1,2-环氧-7-辛烯进行随机共聚。通过氧化将乙烯基转化为OH-基团。此外，通过博的均聚集获得具有一个酒精末端组的PBO。对于在两条链中的OH-基团的变体结束，开发了基于叔丁基引发剂基团的切割的方法。在所有聚合物中，醇基基本上地定量转化为NH _（2） - 群。在几乎定量的转化中再次将DAT和胸腺嘧啶官能团连接到NH _（2） - 群中。使用吡啶-D _（5）作为溶剂，通过〜（1）H-NMR监测所有反应步骤。该方法允许使用高精度确定不同合成步骤的转换。以线性流变学检查材料，以研究氢键对所得超分子结构的动态的影响。结果证实了超分子组之间的指向相互作用的独特存在。

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