Order–disorder transition in supramolecular polymer combs/brushes with polymeric side chains,Polymer Chemistry

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Order–disorder transition in supramolecular polymer combs/brushes with polymeric side chains
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-03-03 , DOI: 10.1039/c9py01915d
Milad Golkaram _{1,

2,

3,

4,

5} , Giuseppe Portale _{1,

2,

3,

4,

5} , Pascal Mulder _{1,

2,

3,

4,

5} , Dina Maniar _{1,

2,

3,

4,

5} , Shirin Faraji _{2,

3,

4,

5,

6} , Katja Loos _{1,

2,

3,

4,

5}

Affiliation

Supramolecular polymer combs/brushes can be used as smart materials which incorporate the properties of linear polymers with branch polymers depending on the temperature, grafting density, branch molecular weight and most importantly type of non-covalent interaction between the main chain and side chains. Three sets of polymers were synthesized and mixed based on a specific interaction between the main chain and the side chain polymers. The first two sets based on the combination of 2,4-diamino-1,3,5-triazine (DAT) : thymine (THY) and 2-ureido-4[1H]-pyrimidinone (UPy) : (1-(6-isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)urea) (ODIN) were a blend and the third one using ODIN : ODIN interactions was used without a main chain. The polymer set using ODIN : ODIN interaction showed long-range ordering due to strong ODIN aggregation, whereas UPy : ODIN-based polymer combs showed comb-like clusters without any ordering. The phase separation in the THY : DAT system was more pronounced and was further improved after the addition of more equivalents of side chains. Moreover, using melt rheology, consistent with the SAXS data, it was concluded that long-range ordering is responsible for the elastic properties and the flow temperature (T_flow) is lower than the order–disorder transition temperature (T_ODT). This work can be considered as a toolkit for the design of bottlebrush and comb polymers as well as supersoft elastomers and stimuli-responsive materials.

中文翻译：

具有聚合物侧链的超分子聚合物梳/刷子的有序无序过渡

超分子聚合物梳子/刷子可以用作智能材料，根据温度，接枝密度，支链分子量以及最重要的是主链和侧链之间非共价相互作用的类型，将线性聚合物与支链聚合物的性能结合在一起。基于主链和侧链聚合物之间的特定相互作用，合成并混合了三组聚合物。前两组基于2,4-二氨基-1,3,5-三嗪（DAT）：胸腺嘧啶（THY）和2-ureido-4 [1 H]-嘧啶酮（UPy）：( 1-（6-异氰酸根合己基）-3-（7-氧代-7,8-二氢-1,8-萘啶-2-基）脲）（ODIN）和第三种一种使用ODIN的方式：使用ODIN交互时不使用主链。由于强烈的ODIN聚集，使用ODIN：ODIN相互作用设置的聚合物显示出长程有序，而基于UPy：ODIN的聚合物梳则显示梳状簇，没有任何有序。在加入更多当量的侧链后，THY：DAT系统中的相分离更加明显，并且进一步得到改善。此外，根据熔体流变学，与SAXS数据一致，得出的结论是，长程有序是导致弹性性能的原因，流动温度（T _flow）低于有序-无序转变温度（T _ODT））。可以将这项工作视为设计洗瓶刷和梳状聚合物以及超软弹性体和刺激响应材料的工具包。

更新日期：2020-04-24

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