Haven Joris J, De Neve Jeroen A, Junkers Tanja
Polymer Reaction Design Group, Institute for Materials Research (imo-imomec), Hasselt University, Campus Diepenbeek, Building D, B-3590 Diepenbeek, Belgium.
IMEC division IMOMEC, Wetenschapspark 1, B-3590 Diepenbeek, Belgium.
ACS Macro Lett. 2017 Jul 18;6(7):743-747. doi: 10.1021/acsmacrolett.7b00430. Epub 2017 Jun 24.
Linear monodisperse 18- and 20-mer acrylates are obtained via consecutive synthesis of two sequence-defined acrylate 9- and 10-mers, followed by disulfide coupling utilizing reversible addition-fragmentation chain transfer (RAFT) end group chemistry. The sequence-defined oligoacrylates are accessed via consecutive single (SUMI) and multiple (MUMI) unit monomer insertions through RAFT polymerization, using the extensive acrylate monomer library as functional building blocks. Aminolysis of the trithiocarbonate macroRAFT end group and in situ oxidation of the thiols to form a disulfide bridge lead to the formation of 18- and 20-mer acrylates. In this approach, one or multiple acrylate building blocks can be inserted in each step by chain extension to form a stable carbon-carbon backbone. Isolation of the targeted monodisperse oligomers, from the statistical mixtures obtained at first, is performed by flash column chromatography with high efficiency. It is shown that the SUMI and MUMI strategy, when combined with flash column chromatography separation, is highly efficient and allows to construct monodisperse materials of very considerable length starting from cheap and very versatile building blocks.
通过连续合成两个序列定义的丙烯酸酯9聚体和10聚体，然后利用可逆加成-断裂链转移（RAFT）端基化学进行二硫键偶联，可得到线性单分散的18聚体和20聚体丙烯酸酯。通过RAFT聚合，利用大量丙烯酸酯单体库作为功能构建单元，通过连续的单（SUMI）和多（MUMI）单元单体插入来获得序列定义的低聚丙烯酸酯。三硫代碳酸酯大分子RAFT端基的氨解以及硫醇的原位氧化以形成二硫键桥，导致18聚体和20聚体丙烯酸酯的形成。在这种方法中，通过链延伸在每个步骤中可以插入一个或多个丙烯酸酯构建单元，以形成稳定的碳-碳主链。首先从获得的统计混合物中分离出目标单分散低聚物，通过快速柱色谱法高效进行。结果表明，SUMI和MUMI策略与快速柱色谱分离相结合时非常高效，并且能够从廉价且用途广泛的构建单元出发构建长度非常可观的单分散材料。
