Laboratoire de Chimie des Polymères Organiques (LCPO), CNRS - ENSCPB - Université de Bordeaux, 16 Avenue Pey-Berland, F-33607, Pessac, Cedex, France.
Macromol Rapid Commun. 2018 May;39(9):e1800043. doi: 10.1002/marc.201800043. Epub 2018 Mar 26.
The synthesis and self-assembly in thin-film configuration of linear ABC triblock terpolymer chains consisting of polystyrene (PS), poly(2-vinylpyridine) (P2VP), and polyisoprene (PI) are described. For that purpose, a hydroxyl-terminated PS-b-P2VP (45 kg mol ) building block and a carboxyl-terminated PI (9 kg mol ) are first separately prepared by anionic polymerization, and then are coupled via a Steglich esterification reaction. This quantitative and metal-free catalyst synthesis route reveals to be very interesting since functionalization and purification steps are straightforward, and well-defined terpolymers are produced. A solvent vapor annealing (SVA) process is used to promote the self-assembly of frustrated PS-b-P2VP-b-PI chains into a thin-film core-shell double gyroid (Q , space group: Ia3¯d) structure. As terraces are formed within PS-b-P2VP-b-PI thin films during the SVA process under a CHCl vapor, different plane orientations of the Q structure ((211), (110), (111), and (100)) are observed at the polymer-air interface depending on the film thickness.
本文描述了由聚苯乙烯（PS）、聚 2-乙烯吡啶（P2VP）和聚异戊二烯（PI）组成的线性 ABC 三嵌段共聚物链在薄膜结构中的合成和自组装。为此，首先通过阴离子聚合分别制备了羟基封端的 PS-b-P2VP（45kgmol）嵌段和羧基封端的 PI（9kgmol），然后通过 Steglich 酯化反应进行偶联。这种定量且无金属催化剂的合成路线非常有趣，因为功能化和纯化步骤简单，并且可以得到结构明确的嵌段共聚物。溶剂蒸气退火（SVA）过程用于促进受挫的 PS-b-P2VP-b-PI 链在薄膜中自组装成核壳双回旋（Q，空间群：Ia3¯d）结构。在 CHCl 蒸气下进行 SVA 过程中，PS-b-P2VP-b-PI 薄膜内形成梯田，因此取决于薄膜厚度，在聚合物-空气界面处观察到 Q 结构的不同平面取向（（211）、（110）、（111）和（100））。
