Synthesis and self-assembly behavior of POSS tethered amphiphilic polymer based on poly(caprolactone) (PCL) grafted with poly(acrylic acid) (PAA) via ROP, ATRP, and CuAAC reaction

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• 作者：Souvik Ata ; Shyam Basak ; Dipakranjan Mal ; Nikhil K. Singha
• 关键词：POSS ; ROP ; Amphiphilic graft copolymer ; Click chemistry ; Worm ; like
• 刊名：Journal of Polymer Research
• 出版年：2017
• 出版时间：February 2017
• 年：2017
• 卷：24
• 期：2
• 全文大小：
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Polymer Sciences; Industrial Chemistry/Chemical Engineering; Characterization and Evaluation of Materials;
• 出版者：Springer Netherlands
• ISSN：1572-8935
• 卷排序：24

文摘

This investigation reports the preparation and self-assembly behavior of polyhedral oligomeric silsesquioxane (POSS) containing poly(caprolactone)-graft-poly(acrylic acid) (POSS-PCL-graft-PAA) polymer. This article focuses on the self-assembly behavior of POSS tethered amphiphilic graft copolymer. In this investigation, POSS tethered alkyne functionalized polycaprolactone (PCL) was prepared by strategic ring opening polymerization (ROP) of ε-caprolactone and α-propargyl-ε-caprolactone using hydroxyl-terminated POSS as an initiator. Azide-terminated poly(tert-butyl acrylate) (PtBA) was grafted onto functional PCL via Cu-catalyzed azide-alkyne “click” (CuAAC) reaction. Finally, hydrolysis of the tert-butyl ester group into acid furnished the POSS tethered PCL-graft-PAA polymer. This amphiphilic graft copolymer was characterized by GPC, NMR, and FT-IR analyses and the morphology of the graft copolymer analyzed by HRTEM and FESEM analyses. On changing the graft copolymer concentration (low to high) in water, the morphology of the final graft copolymer changed from micelles to worm-like and core-shell. The structural motif of POSS plays an important role in this morphological transformation. The pH sensitivity was studied using DLS analysis as well as via release profile of rhodamine B as a model compound.