Synthesis of 伪-, 蠅-, and 伪,蠅-End-Functionalized Poly(n-butyl acrylate)s by Organocatalytic Group Transfer Polymerization Using Functional Initiator and Terminator

详细信息    查看全文

• 作者：Kenji Takada ; Keita Fuchise ; Naoya Kubota ; Takahiro Ito ; Yougen Chen ; Toshifumi Satoh ; Toyoji Kakuchi
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：August 26, 2014
• 年：2014
• 卷：47
• 期：16
• 页码：5514-5525
• 全文大小：768K
• ISSN：1520-5835

文摘

The 伪-functionalized (hydroxyl, ethynyl, vinyl, and norbornenyl), 蠅-functionalized (ethynyl, vinyl, hydroxyl, and bromo), and 伪,蠅-functionalized polyacrylates were precisely synthesized by the N-(trimethylsilyl)bis(trifluoroethanesulfonyl)imide (Me₃SiNTf₂)-catalyzed group transfer polymerization (GTP) of n-butyl acrylate (nBA). The 伪-functionalization and 蠅-functionalization were carried out using the functional triisopropylsilyl ketene acetal as the initiator (initiation approach) and 2-phenyl acrylate derivatives as the terminator (termination approach) for the organocatalytic GTP, respectively. All the polymerizations precisely occurred and produced well-defined end-functionalized poly(n-butyl acrylate)s which had predictable molecular weights and narrow molecular weight distributions. High-molecular-weight polyacrylates were easily synthesized using both approaches. In addition, the 伪,蠅-functionalized (hetero)telechelic polyacrylates were synthesized by the combination of the initiation and termination approaches. The structure of the obtained polyacrylates and degree of functionalization were confirmed by the ¹H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS) measurements. The spectra of the ¹H NMR and MALDI-TOF MS showed that the end-functionalization quantitatively proceeded without any side reactions.