Ring-Expansion/Contraction Radical Crossover Reactions of Cyclic Alkoxyamines: A Mechanism for Ring Expansion-Controlled Radical Polymerization

被引:4
作者
Narumi, Atsushi [1 ]
Kobayashi, Tetsuya [1 ]
Yamada, Masatsugu [1 ]
Binder, Wolfgang H. [2 ]
Matsuda, Keigo [3 ]
Shaykoon, Montaser Shaykoon Ahmed [1 ]
Enomoto, Kazushi [1 ]
Kikuchi, Moriya [4 ]
Kawaguchi, Seigou [1 ]
机构
[1] Yamagata Univ, Grad Sch Organ Mat Sci, Dept Organ Mat Sci, Jonan 4-3-16, Yonezawa, Yamagata 9928510, Japan
[2] Martin Luther Univ Halle Wittenberg, Fac Nat Sci Chem Phys & Math 2, Chair Macromol Chem, Von Danckelmann Pl 4, D-06120 Halle, Germany
[3] Yamagata Univ, Grad Sch Sci & Engn, Dept Chem & Chem Engn, Jonan 4-3-16, Yonezawa, Yamagata 9928510, Japan
[4] Yamagata Univ, Fac Engn, Dept Polymer & Organ Mat Engn, Jonan 4-3-16, Yonezawa, Yamagata 9928510, Japan
来源
POLYMERS | 2018年 / 10卷 / 06期
关键词
cyclic alkoxyamine; radical crossover reaction; ring-expansion reaction; ring-contraction reaction; ring-expansion vinyl polymerization; living radical polymerization; nitroxide-mediated controlled radical polymerization (NMP); macrocyclic polymer; cyclic topology; CATIONIC-POLYMERIZATION; BRUSH POLYMERS; ZWITTERIONIC POLYMERIZATION; METATHESIS POLYMERIZATION; RECENT PROGRESS; POLYSTYRENE; COPOLYMERS; STRATEGIES; CHEMISTRY; INITIATOR;
D O I
10.3390/polym10060638
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Macrocyclic polymers present an important class of macromolecules, displaying the reduced radius of gyration or impossibility to entangle. A rare approach for their synthesis is the ring expansion-controlled radical vinyl polymerization, starting from a cyclic alkoxyamine. We here describe ring-expansion radical crossover reactions of cyclic alkoxyamines which run in parallel to chain-propagation reactions in the polymerization system. The radical crossover reactions extensively occurred at 105-125 degrees C, eventually producing high molecular weight polymers with multiple inherent dynamic covalent bonds (NOC bonds). A subsequent ring-contraction radical crossover reaction and the second ring-expansion radical crossover reaction are also described. The major products for the respective three stages were shown to possess cyclic morphologies by the molecular weight profiles and the residual ratios for the NOC bonds (phi in %). In particular, the high phi values ranging from ca. 80% to 98% were achieved for this cyclic alkoxyamine system. This result verifies the high availability of this system as a tool demonstrating the ring-expansion vinyl polymerization that allows them to produce macrocyclic polymers via a one-step vinyl polymerization.
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页数:10
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