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通过与手性单体共聚,可调控基于非手性单体所制备的螺旋聚合物的光学活性。文中利用[Rh]金属有机催化剂,进行了手性(M1)和非手性(M2)N.炔丙基酰胺单体的共聚反应,聚合物产率高于97%。利用圆二色光谱技术及旋光仪对共聚物的光学活性进行了表征,发现共聚物组成对其光学活性有显著影响,不仅影响共聚物光学活性的大小,甚至还决定看聚合物主链所形成螺旋结构的手性。

An achiral and a chiral substituted acetylene monomer underwent copolymerizations smoothly, providing copolymers high yields (over 97 % ). The molecular weights of the copolymers are moderate (15000- 26400). The obtained copolymers possessed the same composition with the corresponding monomer feed ratio. All the copolymers adopted stable helices under the investigated conditions. However, the composition of the copolymers not only influenced the helical structure of the polymer main chains and further their optical activity, but also exerted large effects on the screw sense of the helices in the polymer backbones. Accordingly, the variation in copolymer composition led to the change of circular dichroism (CD) signal in both intensity and sign.

参考文献

[1] Liu, JZ;Lam, JWY;Tang, BZ .Acetylenic Polymers: Syntheses, Structures, and Functions[J].Chemical Reviews,2009(11):5799-5867.
[2] Zhi, JG;Guan, Y;Cui, JX;Liu, AH;Zhu, ZG;Wan, XH;Zhou, QF .Synthesis and Characterization of Optically Active Helical Vinyl Polymers via Free Radical Polymerization[J].Journal of Polymer Science, Part A. Polymer Chemistry,2009(9):2408-2421.
[3] Wu, S.;Yang, N.;Liu, Y.;Cao, J.;Hu, H.;Sun, Y.;Liu, J. .Optically active helical polymer from radical polymerization of menthyl vinyl ketone[J].Journal of Polymer Science, Part A. Polymer Chemistry,2011(1):293-299.
[4] Zhang, X.A.;Chen, M.R.;Zhao, H.;Gao, Y.;Wei, Q.;Zhang, S.;Qin, A.;Sun, J.Z.;Tang, B.Z. .A facile synthetic route to functional poly(phenylacetylene)s with tunable structures and properties[J].Macromolecules,2011(17):6724-6737.
[5] Deng, JP;Chen, B;Luo, XF;Yang, WT .Synthesis of Nano-Latex Particles of Optically Active Helical Substituted Polyacetylenes via Catalytic Microemulsion Polymerization in Aqueous Systems[J].Macromolecules,2009(4):933-938.
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