Helix-Sense-Selective Radical Polymerization of Methacrylamides

甲基丙烯酰胺的螺旋选择性自由基聚合

• 批准号: 14350485
• 负责人: OKAMOTO Yoshio
• 金额: $ 7.94万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14350485/
• 关键词: Helical Polymer; Isotactic-Specific Polymerization; Methacrylamides; Radical Polymerization; Asymmetric Polymerization; Helix-Sense-Selective Polymerization

In this study, the radical polymerization of N-(triphenylmethyl)methacrylamide (TrMAM) and N-[di(4-butylphenyl)phenylmethyl]-methacrylamide (DBuTrMAM) was carried out in order to attain the helix-sense-selective polymerization leading to optically active polymers. The radical polymerization of TrMAM and DBuTrMAM proceeded in an isotactic-specific manner, and the ^1H NMR spectra of the obtained polymers in D_2SO_4 indicated that the obtained polymers were almost 100% isotactic polymers, which may produce an equimolar mixture of left-and right-handed helices. The poly(DBuTrMAM)s prepared in chiral menthols were optically active, and the polymerization in (+)-menthol and (-)-menthol produced the polymers having the negative and positive specific rotation, respectively. In the circular dichroism (CD) spectra of the poly(DBuTrMAM)s synthesized in menthols at 0℃, the peak patterns suggested that the polymer having an excess single-handed helicity was produced. Although poly(TrMAM)s were insoluble in common organic solvents, the analogous CD patterns were observed in Nujol in for the poly(TrMAM)s obtained in menthols. Triphenylmethyl methacrylate is easily solvolyzed in 10 minutes in methanol-chloroform at 35℃, but TrMAM was quite stable for the solvolysis for a week. Thus, the optically active poly(TrMAM) must afford a much stable chiral stationary phase against alcoholic solvents.

在这项研究中，进行了N-(三苯基甲基)甲基丙烯酰胺(TrMAM)和N-[二(4-丁基苯基)苯基甲基]-甲基丙烯酰胺(DBuTrMAM)的自由基聚合，以获得螺旋顺向选择性聚合，从而得到TrMAM 和 DBuTrMAM 的自由基聚合以全同立构方式进行，并且D_2SO_4中聚合物的^1H NMR谱表明所得聚合物几乎是100%全同立构聚合物，这可能会产生左旋和右旋螺旋的等摩尔混合物。在手性薄荷醇中制备的聚(DBuTrMAM)具有光学活性。 ，并且(+)-薄荷醇和(-)-薄荷醇的聚合分别产生具有负和正比旋光度的圆形聚合物。 0℃下在薄荷醇中合成的聚(DBuTrMAM)的二色性(CD)光谱，峰图表明产生了具有过量单手螺旋性的聚合物。在 Nujol 中观察到在薄荷醇中获得的聚（TrMAM）的类似 CD 图案，甲基丙烯酸三苯甲酯很容易在 10 分钟内溶解。甲醇-氯仿在35℃下溶解，但TrMAM在一周内溶剂解作用相当稳定，因此，光学活性聚(TrMAM)必须提供对醇溶剂非常稳定的手性固定相。

项目成果

N.Hoshikawa, Y.Hotta, Y.Okamoto: "Stereospecific Radical Polymerization of N-Triphenylmethylmethacrylamides Leading to Highly Isotactic Helical Polymers"Journal of American Chemical Society. 125. 12380-12381 (2003)

N.Hoshikawa、Y.Hotta、Y.Okamoto：“N-三苯基甲基甲基丙烯酰胺的立体定向自由基聚合导致高度全同立构螺旋聚合物”美国化学会杂志。

B.Ray, Y.Isobe, K.Morioka, S.Habaue, Y.Okamoto, M.Kamigaito, M.Sawamoto: "Synthesis of Isotactic Poly(N-isopropylacrylamide) by RAFT Polymerization in the Presence of Lewis Acid"Macromolecules. 36. 543-545 (2003)

B.Ray、Y.Isobe、K.Morioka、S.Habaue、Y.Okamoto、M.Kamigaito、M.Sawamoto：“在路易斯酸存在下通过 RAFT 聚合合成全同立构聚（N-异丙基丙烯酰胺）”大分子。

B.Ray, Y.Isobe, K.Matsumoto, S.Habaue, Y.Okamoto, M.Kamigaito, M.Sawamoto: "RAFT Polymerization of N-Isopropylacrylamide in the Absence and Presence of Y(OTf)_3 : Simultaneous Control of Molecular Weight and Tacticity"Macromolecules. 37. 1702-1710 (2004)

B.Ray、Y.Isobe、K.Matsumoto、S.Habaue、Y.Okamoto、M.Kamigaito、M.Sawamoto：“在不存在和存在 Y(OTf)_3 的情况下 N-异丙基丙烯酰胺的 RAFT 聚合：同时控制

Y.Okamoto, S.Habaue, Y.Isobe: "Lewis Acid-Catalyzed Tacticity Control during Radical Polymerization of (Meth)acrylamides"ACS Symposium Series. 854. 59-71 (2003)

Y.Okamoto、S.Habaue、Y.Isobe：“（甲基）丙烯酰胺自由基聚合过程中路易斯酸催化的立构性控制”ACS 研讨会系列。

Y.Okamoto, S.Habaue, Y.Isobe, Y.Suito: "Stereocontrol Using Lewis Acids in Radical Polymerization"Macromolecular Symposia. 195. 75-80 (2003)

Y.Okamoto、S.Habaue、Y.Isobe、Y.Suito：“在自由基聚合中使用路易斯酸进行立体控制”高分子研讨会。