Study on the Synthesis of Cyclic Polymer Using Solid Support

固相载体合成环状聚合物的研究

• 批准号: 11650908
• 负责人: KUBO Masataka
• 金额: $ 2.05万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650908/
• 关键词: Solid Support; Cyclic Polymer; Cyclization; Heterodifunctional Polymer; Living Polymerization; Carbodiimide; ポリアクリル酸エステル; シリカゲル; ポリスチレン

A novel silane coupling agent was prepared by the reaction of (trimethoxy) silylbenzyl chloride with 1-ethy1-3-(3' -dimethylaminopropyl) carbodiimide. It was condensed with silica gel to obtain a carbodiimide immobilized silica gel as a solid dehydration agent. Elemental analysis revealed that 1 g of the functionalized silica gel contained 0.5 mmol of carbodiimide functionality. Then, α-carboxyl-ω-amino heterodifunctional polystyrene which was prepared via living anionic technique was reacted with the solid dehydration agent to obtain a cyclic polystyrene. The characterization of the obtained cyclic polystyrene was done by NMR and MALDI-TOF MS to establish a well-defined structure. Although the isolation yield of the cyclized polymer was still low around 20 %, it was found that unimolecular (intramolecular) cyclization reaction took place selectively. The advantage of this method is its easy isolation of the cyclized polymer only by filtration procedure.

以（三甲氧基）硅基氯化苄与1-乙基- 1-3-（3′-二甲氨基丙基）碳二亚胺为原料，制备了新型硅烷偶联剂。将其与硅胶缩合得到碳二亚胺固定化硅胶作为固体脱水剂。元素分析表明，1 g官能化硅胶含有0.5 mmol的碳二亚胺官能。然后，用活阴离子法制备α-羧基-ω-氨基异二官能聚苯乙烯，并与固体脱水剂反应得到环状聚苯乙烯。通过NMR和MALDI-TOF MS对合成的环状聚苯乙烯进行了表征，确定了结构清晰的环状聚苯乙烯。虽然环化聚合物的分离率仍然很低，约为20%，但发现单分子（分子内）环化反应是选择性发生的。该方法的优点是只需经过过滤就可以很容易地分离出环化聚合物。

项目成果

M.Kubo 他: "Synthesis of Cyclic Poly(methyl methacrylate)"Polymer Bulletin. 47. 25-30 (2001)

M.Kubo 等人：“环状聚（甲基丙烯酸甲酯）的合成”聚合物通报。47. 25-30 (2001)

M.Kubo 他: "Synthesis of Cyclic Poly(methyl methacrylate)by the Intramolecular Cyclization of α-Amino,ω-Carboxyl Heterodifunctional Poly(methyl methacrylate)"Polymer Bulletin. 47. 25-30 (2001)

M. Kubo 等人：“通过 α-氨基、ω-羧基杂双官能聚（甲基丙烯酸甲酯）的分子内环化合成环状聚（甲基丙烯酸甲酯）”聚合物通报 47. 25-30 (2001)。

M.Kubo 他: "Synthesis of a Well-Defined Polystyrene via α-Carboxyl, ω-Amino Heterodifunctional Polystyrene"Journal of Polymer Science : Part A : Polymer Chemistry. 37. 2027-2033 (1999)

M.Kubo 等人：“通过 α-羧基、ω-氨基杂二官能聚苯乙烯合成明确的聚苯乙烯”《聚合物科学杂志：A 部分：聚合物化学》37。2027-2033 (1999)。