Synthesis of Polymeric analogues of Dipolar Aprotic Solvents and Their Use as Phase Transfer Catalysts

偶极非质子溶剂聚合物类似物的合成及其作为相转移催化剂的用途

• 批准号: 63550684
• 负责人: KONDO Shuji
• 金额: $ 1.22万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63550684/
• 关键词: Dipolar aprotic Solvent; Immobilization; Phase transfer catalyst; Cation extraction; Desolvation; Cooperative effect; Chelation; Poly-L-leucine; 相間移動触媒; カチオン吸着; 高分子効果; 反応場

Soluble polymers containing dipolar aprotic solvent moieties such as dimethyl sulfoxide, N,N-dimethylformamides, tetramethylurea, N,N-dimethylmethanesulfonamides and their analogues were prepared by free radical polymerization and copolymerization of corresponding new monomers. These polymers served as effective phase transfer catalysts for several reactions under liquid-liquid two-phase conditions. The catalytic activity of the copolymers containing styrene unit was generally higher than that of homopolymers. It was found that these polymers extract all alkali metal cations more effectively than their monomeric analogues, and that the extraction ability increased with increasing density of active sites, suggesting their cooperative effect. It is reasonable to assume that the catalytic activity is due to both cation extraction ability of the polymers and the activation of anions caused by desolvation in the hydrophobic regions of polymers. Insoluble polymers containing dipolar aprotic solvent moieties as well as partially alkylated poly-L-leucine and Nylon-66 also exhibited phase transfer catalytic activity.

通过自由基聚合和相应新单体的共聚反应，制备了含有偶极非质子溶剂部分的可溶性聚合物，如二甲基亚砜、N，N-二甲基甲酰胺、四甲基脲、N，N-二甲基甲磺酰胺及其类似物。这些聚合物作为有效的相转移催化剂，在液-液两相条件下的几个反应。含苯乙烯单元共聚物的催化活性普遍高于均聚物。结果发现，这些聚合物提取所有的碱金属阳离子更有效地比它们的单体类似物，和提取能力增加的活性位点的密度增加，这表明它们的合作效果。可以合理地假设催化活性是由于聚合物的阳离子萃取能力和聚合物疏水区域中的去溶剂化引起的阴离子活化。含有偶极非质子溶剂部分以及部分烷基化的聚-L-亮氨酸和尼龙-66的不溶性聚合物也表现出相转移催化活性。

项目成果

近藤修寿: "Polymeric Formamides as Liquid-Liquid Phase Transfer Catalysts" J.Polym.Sci.,Polym.Chem.Ed.27. 3383-3391 (1989)

Osamu Kondo：“作为液-液相转移催化剂的聚合甲酰胺”J.Polym.Sci.，Polym.Chem.Ed.27 (1989)。

近藤修寿: "Insoluble Polymeric Sulfoxides as Liquid-Solid-Liquid and Solid-Solid-Liquid Triphase Catalysts" Makromol.Chem.190. 2079-2089 (1989)

Osamu Kondo：“作为液-固-液和固-固-液三相催化剂的不溶性聚合亚砜”Makromol.Chem.190 2079-2089 (1989)。

Shuji Kondo, Masaki Iwasaki, and Kazuichi Tsuda: "Preparation of Polystyrenes Containing Sulfonamide Moieties and Their Use as Phase Transfer Catalysts" J. Macromol. Sci., -Chem.

Shuji Kondo、Masaki Iwasaki 和 Kazuichi Tsuda：“含有磺酰胺部分的聚苯乙烯的制备及其作为相转移催化剂的用途”J. Macromol。

近藤修寿: "Preparation of Polymeric Analogus of Tetramethylurea and Their Use as LiquidーLiqud PhaseーTransfer Catalysts" J.Macromol.Sci.,Chem.A26. 1425-1435 (1989)

Osamu Kondo：“四甲基脲聚合物类似物的制备及其作为液-液相-转移催化剂的用途”J.Macromol.Sci.，Chem.A26 1425-1435 (1989)。

近藤修寿: "Insoluble Polymeric Sulfoxides as LiquidーSolidーLiquid and SolidーSolidーLiquid Triphase Catalysts" Makromol.Chem.190. 2079-2089 (1989)

Osamu Kondo：“不溶性聚合亚砜作为液－固－液和固－固－液三相催化剂”Makromol.Chem.190 2079-2089 (1989)。