Synt6hesis and Ring Opening-Closure Behavior of Polymers Containing a Five-Membered Lactone Unit

五元内酯单元聚合物的合成及开闭环行为

• 批准号: 07651071
• 负责人: KIMURA Takao
• 金额: $ 1.41万
• 依托单位: Utsunomiya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651071/
• 关键词: 4-Butanolides; Diamines; Polyamides; Ring-Opening of Lactone; Reversible Reaction; Hydrolysis; NMR; GPC; 4-ブタノリド誘導体; 五員環ラクトン; 重合; 縮合素ポリマー; モデル反応; 開環-閉環挙動; NMRスペクトル

Bifunctional five-membered lactone monomers were prepared by the chemical transformation of t-butyl methacylate and dimethyl itaconate dimers telomerized using bromotrichloromethane. Polymerizations of these lactone monomers with some aliphatic and aromatic diamines and diols afforded polyamides, polyesters, polyamic acids, and polyimides. The polyamides prepared using aliphatic primary diamines had a high hydrophilicity owing to partial hydrolytic cleavage of the lactone moiety.The ring-opening and -closure reactions of condensation compounds of (2R^<**>,4S^<**>) -4-chloroformyl-2-chloroformylmethyl-2,4-dimenthyl-4-butanolide with monoamines and monools served to elucidate the ring-opening behavior of the resulting condensation polymers. The variation of ring-opening ratio with the passage of time was traced by the ^1H-NMR method. The behavior of model compounds was affected considerably by such factors as pH,solvent, structure of substrate, and so on. As these ring-opening and -closure reactions finally attain equilibrium, the ring-opening of the lactone moiety is presumed to be a reversible reaction. On the other hand, the ring-opening of lactone unit in the model compound derived from aliphatic primary amine proceeded completely in a phosphate buffer solution and it was independent of enzyme.Hydrolysis of titled polyamides is affected by the ring-opening ratio and aromatic site, and the results suggest the scission of end-type.

通过使用溴化氯甲烷的T丁基甲酸盐和二甲基Itaconate二聚体的化学转化来制备双功能五元的内酯单体。这些内酯单体的聚合物具有一些脂肪族和芳香族二醇和二醇，可提供聚酰胺，聚酯，聚酰胺酸和聚酰亚胺。由于内酯部分的部分水解裂解，使用脂肪族原发性二胺制备的聚酰胺具有很高的亲水性。 monools有助于阐明所得冷凝聚合物的开环行为。通过 ^1H-NMR方法可以追溯开环比与时间通过的变化。模型化合物的行为受到诸如pH，溶剂，底物结构等因素的影响。当这些开环和透明反应最终达到平衡时，据推测，内酯部分的环形开环是可逆反应。另一方面，源自脂肪胺胺的模型化合物中的内酯单位在磷酸盐缓冲溶液中完全进行，并且与酶无关。标题为聚酰胺的水解受环式开放率和芳族的影响，并受到芳族的位点的影响，结果暗示了基本类型的比例。

项目成果

Takao Kimura: "Reactivity of Telomers IV. Catalytic Reaction of t-Butyl 2-Bromo-4,4,4-trichloro-2-methylbutyrate with Copper Powder" Polymer Journal. 27. 1194-1201 (1995)

Takao Kimura：“端聚物的反应性 IV。2-溴-4,4,4-三氯-2-甲基丁酸叔丁基酯与铜粉的催化反应”聚合物杂志。

木村隆夫: "芳香族ジアミンを用いた主鎖に五員環ラクトンを含むポリアミドの合成と性質" 高分子論文集. 54. 52-56 (1997)

Takao Kimura：“使用芳香族二胺在主链中含有五元内酯的聚酰胺的合成和性能”Kobunshi Ronshu. 54. 52-56 (1997)。

木村隆夫: "ポリメタクリル酸t-ブチル鎖中の頭-頭結合を模倣した化合物の熱分解" 高分子論文集. 53. 448-452 (1996)

Takao Kimura：“模拟聚甲基丙烯酸叔丁酯链中头对头键的化合物的热分解”Kobunshi Ronshu 53. 448-452 (1996)。

Takao Kimura: "Reactivity of Telomers N.Catalytic Reaction of t-Butyl 2-Bromo-4,4,4,-trichloro-2-methylbutyrate with Copper Powder" Polymer Journal. 27・12. 1194-1201 (1995)

Takao Kimura：“调聚物 N. 2-溴-4,4,4,-三氯-2-甲基丁酸与铜粉的催化反应”，聚合物杂志 27・12 (1995)。

木村隆夫: "芳香族ジアミンを用いた主鎖に五員環ラクトンを含むポリアミドの合成と性質" 高分子論文集. 54・1. 52-56 (1997)

Takao Kimura：“使用芳香族二胺在主链中含有五元内酯的聚酰胺的合成和性能”Kobunshi Ronshu 54·1（1997）。