Synthesis of Polymers with Ultra High Molecular Weight by Solid Phase Ring-opening Polymerization of Novel Macrocyclic Sulfides

新型大环硫醚固相开环聚合合成超高分子量聚合物

• 批准号: 13650939
• 负责人: KAMEYAMA Atsushi
• 金额: $ 2.11万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650939/
• 关键词: Solid Phase; Ring-opening Polymerization; Macrocyclic Sulfide; Triazine Structure; Poly (sulfide); Ultra High Molecular Weight

Synthesis and solid phase ring-opening polymerization of macrocyclic S-aryl thioesters, macrocyclic sulfides containing s-triazine structure were studied. The macrocyclic sulfides were prepared by the reaction of 1-dibutylamino-3, 5-dimercapto-s-triazine (BADMT) with (o-, m-, p-) xylylene dibromide using bases at a dilute condition (0.01 mol/L) in various solvents. The obtained products were worked up using recycle preparative HPLC to isolate macrocyclic dimmers [(o-, m-, p-) CS-2], trimers [(o-, m-, p-) CS-3], tetramers [(o-, m-, p-) CS-4], with moderate yields, respectively.The ring-opening polymerizations of the obtained macrocyclic sulfides in bulk were examined under N_2 atmosphere. Although the ring-opening polymerization of each macrocyclic sulfide without catalysts proceeded over 300℃, the molecular weights of the resulted polymers were not relatively high. On the other hand, the polymerizations were enhanced efficiently by using catalysts such as quaternary onium halides. When the polymerization of o-CS-2 was conducted with tetraphenyphosphonium chloride at 250℃ for 10min, a poly (sulfide) with Mw of 180000 was obtained at a conv. of 23%. The behavior of the solvent free ring-opening polymerization of the macrocyclic sulfides was investigated to found that the ring-opening polymerization occurred rapidly to produce high molecular weight polymers.

大环S-Aryl硫硫代菌，含有S-三嗪结构的大环硫化物的合成和固相环的聚合。大环硫化物是通过1-二丁基氨基-3、5-二甲基氨基-S-三嗪（BADMT）与（O-，M-，M，P-）二溴二酰胺在各种溶液中使用稀释条件（0.01 mol/L）的反应制备的。使用编制的回收HPLC来制定所获得的产物，以分离大环光片[（O-，M-，P-）CS-2]，Trimers [（O-，M-，P-，P-）CS-3]，四聚体[（O-，M-，M-，P-）CS-4]，分别具有持续的固定型，以均匀的量为单位。在N_2大气下检查的。尽管没有催化剂的每个大环硫化物的环环聚合进行了300次，但所得聚合物的分子量并不相关。另一方面，通过使用诸如卤化四元素的催化剂来有效增强聚合。当用四苯基磷酸在250℃下进行O-CS-2的聚合为10分钟时，在Conv中获得了含量为180,000的聚（硫化物）。 23％。研究了大环硫化物的无环开环聚合的行为，发现迅速发生环的聚合以产生高分子量聚合物。

项目成果

A.Kameyama, K.Kimura, T.Nishikubo: "Novel Solid-Phase Polymerization of Macrocyclic S-Aryl Thioesters"J. Polym. Sci., PartA, Polym. Chem. 39. 951-954 (2001)

A.Kameyama、K.Kimura、T.Nishikubo：“大环 S-芳基硫酯的新型固相聚合”J。

A.Kameyama., K.Kimura., T.Nishikubo.: "Novel Solid-Phase Polymerization of Macrocyclic S-Aryl Thioesters"J. Polym. Sci. Part A. Polym. Chem.. 39. 951-954 (2001)

A.Kameyama.、K.Kimura.、T.Nishikubo.：“大环 S-芳基硫酯的新型固相聚合”J。

A.Kameyama., K.Kimura., T.Nishikubo.: "Solid-Phase Thermal Polymerization of Macrocyclic S-Aryl Thioesters with 5-t-Butylisophtaloyl Skeleton using Crown Ether Complexes"High Perform. Polym.. 13(2). S181-S187 (2001)

A.Kameyama.、K.Kimura.、T.Nishikubo.：“使用冠醚配合物对大环 S-芳基硫酯与 5-t-丁基间苯二酰骨架进行固相热聚合”高性能。

A.Kameyama, T.Ide, T.Nishikubo: "Solid-Phase Ring-opening Polymerization of Macrocyclic S-Aryl Thioesters Containing Terephthaloyl Structure"High Perform. Polym.. 15(印刷中). (2003)

A.Kameyama、T.Ide、T.Nishikubo：“含有对苯二甲酰基结构的大环 S-芳基硫酯的固相开环聚合”高性能聚合物。15（出版中）。

A.Kameyama, K.Kimura, T.Nishikubo: "Solid-Phase Thermal Polymerization of Macrocyclic S-Aryl Thioesters with…"High Perform. Polym.. 13. S181-S187 (2001)

A.Kameyama、K.Kimura、T.Nishikubo：“大环 S-芳基硫酯的固相热聚合......”高性能聚合物.. 13. S181-S187 (2001)