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.

研究了含均三嗪结构的大环S-芳基硫酯、大环硫化物的合成及固相开环聚合。与（邻、间、对）二甲苯二溴化物在稀释条件下使用碱（0.01使用循环制备型 HPLC 对产物进行后处理，以分离得到大环二聚体 [(o-, m-, p-) CS-2]、三聚体 [(o-, m-, p-)。 CS-3]，四聚体[(o-，m-，p-) CS-4]，分别具有中等产率。在N_2下检查了所得大环硫化物的开环聚合反应。尽管在没有催化剂的情况下各大环硫化物的开环聚合反应均在300℃以上进行，但所得聚合物的分子量并不较高。另一方面，使用季鎓卤化物等催化剂可以有效地提高聚合反应的效率。 o-CS-2与四苯基氯化鏻在250℃下聚合10min，得到分子量为在23％的转化率下获得180000。 研究了大环硫化物的无溶剂开环聚合反应，发现开环聚合反应快速发生，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)