Basic Research for New Polycondensation Systems Using Transition Metal Catalyst

使用过渡金属催化剂的新型缩聚体系的基础研究

• 批准号: 01470109
• 负责人: IMAI Yoshio
• 金额: $ 3.52万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470109/
• 关键词: Palladium Catalysts; Nickel Catalysts; Block Copolymers; Aromatic Polyamides; Polydimethylsiloxanes; Carbonylation Reaction; Polyphenylene Vinylene; 一酸化炭素; ポリアミド; 重縮合反応

Preparation of aromatic polyamideーpolysiloxane block copolymers were investigated by the carbon monoxide insertion reaction using palladium catalyst starting from aromatic dihalides, aromatic diamines, and amine terminated polydimethylsiloxane oligomers. The following reaction conditions were determined to obtain high molecular weight block copolymers1) Reaction Solvents2) Palladium catalysts3) Amines for hydrogen halides trap4) concentration of monomers5) Pressure of carbon monoxideFinally, the block copolymers which offered fairly tough films were obtained.On the other hand, general synthetic methodology of metal catalyzed polycondensation using nickel catalysts which were inexpensive compared with palladium ones. First, aromatic polyamides possessing fairly high molecular weights were obtain by the carbon monoxide insertion reaction using the nickel catalysts instead of palladium catalysts, whereas the molecular weights were slightlys smaller compared with the case of palladium.Farthermore, nickel catalyst were applied to preparation of the new coupling reaction of geminal dihalide compounds in the presence of zinc powder. The polymer obtained from dichlorodiphenylmethane had only low molecular weight. But, the formation of oligomeric compounds had important meaning, because the reaction was quite new.

以芳香族二卤化物、芳香族二胺和端胺基聚二甲基硅氧烷齐聚物为原料，在钯催化剂作用下，通过一氧化碳插入反应合成了芳香族聚酰胺ー聚硅氧烷嵌段共聚物。确定了获得高相对分子质量嵌段共聚物的反应条件：1)反应溶剂；2)钯催化剂；3)卤化氢胺；4)单体浓度；5)一氧化碳压力；最后，得到了具有较高韧性的嵌段共聚物。另一方面，与钯催化剂相比，镍催化剂用于金属催化缩聚反应的一般方法成本低廉。首先，用镍催化剂代替钯催化剂进行一氧化碳插入反应，得到了相对分子质量较高的芳香族聚酰胺，但与钯催化剂相比，芳香族聚酰胺的相对分子质量略小；此外，在锌粉存在下，将镍催化剂应用于双卤化物的新偶联反应。由二氯二苯基甲烷制得的聚合物只有低分子量。但是，低聚化合物的形成具有重要的意义，因为反应是相当新的。

项目成果

Masaru Yoneyama et al.,: "Novel synthesis of aromatic polyamides by nickelーcatalyzed polycondensation of aromatic dibromides, an aromatic diamines, and carbon monoxide" Makromol. Chem., Rapid Commun.,. 11,. 381-386 (1990)

Masaru Yoneyama 等人：“通过芳香族二溴化物、芳香族二胺和一氧化碳的镍催化缩聚反应合成芳香族聚酰胺”，Makromol，Rapid Commun.，381-386 (1990)。

Masaーaki Kakimoto: "Preparation of aromatic polyamideーpolysiloxane block copolymers by palladium catalyzed polycondensation." J.Polym.Sci.,A___ー,Polym.Chem.

Masaaki Kakimoto：“通过钯催化缩聚制备芳香族聚酰胺-聚硅氧烷嵌段共聚物。”J.Polym.Sci.，A___，Polym.Chem。

Toru Konishi: "Novel synthesis of phenylated poly(pーphenylene vinylene) by nickelーcatalyzed polycondensation of dichーlorodiphenylmethane" Polym.J.

Toru Konishi：“通过镍催化二氯二苯基甲烷缩聚新合成苯化聚（对亚苯基亚乙烯基）” Polym.J.

Masaーaki Kakimoto: "Preparation of aromatic polyamideーpolysiloxane block copolymers by palladium catalyzed polycondensation." J.Polym.Sci.,A,Polym.Chem.

Masaaki Kakimoto：“通过钯催化缩聚制备芳香族聚酰胺-聚硅氧烷嵌段共聚物。”J.Polym.Sci.,A,Polym.Chem。

Masaru Yoneyama: "Novel synthesis of aromatic polyamides by nickelーcatalyzed polycondensation of aromatic dibromides,an aromatic diamine,and carbon monoxide" Makromol.Chem.,Rapid Commun.,. 11. 381-386 (1990)

Masaru Yoneyama：“通过芳香族二溴化物、芳香族二胺和一氧化碳的镍催化缩聚反应合成芳香族聚酰胺”Makromol.Chem.，Rapid Commun.，11. 381-386 (1990)