Synthesis of Polypropellanes via Ring-Opening Polymerization or Coupling Reaction

通过开环聚合或偶联反应合成聚丙烯

• 批准号: 14550833
• 负责人: ISHIZONE Takashi
• 金额: $ 2.3万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550833/
• 关键词: Propellane; Ring-opening polymerization; 1,3-Dehydroadamantane; Poly(1,3-adamantane); Cationic polymerization; Alternating copolymerization; Ring strain; Coupling reaction; 1,3-デヒドロアダマンタ; ラジカル重合; ブロペラン

Cationic ring-opening polymerizations of [3.3.1]propellane derivatives, 1,3-dehydroadamantane (1)and 5-butyl-1,3-dehydroadamantane (2), were carried out with CF_3SO_3H in CH_2Cl_2 at 0℃ for 6-42 h. The central σ-bonds in 1 and 2 were exclusively opened to afford novel poly([3.3.1]propellane)s, poly(1,3-adamantane)s, in good to quantitative yields. The resulting poly(2)possessing flexible butyl substituent was soluble in chloroform, THF, and 1,2-dichlorobenzene, and the degree of polymerization was estimated to be greater than 30, while the poly(1)was hardly soluble in the common organic solvents. All aliphatic poly(1)and poly(2)showed high thermal stability, whose 10% weight loss temperatures were 421 and 486℃, respectively.

[3.3.1]螺桨烷衍生物，1，3-脱氢金刚烷（1）和5-丁基-1，3-脱氢金刚烷（2）在0℃下，以CF_3SO_3H为引发剂，在CH_2Cl_2中进行了阳离子开环聚合反应。1和2中的中心σ-键被完全打开，以良好的定量产率得到新的聚（[3.3.1]螺桨烷）、聚（1，3-金刚烷）。结果表明，具有柔性丁基取代基的聚（2）可溶于氯仿、THF和1，2-二氯苯，聚合度大于30，而聚（1）几乎不溶于常用的有机溶剂。脂肪族聚（1）和聚（2）均表现出较高的热稳定性，其10%失重温度分别为421和486℃。

项目成果

Synthesis of Well-Defined Poly(N-isopropylacrylamide) by the Anionic Polymerization of N-Methoxymethyl-N-isopropylacrylamide

N-甲氧基甲基-N-异丙基丙烯酰胺阴离子聚合合成结构明确的聚(N-异丙基丙烯酰胺)

• 发表时间: 2002
• 期刊: J.Polym.Sci., Part A, Polym.Chem. 40
• 作者: Takashi Ishizone;Mana Ito
• 通讯作者: Mana Ito

Synthesis of Poly(1,3-adamantane)s by Cationic Ring-Opening Polymerization of 1,3-Dehydroadamantanes

1,3-脱氢金刚烷的阳离子开环聚合合成聚(1,3-金刚烷)

• 发表时间: 2004
• 期刊: Macromolecules 37
• 作者: Takashi Ishizone;Shin-ichi Mastuoka;Shiko Sakai;Wataru Harada;Hiroyuki Tajima
• 通讯作者: Hiroyuki Tajima

S.Han, M.Hagiwara, T.Ishizone: "Synthesis of Thermally-sensitive Water-soluble Polymethacrylates by Living Anionic Polymerization of Oligo(ethylene glycol) Methyl Ether Methacrylates"Macromolecules. 36. 8312-8319 (2003)

S.Han、M.Hagiwara、T.Ishizone：“通过低聚（乙二醇）甲醚甲基丙烯酸酯的活性阴离子聚合合成热敏性水溶性聚甲基丙烯酸酯”大分子。

Synthesis of New Crosslinkable Polymers by Chemoselective Polymerizations of 2-(1-Aziridinyl)ethyl Methacrylate

甲基丙烯酸 2-(1-氮丙啶基)乙酯化学选择性聚合合成新型可交联聚合物

• 发表时间: 2003
• 期刊: J.Polym.Sci., Part A, Polym.Chem. 41
• 作者: Takashi Ishizone.Tadahiro Takata;Mamoru Kobayashi
• 通讯作者: Mamoru Kobayashi

K.Sugiyama, H.Azuma, T.Watanabe, T.Ishizone, A.Hirao: "Anionic Polymerization of 2-Haloethyl Methacrylates"Polymer. 44. 4157-4164 (2003)

K.Sugiyama、H.Azuma、T.Watanabe、T.Ishizone、A.Hirao：“甲基丙烯酸 2-卤代乙酯的阴离子聚合”聚合物。