No-Solvent Synthesis of Siloxanes and Silicone Nanotube

硅氧烷和有机硅纳米管的无溶剂合成

• 批准号: 15350020
• 负责人: UNNO Masafumi
• 金额: $ 5.63万
• 依托单位: Gunma University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350020/
• 关键词: siloxane; no-solvent reaction; green chemistry; silanol; regulation of structure; functional material; silsesquioxane; supramolecular structure; 高効率反応; 超分子; 脱水縮合

In this project, we aimed the syntheses of highly regulated silanols, and transformation to the novel siloxanes like nano-tube siloxanes by means of no-solvent reaction.Through this research, we obtained the following new result and published them.1)The stereospecific new reaction we invented made possible the synthesis of six-membered silanol, cyclotrisiloxanetriols (all two isomers) and eight-membered silanol, cyclotetrasiloxanetetraols (all four isomers). These are all new compounds, and especially cyclotetrasiloxanetetraols are very good precursors of ladder silsesquioxanes. Starting cyclotetrasiloxanetetraols, we obtained pentacyclic, heptacyclic, nonacyclic, and polycyclic laddersiloxanes. These are next-generation thermostable materials with low dielectric constant. We are currently investigation the application.2)By investigating starting compounds and reagents, we could extend the no-solvent reaction to the common synthesis of siloxanes. For example, the reaction of silanols with p-toluenesulfonic acid afforded strained siloxanes those could not be obtained by usual solution reaction. Additionally, hydrobromic acid and hydroiodic acid are good additives for the preparation of siloxanes inaccessible by solvent reactions. With these results, we can utilize cost-saving environmental-friendly no-solvent reaction of siloxanes.

在这个项目中，我们旨在通过无溶剂反应的方式转化为高度受调节的硅烷醇的合成，并转变为纳米管硅氧烷等新型硅氧烷，如纳米管硅氧烷。通过这项研究，我们获得了以下新结果。我们获得了以下新的结果并发表了它们。八元的硅烷醇，环氧苯甲酸（所有四个异构体）。这些都是新化合物，尤其是环氧苯甲酸盐是梯子硅质盐的非常好的前体。开始环乙二醇盐，我们获得了五囊，七囊，非囊性和多环甲氧烷。这些是具有低介电常数的下一代热稳定材料。我们目前正在研究应用程序。2）通过研究起始化合物和试剂，我们可以扩展对硅氧烷共同合成的无溶反应。例如，硅烷酚与p酚二磺酸的反应得到了菌株，这些硅氧烷可通过通常的溶液反应获得。另外，氢无酸和氢气酸是良好的添加剂，用于制备溶剂反应无法接近的硅氧烷。通过这些结果，我们可以利用Siloxanes的节省成本的环境友好反应。

项目成果

Anion recognition by a silanediol-based receptor

• DOI: 10.1021/ol061822p
• 发表时间: 2006-09-28
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Kondo, Shin-ichi;Harada, Tomomi;Unno, Masafumi
• 通讯作者: Unno, Masafumi

M.Unno, T.Tanaka, H.Matsumoto: "Tip-substituted cage and cyclic silanols"J.Organometallic Chem.. 686. 175-182 (2003)

M.Unno、T.Tanaka、H.Matsumoto：“尖端取代的笼和环状硅烷醇”J.Organometalic Chem.. 686. 175-182 (2003)

Photo-initiated Bromination of octakis(1,1,2-trimethylpropyl)octasila-cubane with Tetrabromomethane

四溴甲烷光引发八(1,1,2-三甲基丙基)八硅立方烷溴化

• 发表时间: 2004
• 期刊: Silicon Chem. 1
• 作者: M.Unno;H.Masuda;H.Matsumoto
• 通讯作者: H.Matsumoto

Organosilicon Chemistry VI

有机硅化学VI

• 发表时间: 2005
• 作者: T.Hatsui;H.Setoyama;N.Kosugi;I.L.Bradeanu;E.Ruhl;Masafumi Unno(分担)
• 通讯作者: Masafumi Unno(分担)

Supramolecular aggregates of silanols and solid-state synthesis of siloxanes

硅烷醇的超分子聚集体和硅氧烷的固态合成

• 发表时间: 2005
• 期刊: Molecular Crystals and Liquid Crystals 440
• 作者: M.Unno;K.Takada;Y.Kawa-guchi;H.Matsumoto
• 通讯作者: H.Matsumoto