Design and Construction of Synthetic Procedure of Nano-materials Exhibiting either No-shrinkage or Expansion on Polymerization

聚合不收缩或膨胀纳米材料合成工艺的设计与构建

• 批准号: 15350126
• 负责人: ENDO Takeshi
• 金额: $ 9.22万
• 依托单位: Yamagata 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 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15350126/
• 关键词: Nano-material; No-shrinkage; Expansion; Three-dimensional structure; Volume-shrinkage; 非収縮性

Ring-opening methathesis polymerization of norbomenes bearing cyclic carbonate structures afforded the corresponding polynortbomenes. The volume shrinkages in the polymerization, significantly lower than typical single-ring-opening polymerizations, depended on the ring-size of the carbonate rings, the molecular weights of the polymers, and the cis-trans contents in the main chains. Copolymeriation of the norbomenes bearing carbonate structures with cyclooctene also afforded the polymers with controllable volume changes. The resulting polymers having carbonate rings can be crosslinked via cationic ring-opening polymerization to obtain three-dimensional polymers. These results have demonstrated that low volume shrinkage system has been also constructed for metathesis polymerization, which has been focused on as an industrially important polymerization method.In the cationic cross-linking of the polymers bearing spiroorthocarbonate (SOC) structures in the side chains, we have found that the copolymer component highly affects the volume change behavior during the crosslinking. That is, the crosslinking of the copolymers containing the units from electron-donating monomers expands the volume even if the SOC contents were lower. In contrast, that of the copolymers containing the units from electron-withdrawing monomers exhibits moderate volume expansion, which increased as the increase of the SOC units.

含环碳酸盐结构的脱甲烯开环聚合得到相应的多脱甲烯。聚合过程中的体积收缩率明显低于典型的单环开环聚合，这取决于碳酸盐环的环尺寸、聚合物的分子量和主链中的顺反式含量。含碳酸盐结构的去甲烯与环烯的共聚也使聚合物具有可控的体积变化。所得到的具有碳酸盐环的聚合物可以通过阳离子开环聚合交联得到三维聚合物。这些结果表明，低体积收缩体系也已被构建为复分解聚合，已成为工业上重要的聚合方法。在侧链中含有螺正碳酸酯（SOC）结构的聚合物的阳离子交联中，我们发现共聚物组分对交联过程中的体积变化行为有很大的影响。也就是说，含有供电子单体单元的共聚物的交联使体积扩大，即使SOC含量较低。而含吸电子单体单元的共聚物则表现出适度的体积膨胀，体积膨胀随有机碳单元的增加而增大。

项目成果

Unusual Cationic Ring-Opening Behavior of a Novel Six-Membered Ring Spiro-Orthocarbonate Bearina Adamantane Backbones

新型六元环螺环原碳酸酯 Bearina 金刚烷主链的异常阳离子开环行为

• 发表时间: 2004
• 期刊: Journal of Polymer Science : Part A : Polymer Chemistry 42
• 作者: Tetsuo HINO;Yoshinori ITO;T.ENDO
• 通讯作者: T.ENDO

高橋 栄治: "Photocationic and Radical Polymerizations of Epoxides and Acrylates by Novel Sulfonium Salts"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3816-3827 (2003)

Eiji Takahashi：“新型锍盐对环氧化物和丙烯酸酯的光阳离子和自由基聚合”《高分子科学杂志》A 部分：高分子化学 41. 3816-3827 (2003)。

The Crosslinking Reaction of Bicyclic Bis(γ-lactone) with Triglycidyl Isocyanurate and Properties

双环双(γ-内酯)与异氰脲酸三缩水甘油酯的交联反应及性能

• 发表时间: 2004
• 期刊: Journal of Network Polymer, Japan(ネットワークポリマー) 25・2
• 作者: T.Wuernisha;F.Sano;Y.Takahashi;T.Kamiyama;Y.Takano;K.Sekizawa;Chenxi ZHANG
• 通讯作者: Chenxi ZHANG

Benzylpyrazinium Salts as Thermally Latent Initiators in the Polymerization of Glycidyl Phenyl Ether : Substituent Effect on the Initiator Activity and Mechanistic Aspects

苄基吡嗪鎓盐作为缩水甘油基苯基醚聚合中的热潜在引发剂：取代基对引发剂活性和机理的影响

• 发表时间: 2004
• 期刊: Macromolecules 37・15
• 作者: Y.-G.Choi;G.Sakai;K.Shimanoe;N.Miura;N.Yamazoe;Moon Suk Kim
• 通讯作者: Moon Suk Kim

The Crossliniking Reaction of Bicyclic Bis(γ-lactone) with Triglycidyl Isocyanurate and Properties (Japanese)

双环双(γ-内酯)与异氰脲酸三缩水甘油酯的交联反应及性能（日文）

• 发表时间: 2004
• 期刊: Journal of Network Polymer, Japan(ネットワークポリマー) 25(2)
• 作者: Chenxi ZHANG;Bungo OCHIAI;T.ENDO
• 通讯作者: T.ENDO