Poly[3]rotaxane : Synthesis and Property of The Novel Polymer

聚[3]轮烷：新型聚合物的合成与性能

• 批准号: 15350072
• 负责人: TAKATA Toshikazu
• 金额: $ 9.66万
• 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 (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350072/
• 关键词: polyrotaxane; poly[3]rotaxane; dynamic covalent chemistry; polyrotaxane network; rotaxane; polymer sythesis; thiol-disulfide interchange; topological gel; 合成; 可逆的開裂; チオール-ジスルフィド交換反応; リサイクル特性; 還元反応; ポリ[3]ロタキサン; チオールジスルフィド交換反応

The present research has been carried out to study the synthesis and property of novel polymer "poly[3]rotaxane" by using protocol of reversible covalent bond cleavage. A dumbbell molecule was designed as an axle component which contained two secondary ammonium moieties on it and two bulky groups at the termini, by using thiol-disulfide interchange reaction. A mixture of the dumbbell molecule and a isophthaloyl diamide possessing two dibenzo-24-crown-8-ether moieties was treated with a catalytic amount of benzenethiol to give 65% yield of poly[3]rotaxane with Mn 25000. The effects of the structures of the components, solvent, catalyst, and concentration on the polymerization were studied in detail. When the axle component having longer alkyl chain was employed, the polymerization was sluggish to require much longer reaction time (more than 1 week) to reach the equilibrium. However, the molecular weight of the resulting polymers were higher than that from shorter alkyl chain derivative, … More probably because of the suppression of the formation of 1:1 adduct of the two componets, i.e. the axle and wheel monomers.Thermal analyses and decomposition of poly[3]rotaxane were examined. Glass transition temperature and 5% weight loss temperature were 140℃ and 330℃, respectively, as determined by TGA and DSC analyses. Poly[3]rotaxane was treated with triohenylphosphine-water system as a typical reducing system for disulfide, and the corresponding reduced form of the dumbbell (a thiol) and the homofitopic crown ether (the wheel molecule) as the starting materials were recovered, suggesting the recycling property of poly[3]rotaxane.The synthetic method of poly[3]rotaxane was extended to the corresponding network polymer, polyrotaxane network. Poly(crown ether) was used instead of the homoditopic crown ether resulted in the formation of solvent-insoluble gel material which was well swelled in DMF by the reaction with the dumbbell molecule. The gelled polymer as polyrotaxane network was translucent when dried but transparent when swelled in DMF. The property of the elastic swelled gel was controllable by changing the conditions, monomer feed ratio, concentration, solvent and so on Less

项目成果

Efficient Synthesis of [2] and [3] Rotaxanes via Transition Metal-catalyzed Hydrosilylation of Alkyne

通过过渡金属催化炔烃氢化硅烷化高效合成[2]和[3]轮烷

• 发表时间: 2005
• 期刊: Tetrahedron Lett. 46・22
• 作者: H.Sasabe;N.Kihara;Kazuhiko Mizuno;A.Ogawa;T.Takata
• 通讯作者: T.Takata

環状・筒状超分子新素材の応用技術(第1章、環・筒・管の特性を活かした超分子材料)(高田十志和監修)

新型圆形、圆柱形超分子材料的应用技术（第一章，利用环、管、管特性的超分子材料）（高田敏和指导）

• 发表时间: 2006
• 作者: T.Oku;Y.o Furusho;T.Takata;Y.Furusho;T.Oku;T.Oku;高田十志和
• 通讯作者: 高田十志和

Novel Concept for Recyclable Crosslinked Polymer : Topologically Networked Polyrotaxane Capable of Undergoing Reversible Crosslinking and Decrosslinking

可回收交联聚合物的新概念：能够进行可逆交联和解交联的拓扑网络化聚轮烷

• 发表时间: 2004
• 期刊: Angew. Chem. Int. Ed. 43
• 作者: T.Oku;Y.Furusho;T.Takata
• 通讯作者: T.Takata

Dynamic Covalent Chemistry in Rotaxane Synthesis. Slipping Approach to [2]Rotaxane Utilizing Reversible Cleavage Rebondage of Trityl Thioether Linkage

轮烷合成中的动态共价化学。

• 发表时间: 2004
• 期刊: Chem.Lett 33[1]
• 作者: Yoshio Furusho;Tomoya Oku;G.Abraham Rajkumar;Toshikazu Takata
• 通讯作者: Toshikazu Takata

Yoshio Furusho, Toshikazu Tahaka ほか: "Dynamic Covalent Approach to [2]- and [3]Rotaxanes by Utilizing the Reversible Thiol-Disulfide Interchange Reaction"Chem.Eur.J.. 9. 2895-2903 (2003)

Yoshio Furusho、Toshikazu Tahaka 等人：“通过利用可逆硫醇-二硫化物交换反应实现[2]-和[3]轮烷的动态共价方法”Chem.Eur.J.. 9. 2895-2903 (2003)