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

本研究采用可逆共价键断裂方法，设计了一种含有两个仲铵基团的哑铃分子作为轴组分，研究了新型聚合物“聚[3]轮烷”的合成及其性能。通过使用硫醇-二硫化物交换反应在末端形成两个大基团哑铃分子和具有两个的间苯二甲酰二酰胺的混合物。用催化量的苯硫酚处理二苯并-24-冠-8-醚部分，得到产率65%的聚[3]轮烷，Mn为25000。组分结构、溶剂、催化剂和浓度对聚[3]轮烷的影响当使用具有较长烷基链的轴组分时，聚合反应缓慢，需要更长的反应时间（超过1周）。然而，所得聚合物的分子量高于较短烷基链衍生物的分子量，……更可能是因为抑制了两种组分（即车轴和车轮单体）形成 1:1 加合物。通过TGA和DSC分析测定聚[3]轮烷的热分析和分解温度分别为140℃和330℃。以三苯基膦-水体系作为二硫化物的典型还原体系对聚[3]轮烷进行处理，回收了相应的还原形式的哑铃（硫醇）和同配位冠醚（轮分子）作为起始原料，表明聚[3]轮烷的回收性能。将聚[3]轮烷的合成方法推广到相应的网络聚合物，用聚冠醚网络代替。同二位冠醚通过与哑铃分子反应形成不溶于溶剂的凝胶材料，该凝胶材料在DMF中充分溶胀，该凝胶聚合物作为聚轮烷网络在干燥时是半透明的，但在DMF中溶胀时是透明的，具有弹性溶胀的性质。凝胶可通过改变条件、单体投料比、浓度、溶剂等来控制。

项目成果

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

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

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

Synthesis and Shuttling Behavior of Rotaxanes Consisting of Crown Ether Wheel and Disulfide Dumbbell with Two Ammonium Center

冠醚轮与双铵中心二硫哑铃轮烷的合成及穿梭行为

• 发表时间: 2004
• 期刊: Bull.Korean Chem.Soc 25
• 作者: Yoshio Furusho;Ryoko Sannoh;Tomoya Oku;Toshikazu Takata
• 通讯作者: Toshikazu Takata