Cyclodextrin as Macrocyclic Monomer. Synthesis of Polysaccharide by Its Ring-Opening Polymerization

环糊精作为大环单体。

• 批准号: 11650904
• 负责人: SUZUKI Masahito
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650904/
• 关键词: Cyclodextrin; Cationic Polymerization; Ring-Opening Polymerizarion; Polysaccharide; 糖差高分子

1.α-,β-,and γ-O-permethylated cyclodextrins (MeCDs) were found to act as macrocyclic monomers and undergo cationic ring-opening polymerization giving linear polyglucopyranose.2.The relative reactivity of these three MeCDs is unusual : the monomer having the smaller ring-strain has the higher reactivity, which increases in an order of α,β,and γ. This is due to the unique shape of CD ; the propagating end has to go into the CD cavity to open the CD ring, so that the monomer having the larger ring size is preferable for the polymerization.3.The polymerization of γ-MeCD under appropriate conditions produces a unique glucan having large intervals (=1633,MW of γ-MeCD) in the molecular weight distribution.4.The combination of a functionalized initiator with an activator conducts the polymerization of MeCD to give the end-fuctionalized glucan to some extent.5.MeCD and THF are copolymerizable to yield the corresponding hybrid polymer.6.MeCDs selectively modified at the C6 hydroxy groups of the glucose units are also polymerizable.7.The C2 mono-modified MeCDs are successfully prepared and subjected to the polymerization.

1.α-、β-和γ-O-全甲基化环糊精（MeCD）作为大环单体，通过阳离子开环聚合得到线性聚吡喃葡萄糖; 2.这3种MeCD的相对反应活性不同，环张力越小的单体反应活性越高，反应活性依次为α、β和γ。这是由于CD的独特形状; 3. γ-MeCD在合适的条件下进行聚合反应，得到了一种独特的具有大间距的葡聚糖（=1633，4.官能化引发剂与活化剂的组合进行MeCD的聚合，得到末端-在一定程度上官能化葡聚糖。5. MeCD和THF可共聚以产生相应的杂化聚合物。6.在葡萄糖单元的C6羟基处选择性修饰的MeCD也是可聚合的。7.成功地制备了C2单修饰的MeCD并进行聚合。

项目成果

Cyclodextrin as a Macrocyclic Monomer : Cationic Ring-Opening Polymerization of O-Permethylcyclodextrins

环糊精作为大环单体：O-全甲基环糊精的阳离子开环聚合

• 发表时间: 2001
• 期刊: Macromolecular Rapid Communications 22
• 作者: Masato Suzuki;Osamu Numata;Tomofumi Shimazaki
• 通讯作者: Tomofumi Shimazaki

Preparation of unique glucan with large intervalsin molecular weight distribution, Controlled ring-opening polymerization of O-permethylcyclodextrin

独特的大分子量分布葡聚糖的制备、O-全甲基环糊精的可控开环聚合

• 发表时间: 2003
• 期刊: Organic and Biomolecular Chemistry 1
• 作者: M.Suzuki;T.Shimazaki
• 通讯作者: T.Shimazaki

Masato Suzuki: "Cyclodextrin as a Macrocyclic Monomer Cationic Ring-Opening Polymerization of O-permethylcyclodextrins"Macromolecular Rapid Communications. 22・7. 1354-1357 (2001)

铃木正人：“环糊精作为 O-全甲基环糊精的大环单体阳离子开环聚合”，《高分子快速通讯》22·7（2001）。

Preparation of a unique glucan with large intervals in molecular weight distribution. Controlled ring-opening polymerization of O permethylcyclodextrin,

制备具有大分子量分布区间的独特葡聚糖。

• 发表时间: 2003
• 期刊: Organic and Biomolecular Chemistry 1
• 作者: Masato Suzuki;Tomofumi Shimazaki
• 通讯作者: Tomofumi Shimazaki

Fcile preparation of mono-2-modified eicosu-o-methyl-cyclomeltoheptaoses(-β-cyclodextrins)

单-2-修饰二十碳五烯基-邻-甲基-环甲基环七糖(-β-环糊精)的简便制备

• 发表时间: 2002
• 期刊: Carbohydrate Research 337
• 作者: M.Suzuki;Y.Nozoe
• 通讯作者: Y.Nozoe