Controlled synthesis and some functional properties of C60-glycopolymer conjugates and glycopolymers with unique architectures

具有独特结构的 C60-糖聚合物缀合物和糖聚合物的受控合成和一些功能特性

• 批准号: 13650935
• 负责人: MINODA Masahiko
• 金额: $ 2.05万
• 依托单位: Kyoto 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: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650935/
• 关键词: glycopolymer; living polymerization; stable nitroxyl radical; atom transfer radical polymerization; AB-book copolymer; macromonomer; C60-glycopolymer conjugate; multi-branched polymer; リビングラジカル重合; 2元ブロック共重合体; C_<60>コンジュゲート; 分子構造の精密制御; 末端反応性ポリマ

Carbohydrate-carrying synthetic polymers, which are referred to as "glycopolymers", provide very promising functional materials in a variety of scientific fields. In this study were synthesized AB block copolymer-type glycopolymers, fullerene (C_<60>)-glycopolymer conjugates, and multi-branched glycopolymers with well-defined molecular architectures through the living radical polymerization technique.1. Two types of styrene derivatives having a pendant D-glucosamine or lactose residue, where hydroxyl groups are protected by acetyl functions, were polymerized at 90??-125?? In N,N-dimethylformamide with the initiators (BS-TEMPO or BS-DBN) to give nitroxyl-end-capped glycopolymers with controlled molecular weights and narrow molecular weight distributions (MWDs) (M_w/M_s < 1.2). The alkoxyamine initiators were prepared from styrene, benzoyl peroxide, and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or di-f-butyl nitroxide (DBN). Saccharide-substituted AB-block copolymers were successfully … More synthesized by the post-polymerization of styrene utilizing the isolated TEMPO- or DBN-end-capped glycopolymers. All the copolymers possessed relatively narrow MWDs and controlled compositions. The block copolymers were converted into the amphiphilic counterparts quantitatively by treating them with hydrazine monohydrate. The solubility of the lactose-carrying amphiphilic block copolymers in various solvents strongly depended on their segment composition.2. Fullerene (C_<60>)-glycopolymer conjugates were successfully synthesized through the radical addition reaction of the TEMPO- or DBN-end-capped block copolymer-type glycopolymers to C_<60> at 145℃ In 0-dichlorobenzene (ODCB) or ODCB/DMF (3/2, v/v) mixture. GPC and UV-vis spectroscopic analyses indicated that the conjugates possess 1,4-bisadduct structure, where a couple of glycopolymers are covalently connected to Coo at 1,4-positions.3. Multi-branched glycopolymers with controlled chain lengths for both the backbone and the side chain were synthesized through atom transfer radical polymerization (ATRP) of glucose-carrying poly(vinyl ether) macromonomers which have been synthesized living cationic polymerization. Less

碳水化合物合成聚合物，被称为“糖共聚物”，在各种科学领域提供了非常有前途的功能材料。本研究通过活性自由基聚合技术合成了AB嵌段共聚型糖共聚物、富勒烯(C_&lt；60&gt；)-糖共聚物以及分子结构明确的多支链糖共聚物。两种含侧链D-氨基葡萄糖或乳糖残基的苯乙烯衍生物在90℃-125℃下聚合，其中羟基由乙酰基保护。在N，N-二甲基甲酰胺中，用引发剂(BS-TEMPO或BS-DBN)合成了分子量可控、分子量分布窄的含氮氧基封端糖基共聚物(M_w/M_S和lt；1.2)。以苯乙烯、过氧化苯甲酰和2，2，6，6-四甲基-1-哌啶氧基(TEMPO)或二正丁基氮氧化物(DBN)为引发剂，制备了烷氧胺引发剂。糖取代AB-嵌段共聚物成功的…更多是通过使用分离的TEMPO-或DBN-端封端的糖共聚物进行苯乙烯的后聚合而合成的。所有的共聚物都具有相对较窄的相对分子质量分布和可控的组成。用一水合肼处理嵌段共聚物，定量地将其转化为两亲聚合物。含乳糖的两亲嵌段共聚物在不同溶剂中的溶解度强烈依赖于其链段组成。在0-二氯苯或邻二氯苯/二甲基甲酰胺(3/2，v/v)混合溶剂中，通过145℃的自由基加成反应，成功地合成了富勒烯(C&lt；60&gt；)-糖共聚物偶联物。凝胶渗透色谱(GPC)和紫外-可见光谱(UV-Vis)分析表明，该化合物具有1，4-双加合物结构，其中几个糖共聚物以1，4-位共价连接到COO上。通过原子转移自由基聚合(ATRP)方法，以活性阳离子聚合法制备了载葡萄糖聚乙烯基醚大分子单体，合成了主链和侧链链长均可控制的多支化糖基共聚物。较少

项目成果

M.Minoda: "Controlled synthesis of glycopolymers with various molecular architectures by TEMPO-mediated polymerization"Book of Abstracts, 224th ACS National Meeting, Boston, MA. ORGN223 (2002)

M.Minoda：“通过 TEMPO 介导的聚合控制具有各种分子结构的糖聚合物的合成”摘要书，第 224 届 ACS 全国会议，马萨诸塞州波士顿。

K.Yamada: "Amphiphilic block and statistical copolymers with pendant glucose residues : Controlled synthesis by living cationic polymerization and effect of copolymer architecture on their properties"J. Polym. Sci., Part A : Polym. Chem.. 39. 459-467 (200

K.Yamada：“具有侧链葡萄糖残基的两亲嵌段和统计共聚物：通过活性阳离子聚合控制合成以及共聚物结构对其性能的影响”J。

M.Minoda: "Synthesis of AB-block glycopolymers with well-defined structure by precision radical polymerization"Prepr. of 1st International Cellulose Conference (ICC2002). 141 (2002)

M.Minoda：“通过精确自由基聚合合成具有明确结构的AB嵌段糖聚合物”Prepr。

M. Minoda: "Controlled synthesis of glycopolymers with various molecular architectures by TEMPO-mediated polymerization,"Bookof Abstracts, 224th ACS National Meeting,. Boston MA, ORGN. 223 (2002)

M. Minoda：“通过 TEMPO 介导的聚合控制具有各种分子结构的糖聚合物的合成”，Bookof Abstracts，第 224 届 ACS 全国会议。

K.Yamada: "A survey of catalyst system for living cationic polymerization of glucose-carrying vinyl ethers with acetyl and isopropylidene protecting groups"Polymer International. 50. 531-537 (2001)

K.Yamada：“带有乙酰基和异亚丙基保护基团的葡萄糖携带乙烯基醚的活性阳离子聚合催化剂体系的调查”Polymer International。