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

含糖合成聚合物被称为“糖共聚物”，在许多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具有明确分子结构的AB嵌段共聚物型含糖共聚物、富勒烯（C_<60>）-含糖共聚物共轭物和多支链含糖共聚物.两种类型的苯乙烯衍生物具有侧链D-葡糖胺或乳糖残基，其中羟基被乙酰基官能团保护，在90 ° C下聚合。一百二十五？在N，N-二甲基甲酰胺中，以BS-TEMPO或BS-DBN为引发剂，合成了分子量可控、分子量分布窄（Mw/Ms &lt; 1.2）的硝酰基封端含糖共聚物。烷氧基胺引发剂由苯乙烯、过氧化苯甲酰和2，2，6，6-四甲基-1-哌啶氧基（克里思）或二叔丁基氮氧化物（DBN）制备。顺丁烯二酰亚胺取代的AB-嵌段共聚物成功地 ...更多信息 利用分离的克里思-或DBN-封端的糖共聚物通过苯乙烯的后聚合来合成。所有的共聚物具有相对较窄的分子量分布和控制的组成。通过用一水合肼处理嵌段共聚物，将其定量转化为两亲性对应物。含乳糖两亲嵌段共聚物在不同溶剂中的溶解度与其链段组成密切相关.在<60>邻二氯苯（ODCB）或ODCB/DMF（3/2，v/v）混合溶剂中，145℃下，通过克里思或DBN封端的嵌段共聚物型含糖共聚物与富勒烯（C_2）的自由基加成反应，成功地合成了C_2-含糖共聚物共轭物<60>。凝胶渗透色谱和紫外可见光谱分析表明，偶联物具有1，4-双加合结构，其中一对糖共聚物在1，4-位共价连接到Coo上.采用原子转移自由基聚合（ATRP）方法合成了主链和侧链长度可控的多支链含糖聚乙烯基醚大单体。少

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