Synthesis and properties of a new class of sugar-carrying amphiphilic block copolymers

一类新型含糖两亲性嵌段共聚物的合成及性能

• 批准号: 07455373
• 负责人: MIYAMOTO Takeaki
• 金额: $ 4.99万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07455373/
• 关键词: glycopolymer; pendant glucose; pendant glucosamine residue; amphiphilic block copolymer; living cationic polymerization; polymeric thin film; microphase-separated structure; interfacial property; 両親媒性ポリマー; ブロックコポリマー; ランダムコポリマー; ビニルエーテル; ポリマー超薄

In this research project, we have succeeded in synthesizing a new class of sugar-carrying amphiphilic block copolymers- [CH_2CH (OCH_2CH_2OR)] _m- [CH_2CH (OiBu)] _n-by living cationic polymerization, where R is a D-glucose or D-glucosamine residue. To obtain them, sequential living block copolymerization of isobutyl vinyl ether and the vinyl ether carrying a monosaccharide whose hydroxyl and/or amino groups are protected was conducted using a HI/Znl_2 or TFA/EtAlCl_2 initiating system. The obtained block copolymers had a narrow molecular weight distribution (M_w/M_n-1.1) and a controlled composition. Quantitative deprotection of the resulting precursor polymers was successfully achieved to afford the target amphiphiles. The solubility of the amphiphilic block copolymers in various solvents depended strongly on the block composition (m/n).The solvent-cast thin films of the glucose-carrying block copolymer were observed, under a transmission electron microscope, to exhibit various microphase-separated surface morphologies such as spheres, cylinders, and lamellae, depending on composition. The contact angle measurement revealed that the block copolymer film changes its surface properties depending on the environmental condition, the hydrophobic isobutyl segment on the surface can be replaced with hydrophilic segment by soaking it in water. To more precisely control its fine structure, we applied the Langmuir-Blodgett (LB) technique to this block copolymer. The block copolymer, spread from a mixture solution of chloroform and methanol onto the water surface, was found to form a stable monolayr, which is successfully transferred onto a substrate by the LB technique. The layred structure of the LB film was demonstrated to be controlled by blending the homopolymer.

在本研究项目中，我们通过活性阳离子聚合成功地合成了一类新型的含糖两亲嵌段共聚物-[CH_2CH(OCH_2CH_2OR)]_m-[CH_2CH(OiBu)]_n，其中R为D-葡萄糖或D-氨基葡萄糖残基。异丁基乙烯基醚与带有羟基和/或氨基保护的单糖的乙烯基醚在HI/ZnCl2或TFA/EtAlCl2引发体系中进行了序贯活性嵌段共聚。得到的嵌段共聚物具有窄的分子量分布(Mw/Mn-1.1)和可控的组成。成功地实现了对前驱体聚合物的定量脱保护，得到了目标两亲性化合物。两亲嵌段共聚物在不同溶剂中的溶解度与嵌段组成(m/n)密切相关。在透射电子显微镜下观察到载糖嵌段共聚物的溶剂浇铸薄膜呈现出不同的微相分离表面形态，如球状、圆柱状和片状。接触角测量表明，嵌段共聚物膜的表面性质随环境条件的变化而变化，表面疏水的异丁基链段可以通过将其浸泡在水中而被亲水链段取代。为了更精确地控制其精细结构，我们将Langmuir-Blodgett(LB)技术应用于这种嵌段共聚物。这种嵌段共聚物从氯仿和甲醇的混合溶液中扩散到水面上，形成了稳定的单分子层，并通过LB技术成功地转移到了底物上。结果表明，均聚物共混可以控制LB膜的层状结构。

项目成果

T. Miyamoto: "糖を側鎖に有する両親媒性ブロック共重合体の精密合成" 日本化学繊維研究所講演集. 52. 67-75 (1995)

T. Miyamoto：“侧链含糖的两亲性嵌段共聚物的精确合成”日本化学纤维研究所讲座 52. 67-75 (1995)。

T.Miyamoto et al.: "Synthesis of Glycopolymers and Their Application to Biofunctional Materials" Kobunshi. 45. 553-557 (1996)

T.Miyamoto 等人：“糖聚合物的合成及其在生物功能材料中的应用”Kobunshi。

Kenji Yamada: "Controlled Synthesis of Glycopolymers with Pendant D-Glucosamine Residues by Living Cationic Polymerization" Journal of Polymer Science : Part A : Polymer Chemistry.

Kenji Yamada：“通过活性阳离子聚合控制含 D-葡萄糖胺残基的糖聚合物的合成”《高分子科学杂志》：A 部分：高分子化学。

K.Yamada et al.: "Controlled Synthesis of Glycopolymers with Pendant D-Glucosamine Residues by Living Cationic Polymerization" Journal of Polymer Science : PartA : Polymer Chemistry. 35. 751-757 (1997)

K.Yamada 等人：“通过活性阳离子聚合控制具有侧链 D-葡萄糖胺残基的糖聚合物”，《聚合物科学杂志》：A 部分：聚合物化学。

K. Yamada: "Controlled Synthesis of Amphiphilic Block Copolymers with Pendant Glucose Residues by Living Cationic Polymerization" J. Polym. Sci., Part A : Polym. Chem.(発表予定). (1996)

K. Yamada：“通过活性阳离子聚合控制两亲性嵌段共聚物的合成”，J. Polym.，A 部分：Polym Chem。