京都大学教育研究振興財団助成事業
成 果 報 告 書
2022 年 5 月 2 日
公益財団法人京都大学教育研究振興財団会 長藤洋 作

様

所属部局

工学研究科・高分子化学専攻・先端機能高分子講座C職名

講師

氏

名

ランデンベーガー キラ ベス

令和 3 年度 ・助 成 の 種 類

研究活動推進助成

申請時の科研費
研 究 課 題 名

新しい分子間相互によるポリマー構造および性質の影響の検討

上記以外で助成金を 充 当 し た
研 究 内 容なし
（所属・職名・氏名）

助成金充当に関わる共同研究者

発表学会文献等成 果 の 概 要

京都大学大学院工学研究科・修士課程・隆永鈴木 および 西村希望
京都大学大工学研究科・学部・栃谷魁斗（この研究成果を発表した学会・文献等）
第70回高分子討論会 「ハロゲン結合可能なビニルエーテルモノマーによるポリマー合成及びその解析〜自己組織化を目指して〜」、2021/9/7 鈴木隆永 、オンライン
ACS Spring 2022 「Investigation of the influence of polymer structure on the halogen bonding
ability of novel poly(vinyl ether)s containing perfluoroiodobenzene moieties」、 2022/3/22、 鈴木隆永、 栃谷魁斗、 ランデンベーガー キラ ベス、オンライン

研究内容・研究成果・今後の見通しなどについて、 簡略に、A４版・和文で作成し、添付して下さい。（タイトルは「成果の概要／報告者名」）
交付 を 受 けた 助成 金額

1,000,000円

使 用 し た 助 成 金 額

1,000,000円

返納すべき助成金額0円

費
会

計報

告助成金の使途内訳

当財団の助成について目金額

化合物および実験用消耗品

304,689

実験用のグラス器具

213,675

国際学会参加費

23,371

ロータリーエバポレータ

146,960

純水器

138,330

冷却水循環装置

172,975（今回の助成に対する感想、今後の助成に望むこと等お書き下さい。助成事業の参考にさせていただきます。）

支援があるために研究が続きましたので感謝しています。

成果の概要/ランデンベーガー

キラベス

研究内容
This research aims to develop novel self-assembling polymers using halogen bonding interactions
and poly(vinyl ether)s as a means to investigate the effects of polymer backbones on self-assembly
properties, with the purpose of forming better supramolecular polymer networks (SPN). Halogen
bonding is the intermolecular interaction between the electron-poor -hole on a halogen (I, Br or Cl)
and an electron-rich Lewis base (often O or N), and while potentially as strong as hydrogen bonding, it
is, comparatively, underrepresented. For polymer self-assembly materials, poly(vinyl ether)s, with amore flexible backbone than most other polymers, are also underrepresented. SPN are network
structures of polymers held together by directional and specific non-covalent interactions at netpoints
and have great potential as self-healing materials.
The research supported by this grant enabled steps towards the formation of SPN and consisted ofthree main research focuses: 1) synthesis of polymer structures using novel halogen bonding vinyl ether
monomers that were previously developed in our lab, 2) development of halogen bond acceptors, and3) investigation of the halogen bonding ability of the formed materials and any self-assembly structures.

研究成果
A variety of polymer structures were successfully synthesized using the novel halogen bonding vinyl
ether monomers developed in our lab and included AB block copolymers and random copolymers.
Initial investigations were also made into the synthesis of ABA triblock copolymers, but these studies
are still ongoing. Copolymers were created using isobutyl vinyl ether (IBVE) as the comonomer, as thisshould not participate in halogen bonding. For the samples created a 1:2 ratio of halogen bonding vinylether monomer to IBVE was synthesized. Controlled polymerization was achieved for all samples.
Synthesis of star-shaped polymers was also investigated. Star-shaped polymers offer increased
contact points and are expected to ease the formation of SPN. An extensive study into determining
amenable conditions for the formation of star-shaped polymers using these novel vinyl ether monomers
was carried out. All three halogen bonding monomers allowed for the formation of well-developed starshaped polymers, but ratio of crosslinker varied with the type of monomer.
Various attempts were made to create poly(vinyl ether) acceptors for halogen bonding, but efforts
have not yet produced materials that are well-suited for the formation of SPN. Early efforts to create abifunctional charge transfer agent/initiator for a RAFT/living cationic polymerization system mainly
produced unwanted products and the sample could not be readily purified. Subsequent efforts to do
post-polymerization reactions are still in the early stages and have not yet produced results.
Halogen bonding was observed, using 19FNMR spectroscopy, in all samples containing the halogen
bonding vinyl ether units. When using triethylamine (a single-point acceptor), the monomer species
showed greater halogen bonding ability than the polymer species. When using tris[2(dimethylamino)ethyl]amine (Me6TREN) (a four-point acceptor), however, a reverse trend was noted
and polymer species showed superior halogen bonding ability. This encouraging result indicated thatpolymer-polymer interactions will be the most effective in forming supramolecular materials based on
halogen bonding. Star-shaped polymers showed a reduced halogen bonding ability, but this is due tosteric hinderance and formation of block star-shaped polymers should counter this effect.

今後の見通しThere is still much research left to do to effectively develop SPN based on halogen bonding
poly(vinyl ether)s. In particular, active research is continuing on the development of poly(vinyl ether)sthat function as acceptors for halogen bonding. A variety of post-polymerization reactions are currently
under consideration. Additionally, development of an even wider range of polymer structures using thehalogen bonding vinyl ethers is also planned. Finally, while halogen bonding was observed, formationof self-assembly structures was not achieved during this grant period; with appropriate acceptors
creation of self-assembly structures and investigation of conditions that facilitate this is planned.