{"created":"2023-06-19T10:29:42.633654+00:00","id":9689,"links":{},"metadata":{"_buckets":{"deposit":"c93f4cbd-2e53-4db8-b238-f49e258ad0ba"},"_deposit":{"created_by":18,"id":"9689","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"9689"},"status":"published"},"_oai":{"id":"oai:muroran-it.repo.nii.ac.jp:00009689","sets":["41:227"]},"author_link":["55188"],"item_81_date_granted_17":{"attribute_name":"学位授与年月日","attribute_value_mlt":[{"subitem_dategranted":"2018-03-23"}]},"item_81_degree_grantor_10":{"attribute_name":"学位授与機関","attribute_value_mlt":[{"subitem_degreegrantor":[{"subitem_degreegrantor_language":"ja","subitem_degreegrantor_name":"室蘭工業大学"},{"subitem_degreegrantor_language":"en","subitem_degreegrantor_name":"Muroran Institute of Technology"}],"subitem_degreegrantor_identifier":[{"subitem_degreegrantor_identifier_name":"10103","subitem_degreegrantor_identifier_scheme":"kakenhi"}]}]},"item_81_degree_name_11":{"attribute_name":"学位名","attribute_value_mlt":[{"subitem_degreename":"博士（工学）","subitem_degreename_language":"ja"}]},"item_81_description_25":{"attribute_name":"フォーマット","attribute_value_mlt":[{"subitem_description":"application/pdf","subitem_description_type":"Other"}]},"item_81_description_7":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"Half-esters are among the most important building blocks for organic synthesis of a variety of compounds including pharmaceuticals and polymers. Most typically, they are prepared by monohydrolysis of symmetric diesters. Therefore, it is important to develop an efficient methodology for selective monohydrolysis of symmetric diesters. Ring-opening metathesis polymerization (ROMP) has been attracted great attention of homogeneous catalysis emerging, owing to its important implications in polymer chemistry as well as material chemistry. The interesting features of ROMP include the fact that appropriate selection of the catalyst system enables polymerization of various types of cyclic olefins bearing even polar substituents. Polycycloolefins synthesized by ROMP are applicable for organic synthesis of an array of compounds relevant to cell signaling, DNA diagnostics, drug delivery, antibacterial materials, photo and electrochromic devices, and transistors. In many applications, the instability of the unsaturated polymers to chemical and thermal degradation is a concern. Hence, ROMP of cycloolefins, followed by hydrogenation, may enable synthesis of high molecular weight, narrow polydispersity polyolefins with desirable optical characteristics, because these ROMP polymers have poor thermal stability due to the unsaturation. Based on these backgrounds, the author first aimed at improving highly efficient selective monohydrolysis reactions in the aqueous media for several bulky symmetric diesters. The doubly functionalized norbornadiene derivatives with ester and carboxyl groups obtained from the monohydrolsis reaction were polymerized by ROMP for synthesis of various polymers with the norbornadiene skeleton. Then synthesized polymers were hydrogenated and epoxidized, which are expected to exhibit higher thermal stability. More specifically, the following results were described: 1. Through the highly efficient and practical monohydrolysis of symmetric diesters using the aqueous media, the corresponding half-esters having a norbornadiene skeleton are rapidly obtained in very high yields. A larger proportion of a water-miscible polar aprotic co-solvent, DMSO, and aqueous KOH help accelerate the selective monohydrolysis reaction of several bulky symmetric diesters. Although certain bulky diesters had low reactivity, the co-solvent system can improve the reaction efficiency significantly. 2. A precise, controlled, and efficient methodology was described, using Grubbs’ 2nd generation catalyst based on living ROMP. Polynorbornadienes bearing various ester and carboxyl group were obtained in high yields. 3. The synthesized polymers were successfully hydrogenated for synthesis of the doubly functionalized saturated polynorbornadienes containing various ester groups. The epoxidation reagent, MCPBA, was an available reagent for converting the polynorbornadiene double bond into the corresponding epoxide.","subitem_description_language":"ja","subitem_description_type":"Abstract"},{"subitem_description":"本研究では、環境に優しく実用的な条件下での対称ジエステルのモノ加水分解反応を利用して、その生成物から種々の高分子のライブラリー合成を行った。対称化合物の非対称化反応は、一般に原料の対称化合物が安価で市販されているか安価で大量に合成できるため費用効果的な反応である。しかし対称化合物における二つの置換基が等価であるためそれを実用的な条件下で区別するのは困難であるとされていた。対称ジエステルのモノ加水分解反応により生成するハーフエステルは天然物や薬物合成の原料や高分子合成のためのモノマーなどとしてよく使用されている重要なシントンである。著者の所属する研究室では安価で環境に優しい方法で、かつ予測ができるような形で多様な対称ジエステルの高選択的モノ加水分解反応を可能とする反応を研究している。本研究ではまず対称ジエステルのモノ加水分解反応の条件を改良し、従来まで困難であった嵩高い対称ジエステルのモノ加水分解反応の検討を行った。特に非プロトン性で高極性の共溶媒を比較的高濃度で用いることで、超音波反応装置でも不可能であった、嵩高い対称ジエステルのモノ加水分解も効率よく進行させることを見出した。さらに本研究ではこの反応によって得られたノルボルナジエン骨格を有するハーフエステルから、種々のエステルや他の置換基を持った誘導体へと変換し、開環メタセシス反応により多様な特性を持った高分子のライブラリーを合成した。Grubbs触媒を用いた開環メタセシス反応により種々のアルケン類から高分子を効率的に合成する事はよく知られている。特にノルボルナジエン骨格を持つアルケンはひずんだ構造のため、この開環メタセシス反応により高分子を効率的に合成する事が知られている。これで生成する高分子は５員環構造を主鎖に持ち、対応するビニルポリマーより剛直性があり、側鎖官能基が主鎖に覆われにくくなるため、高い機能発現が期待され、細胞伝達系の研究、ドラッグデリバリー、抗バクテリア材料、発光材料、生体材料など多方面に応用されている。著者が研究している上記モノ加水分解反応は特にノルボルナジエン骨格を有するハーフエステルを高収率で生成しているので、そのような高分子の合成には最適である。また、特に高分子の中でも一般に不飽和結合を含んだ高分子は飽和高分子に比べて不安定である傾向があるため、熱的または化学的分解が懸念される。そこで上記の開環メタセシス反応により合成された種々の高分子に水素添加やエポキシ化を行って不飽和結合を飽和結合へと変換し、種々の物性の向上をはかった。水を主溶媒とする有機反応は典型的な環境調和型反応であるが、有機化合物の疎水性のためその成功例は限られている。本研究により、数少ない水中での有機反応の条件を再検討し、新規機能性高分子合成への応用へと展開できたため、本研究はその実用性の幅を拡大し、種々の有用な物質創製に大きく貢献すると考えられる。","subitem_description_language":"ja","subitem_description_type":"Abstract"}]},"item_81_dissertation_number_13":{"attribute_name":"学位授与番号","attribute_value_mlt":[{"subitem_dissertationnumber":"甲第420号"}]},"item_81_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.15118/00009641","subitem_identifier_reg_type":"JaLC"}]},"item_81_subject_9":{"attribute_name":"日本十進分類法","attribute_value_mlt":[{"subitem_subject":"431","subitem_subject_scheme":"NDC"}]},"item_81_text_12":{"attribute_name":"学位の種別","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"課程博士"}]},"item_81_text_14":{"attribute_name":"報告番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"甲第420号"}]},"item_81_text_15":{"attribute_name":"学位記番号","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"博甲第420号"}]},"item_81_text_16":{"attribute_name":"研究科・専攻","attribute_value_mlt":[{"subitem_text_language":"ja","subitem_text_value":"工学専攻"}]},"item_81_version_type_24":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open access","subitem_access_right_uri":"http://purl.org/coar/access_right/c_abf2"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorAffiliations":[{"affiliationNameIdentifiers":[],"affiliationNames":[{"affiliationName":""}]}],"creatorNames":[{"creatorName":"SHI, Jianjun","creatorNameLang":"en"},{"creatorName":"石, 建軍","creatorNameLang":"ja"}],"familyNames":[{},{}],"givenNames":[{},{}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-06-06"}],"displaytype":"detail","filename":"A420.pdf","filesize":[{"value":"7.7 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"A420","objectType":"fulltext","url":"https://muroran-it.repo.nii.ac.jp/record/9689/files/A420.pdf"},"version_id":"e0772d91-02b7-44b3-86ac-9be4bb662c7b"},{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2018-06-06"}],"displaytype":"detail","filename":"A420_summary.pdf","filesize":[{"value":"162.8 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"A420_summary","objectType":"abstract","url":"https://muroran-it.repo.nii.ac.jp/record/9689/files/A420_summary.pdf"},"version_id":"175eca1c-37d2-4d16-8df3-456a1e596463"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"doctoral thesis","resourceuri":"http://purl.org/coar/resource_type/c_db06"}]},"item_title":"SYNTHETIC STUDIES OF POLYMERS BY RING OPENING METATTHESIS POLYMERIZATION USING HALF-ESTERS OBTAINED BY PRACTICAL SELECTIVE MONOHYDROLYSIS REACTION","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"SYNTHETIC STUDIES OF POLYMERS BY RING OPENING METATTHESIS POLYMERIZATION USING HALF-ESTERS OBTAINED BY PRACTICAL SELECTIVE MONOHYDROLYSIS REACTION","subitem_title_language":"en"},{"subitem_title":"実用的な選択的モノ加水分解反応によって得られるハーフエステルを用いた開環メタセシス反応による高分子合成研究","subitem_title_language":"ja"}]},"item_type_id":"81","owner":"18","path":["227"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2018-06-06"},"publish_date":"2018-06-06","publish_status":"0","recid":"9689","relation_version_is_last":true,"title":["SYNTHETIC STUDIES OF POLYMERS BY RING OPENING METATTHESIS POLYMERIZATION USING HALF-ESTERS OBTAINED BY PRACTICAL SELECTIVE MONOHYDROLYSIS REACTION"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2024-01-22T02:38:38.859031+00:00"}