{"created":"2024-10-24T02:06:13.567976+00:00","id":2000527,"links":{},"metadata":{"_buckets":{"deposit":"11c64cbe-6022-4e11-a30b-38ca10f18179"},"_deposit":{"created_by":29,"id":"2000527","owners":[29],"pid":{"revision_id":0,"type":"depid","value":"2000527"},"status":"published"},"_oai":{"id":"oai:ir.kagoshima-u.ac.jp:02000527","sets":["35:67"]},"author_link":["10999","125837","24217"],"control_number":"2000527","item_6_biblio_info_5":{"attribute_name":"bibliographic_information","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2016","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"2","bibliographicPageEnd":"40","bibliographicPageStart":"32","bibliographicVolumeNumber":"15","bibliographic_titles":[{"bibliographic_title":"Journal of Computer Chemistry, Japan","bibliographic_titleLang":"en"}]}]},"item_6_date_6":{"attribute_name":"作成日","attribute_value_mlt":[{"subitem_date_issued_datetime":"2016","subitem_date_issued_type":"Issued"}]},"item_6_description_4":{"attribute_name":"要約(Abstract)","attribute_value_mlt":[{"subitem_description":"ウレタン樹脂の製造と物性に関する基本的情報である，イソシアナートのウレタン化反応性と触媒作用，生成するカルバミン酸とそのエステルの脱炭酸と安定性および副生物の挙動について，計算化学を用いて検 討した．その際各節に示す基本的な実験結果につき，反応過程のエネルギーと立体化学変化をMOPAC-PM6 法 でシミュレーションして解析した．置換フェニルイソシアナートとアルコールとのウレタン化反応性が，フロンティア軌道HOMOとLUMOのエネルギーを利用する置換基分子のMullikenの電気陰性度値((IP + EA)/2)，と大きい相関係数で表されることを示す．そのウレタン化反応は，1：2モル比の6員環錯体を経て，遷移状態の活性化エネルギー(Ea)は4∼13 kcal mol−1 と検証された．メチルアミンとのウレア化は反応性が高いが，それは会合体を形成し易く，Ea が小さいためと判断された．遷移状態構造の結果からは，3分子間の水素結合とその役割が理解される．第3級アミンの触媒作用は，上記1：2 錯体中のプロトンの捕捉促進とNCOへの受け渡しで，Eaを低下させると解析された．イソシアナートと水の反応で生成するカルバミン酸の不安定で発泡の事実等に関しては，分解の素過程の Ea が11 kcal mol−1と低く，アミンと CO2 に分解すると検証された．","subitem_description_language":"ja","subitem_description_type":"Other"},{"subitem_description":"Urethane resins show peculiar coatings, adhesives and cushions. The urethane formations from isocyanates with alcohols etc. are accompanied by carbamic acids, the esters, and their decomposed compounds for material performances. The steric and energy changes in the basic reaction processes of isocyanates、and the catalytic reaction by triethylamine were speculated by MOPAC-PM6 simulation, and the simulations compared with them by other methods. Thus, K. C. Frischs' analysis that the reactivities between substituted phenylisocyanates and an alcohol are related to Hammett substituent constants,σ (R = 0.97), was correlated with Mulliken's electronegativity, (IP + EA)/2 by PM6 method (R = 0.97). The reactions were speculated to proceed via hydrogen-bondings and six-membered ring 1:2 complexes of isocyanate with alcohol (water or amine) and by the activation energy of Ea = 4∼13 kcal mol−1. The higher reactivity is pointed out by the calculated smaller Ea value. The calculations including PM6-D3H4 were also effective for the reactivity of X-NCO. The 4 molecules' catalytic reaction of PhNCO with 2MeOH by Et3N was speculated to be accelerated from Ea = 7.23 kcal mol−1 to Ea = 3.92 kcal mol−1. The transition state structure showed the easy proton transfer by Et3N. Hydrolyses of carbamic acid and the methyl carbamate ester were compared for urethane properties, and the decomposition of the acid to diphenylurea via aniline etc. and the stability of the ester were speculated by the calculated Ea and transition state structures.","subitem_description_language":"en","subitem_description_type":"Other"}]},"item_6_publisher_23":{"attribute_name":"公開者・出版者","attribute_value_mlt":[{"subitem_publisher":"日本コンピュータ化学会","subitem_publisher_language":"ja"}]},"item_6_relation_11":{"attribute_name":"item_6_relation_11","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://doi.org/10.2477/jccj.2015-0073","subitem_relation_type_select":"DOI"}}]},"item_6_rights_12":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"(c) 2016 Society of Computer Chemistry, Japan","subitem_rights_language":"en"}]},"item_6_source_id_7":{"attribute_name":"item_6_source_id_7","attribute_value_mlt":[{"subitem_source_identifier":"13473824","subitem_source_identifier_type":"EISSN"}]},"item_6_source_id_9":{"attribute_name":"item_6_source_id_9","attribute_value_mlt":[{"subitem_source_identifier":"AA11657986","subitem_source_identifier_type":"NCID"}]},"item_6_version_type_14":{"attribute_name":"出版タイプ","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":[{"creatorNames":[{"creatorName":"染川, 賢一","creatorNameLang":"ja"},{"creatorName":"Somekawa, Kenichi","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"10999","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"満塩, 勝","creatorNameLang":"ja"},{"creatorName":"Mitsushio, Masaru","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"125837","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"上田, 岳彦","creatorNameLang":"ja"},{"creatorName":"Ueda, Takehiko","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"24217","nameIdentifierScheme":"WEKO"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_access","date":[{"dateType":"Available","dateValue":"2024-10-24"}],"displaytype":"detail","filename":"15_2015-0073.pdf","filesize":[{"value":"2.7 MB"}],"format":"application/pdf","mimetype":"application/pdf","url":{"label":"15_2015-0073","objectType":"fulltext","url":"https://ir.kagoshima-u.ac.jp/record/2000527/files/15_2015-0073.pdf"},"version_id":"e2e0bfd6-660d-4e1e-bdd2-58e64c7c3770"}]},"item_keyword":{"attribute_name":"キーワード","attribute_value_mlt":[{"subitem_subject":"イソシアナート","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"ウレタン","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"PM6","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"シミュレーション","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"活性化エネルギー","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"カルバミン酸","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"6員環1：2錯体","subitem_subject_language":"ja","subitem_subject_scheme":"Other"},{"subitem_subject":"Urethane","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"Isocyanate","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"Carbamic acid","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"Activation energy","subitem_subject_language":"en","subitem_subject_scheme":"Other"},{"subitem_subject":"Six-membered 12 complex","subitem_subject_language":"en","subitem_subject_scheme":"Other"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"jpn"}]},"item_resource_type":{"attribute_name":"item_resource_type","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"イソシアナートのウレタン化反応過程におけるエネルギー，立体変化および置換基効果の分子シミュレーション","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"イソシアナートのウレタン化反応過程におけるエネルギー，立体変化および置換基効果の分子シミュレーション","subitem_title_language":"ja"},{"subitem_title":"Molecular Simulation of Potential Energies, Steric Changesand Substituent Effects in Urethane Formation Reactionsfrom Isocyanates","subitem_title_language":"en"}]},"item_type_id":"6","owner":"29","path":["67"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2024-10-24"},"publish_date":"2024-10-24","publish_status":"0","recid":"2000527","relation_version_is_last":true,"title":["イソシアナートのウレタン化反応過程におけるエネルギー，立体変化および置換基効果の分子シミュレーション"],"weko_creator_id":"29","weko_shared_id":-1},"updated":"2024-10-24T02:27:28.617140+00:00"}