{"created":"2023-06-20T07:14:43.602262+00:00","id":2007599,"links":{},"metadata":{"_buckets":{"deposit":"933f9d6c-a275-416c-88cb-f467cb6afe26"},"_deposit":{"created_by":18,"id":"2007599","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"2007599"},"status":"published"},"_oai":{"id":"oai:repository.dl.itc.u-tokyo.ac.jp:02007599","sets":["6:18:19","9:10:11"]},"author_link":[],"control_number":"2007599","item_1623051606154":{"attribute_name":"出版タイプ","attribute_value_mlt":[{"subitem_version_type":"AM"}]},"item_2_biblio_info_7":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2022-03-25","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"11","bibliographicPageEnd":"1532","bibliographicPageStart":"1524","bibliographicVolumeNumber":"55","bibliographic_titles":[{"bibliographic_title":"Accounts of Chemical Research","bibliographic_titleLang":"en"}]}]},"item_2_description_5":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"Carbon dioxide (CO2) has long been considered a sustainable comonomer for polymer synthesis due to its abundance, easy availability, and low toxicity. Polymer synthesis from CO2 is highly attractive and has received continuous interest from synthetic chemists. In this regard, alternating copolymerization of CO2 and epoxides is one of the most well-established methods to synthesize aliphatic polycarbonates. Moreover, binucleophiles including diols, diamines, amino alcohols, and diynes have been reported to copolymerize with CO2 to give polycarbonates, polyureas, polyurethanes, and polyesters, respectively. Nevertheless, little success has been made for incorporating CO2 into the most widely used polyolefin materials.\nAlthough extensive studies have been focused on the copolymerization of olefins and CO2, most of the attempted reactions resulted in olefin homopolymerization owing to the endothermic property and high energy barriers of CO2 insertion during the chain propagation process. In this Account, we show how this challenge is addressed by taking advantage of a metastable lactone intermediate, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVP), which is produced from CO2 and butadiene via palladium catalysis. Homopolymerization of EVP furnishes CO2/butadiene copolymers with up to 29 wt % of CO2 content. This reaction strategy represents a breakthrough for the long-standing challenge of inherent kinetic and thermodynamically unfavorable CO2/olefin copolymerization. A new class of polymeric materials bearing repeating bicyclic lactone and unsaturated lactone units can be obtained. Importantly, one-pot copolymerization of CO2/butadiene or terpolymerization of CO2/butadiene/diene can be achieved to afford copolymers through a two-step reaction protocol. Interestingly, the bicyclic lactone units in the polymer chain can undergo ring-opening through hydrolysis and aminolysis, while reversible ring-closing of the hydrolyzed or aminolyzed units was also achieved simply by heating.\nOver the past few years, more and more studies have utilized EVP as an intermediate to synthesize copolymers from olefins, butadiene, and CO2. Recently, we successfully incorporated CO2 into the most widely used polyethylene materials via the direct copolymerization of EVP and ethylene. Taking advantage of the bifunctional reactivity of EVP, we were able to access two types of main-chain-functionalized polyethylenes through palladium-catalyzed coordination/insertion copolymerization and radical copolymerization. Besides polyethylenes, CO2 was also incorporated into poly(methyl methacrylate), poly(methyl acrylate), polystyrene, polymethyl acrylate, polyvinylchloroacetate, and poly(vinyl acetate) materials via radical copolymerization of EVP and olefin monomers. The EVP/olefin copolymerization strategy provides a novel avenue for the synthesis of highly versatile copolymers from an olefin, CO2, and butadiene.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_2_publisher_20":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"American Chemical Society","subitem_publisher_language":"en"}]},"item_2_relation_25":{"attribute_name":"関係URI","attribute_value_mlt":[{"subitem_relation_type":"isVersionOf","subitem_relation_type_id":{"subitem_relation_type_id_text":"https://doi.org/10.1021/acs.accounts.2c00162","subitem_relation_type_select":"URI"}}]},"item_2_rights_12":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Accounts of Chemical Research], copyright [© 2022 American Chemical Society] after peer review and technical editing by the publisher. To access the final edited and published work see [https://doi.org/10.1021/acs.accounts.2c00162]."}]},"item_2_source_id_8":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"00014842","subitem_source_identifier_type":"PISSN"}]},"item_2_text_4":{"attribute_name":"著者所属","attribute_value_mlt":[{"subitem_text_language":"en","subitem_text_value":"Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorAffiliations":[{"affiliationNames":[{"affiliationName":"The University of Tokyo","affiliationNameLang":"en"}]}],"creatorNames":[{"creatorName":"Tang, Shan","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"0000-0001-5662-8401","nameIdentifierScheme":"ORCID","nameIdentifierURI":"https://orcid.org/0000-0001-5662-8401"}]},{"creatorAffiliations":[{"affiliationNames":[{"affiliationName":"The University of Tokyo","affiliationNameLang":"en"}]}],"creatorNames":[{"creatorName":"Nozaki, Kyoko","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"0000-0002-0321-5299","nameIdentifierScheme":"ORCID","nameIdentifierURI":"https://orcid.org/0000-0002-0321-5299"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_access","date":[{"dateType":"Available","dateValue":"2023-06-20"}],"displaytype":"detail","filename":"acs_accounts2c00162.pdf","filesize":[{"value":"874.6 KB"}],"format":"application/pdf","license_note":"© 2022 American Chemical Society","licensetype":"license_note","mimetype":"application/pdf","url":{"objectType":"fulltext","url":"https://repository.dl.itc.u-tokyo.ac.jp/record/2007599/files/acs_accounts2c00162.pdf"},"version_id":"c268c373-3347-4e52-bf24-a3b7b25b6407"}]},"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":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"Advances in the Synthesis of Copolymers from Carbon Dioxide, Dienes, and Olefins","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Advances in the Synthesis of Copolymers from Carbon Dioxide, Dienes, and Olefins","subitem_title_language":"en"}]},"item_type_id":"2","owner":"18","path":["11","19"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2023-06-20"},"publish_date":"2023-06-20","publish_status":"0","recid":"2007599","relation_version_is_last":true,"title":["Advances in the Synthesis of Copolymers from Carbon Dioxide, Dienes, and Olefins"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-06-20T07:19:37.307868+00:00"}