Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene
Chemically initiated oxidative polymerization stands out as the most suitable method for the large‐scale and controllable synthesis of perfluoropolyether (PFPE). However, the mechanism and related reaction kinetics of this synthesis reaction remain elusive. In this study, PFPE was synthesized throug...
Gespeichert in:
| Veröffentlicht in: | AIChE journal 2024-11, Vol.70 (11), p.n/a |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | n/a |
|---|---|
| container_issue | 11 |
| container_start_page | |
| container_title | AIChE journal |
| container_volume | 70 |
| creator | Chen, Xin‐Tuo Zhang, Liang‐Liang Zhou, Li‐Yang Wang, Shu‐Hua Chen, Jian‐Feng |
| description | Chemically initiated oxidative polymerization stands out as the most suitable method for the large‐scale and controllable synthesis of perfluoropolyether (PFPE). However, the mechanism and related reaction kinetics of this synthesis reaction remain elusive. In this study, PFPE was synthesized through the copolymerization of hexafluoropropylene and oxygen, initiated by fluorine. Subsequently, the synthesis mechanism of this chemically initiated oxidative polymerization was first explored using density functional theory. Simulation results yielded a comprehensive reaction network of the synthesis process, including chain initiation, propagation, decomposition, transfer, and termination. Meanwhile, a detailed kinetic model was constructed based on theoretical reaction rates of relevant elementary reactions. The effects of reaction operating conditions on the molecular weight of PFPE were experimentally investigated, with results in good agreement with the kinetic model. This work stablishes a solid foundation for optimizing and controlling the PFPE synthesis process. |
| doi_str_mv | 10.1002/aic.18534 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_3115757511</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>3115757511</sourcerecordid><originalsourceid>FETCH-LOGICAL-c2224-39ec8e1743f496f1219c758e3982c4be50e11b6199ca217e7cab94ff948bc55b3</originalsourceid><addsrcrecordid>eNp1kE9PwzAMxSMEEmNw4BtE4sShW5w2a3OcJv5JQ1zgXKWpo2a0zWhaWPn0ZJQrsiXrWT_7SY-Qa2ALYIwvldULyEScnJAZiCSNhGTilMwYYxCFBZyTC-93QfE04zNSPaOuVGt9Q1Vb0nfbYm-1p74fypE6Q_sKqa6wsVrV9Uhta3ureiypO9hS9fYT6d7VY4Od_Q7StcejCg_K1IPr3D70WGOLl-TMqNrj1d-ck7f7u9fNY7R9eXjarLeR5pwnUSxRZwhpEptErgxwkDoVGcYy4zopUDAEKFYgpVYcUky1KmRijEyyQgtRxHNyM_0Nzh8D-j7fuaFrg2UeA4g0FECgbidKd877Dk2-72yjujEHlh-DzEOQ-W-QgV1O7JetcfwfzNdPm-niBwuEdmY</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>3115757511</pqid></control><display><type>article</type><title>Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene</title><source>Wiley Online Library Journals Frontfile Complete</source><creator>Chen, Xin‐Tuo ; Zhang, Liang‐Liang ; Zhou, Li‐Yang ; Wang, Shu‐Hua ; Chen, Jian‐Feng</creator><creatorcontrib>Chen, Xin‐Tuo ; Zhang, Liang‐Liang ; Zhou, Li‐Yang ; Wang, Shu‐Hua ; Chen, Jian‐Feng</creatorcontrib><description>Chemically initiated oxidative polymerization stands out as the most suitable method for the large‐scale and controllable synthesis of perfluoropolyether (PFPE). However, the mechanism and related reaction kinetics of this synthesis reaction remain elusive. In this study, PFPE was synthesized through the copolymerization of hexafluoropropylene and oxygen, initiated by fluorine. Subsequently, the synthesis mechanism of this chemically initiated oxidative polymerization was first explored using density functional theory. Simulation results yielded a comprehensive reaction network of the synthesis process, including chain initiation, propagation, decomposition, transfer, and termination. Meanwhile, a detailed kinetic model was constructed based on theoretical reaction rates of relevant elementary reactions. The effects of reaction operating conditions on the molecular weight of PFPE were experimentally investigated, with results in good agreement with the kinetic model. This work stablishes a solid foundation for optimizing and controlling the PFPE synthesis process.</description><identifier>ISSN: 0001-1541</identifier><identifier>EISSN: 1547-5905</identifier><identifier>DOI: 10.1002/aic.18534</identifier><language>eng</language><publisher>Hoboken, USA: John Wiley & Sons, Inc</publisher><subject>Chemical synthesis ; computational chemistry ; Controllability ; Copolymerization ; Decomposition reactions ; Density functional theory ; Fluorine ; free radical ; Initiation (polymerization) ; Kinetics ; Molecular weight ; perfluoropolyether ; Polymerization ; Reaction kinetics ; Scale (corrosion) ; Termination (polymerization)</subject><ispartof>AIChE journal, 2024-11, Vol.70 (11), p.n/a</ispartof><rights>2024 American Institute of Chemical Engineers.</rights><rights>2024 American Institute of Chemical Engineers</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c2224-39ec8e1743f496f1219c758e3982c4be50e11b6199ca217e7cab94ff948bc55b3</cites><orcidid>0000-0002-6812-6860</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Faic.18534$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Faic.18534$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,777,781,1412,27905,27906,45555,45556</link.rule.ids></links><search><creatorcontrib>Chen, Xin‐Tuo</creatorcontrib><creatorcontrib>Zhang, Liang‐Liang</creatorcontrib><creatorcontrib>Zhou, Li‐Yang</creatorcontrib><creatorcontrib>Wang, Shu‐Hua</creatorcontrib><creatorcontrib>Chen, Jian‐Feng</creatorcontrib><title>Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene</title><title>AIChE journal</title><description>Chemically initiated oxidative polymerization stands out as the most suitable method for the large‐scale and controllable synthesis of perfluoropolyether (PFPE). However, the mechanism and related reaction kinetics of this synthesis reaction remain elusive. In this study, PFPE was synthesized through the copolymerization of hexafluoropropylene and oxygen, initiated by fluorine. Subsequently, the synthesis mechanism of this chemically initiated oxidative polymerization was first explored using density functional theory. Simulation results yielded a comprehensive reaction network of the synthesis process, including chain initiation, propagation, decomposition, transfer, and termination. Meanwhile, a detailed kinetic model was constructed based on theoretical reaction rates of relevant elementary reactions. The effects of reaction operating conditions on the molecular weight of PFPE were experimentally investigated, with results in good agreement with the kinetic model. This work stablishes a solid foundation for optimizing and controlling the PFPE synthesis process.</description><subject>Chemical synthesis</subject><subject>computational chemistry</subject><subject>Controllability</subject><subject>Copolymerization</subject><subject>Decomposition reactions</subject><subject>Density functional theory</subject><subject>Fluorine</subject><subject>free radical</subject><subject>Initiation (polymerization)</subject><subject>Kinetics</subject><subject>Molecular weight</subject><subject>perfluoropolyether</subject><subject>Polymerization</subject><subject>Reaction kinetics</subject><subject>Scale (corrosion)</subject><subject>Termination (polymerization)</subject><issn>0001-1541</issn><issn>1547-5905</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNp1kE9PwzAMxSMEEmNw4BtE4sShW5w2a3OcJv5JQ1zgXKWpo2a0zWhaWPn0ZJQrsiXrWT_7SY-Qa2ALYIwvldULyEScnJAZiCSNhGTilMwYYxCFBZyTC-93QfE04zNSPaOuVGt9Q1Vb0nfbYm-1p74fypE6Q_sKqa6wsVrV9Uhta3ureiypO9hS9fYT6d7VY4Od_Q7StcejCg_K1IPr3D70WGOLl-TMqNrj1d-ck7f7u9fNY7R9eXjarLeR5pwnUSxRZwhpEptErgxwkDoVGcYy4zopUDAEKFYgpVYcUky1KmRijEyyQgtRxHNyM_0Nzh8D-j7fuaFrg2UeA4g0FECgbidKd877Dk2-72yjujEHlh-DzEOQ-W-QgV1O7JetcfwfzNdPm-niBwuEdmY</recordid><startdate>202411</startdate><enddate>202411</enddate><creator>Chen, Xin‐Tuo</creator><creator>Zhang, Liang‐Liang</creator><creator>Zhou, Li‐Yang</creator><creator>Wang, Shu‐Hua</creator><creator>Chen, Jian‐Feng</creator><general>John Wiley & Sons, Inc</general><general>American Institute of Chemical Engineers</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7ST</scope><scope>7U5</scope><scope>8FD</scope><scope>C1K</scope><scope>L7M</scope><scope>SOI</scope><orcidid>https://orcid.org/0000-0002-6812-6860</orcidid></search><sort><creationdate>202411</creationdate><title>Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene</title><author>Chen, Xin‐Tuo ; Zhang, Liang‐Liang ; Zhou, Li‐Yang ; Wang, Shu‐Hua ; Chen, Jian‐Feng</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2224-39ec8e1743f496f1219c758e3982c4be50e11b6199ca217e7cab94ff948bc55b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Chemical synthesis</topic><topic>computational chemistry</topic><topic>Controllability</topic><topic>Copolymerization</topic><topic>Decomposition reactions</topic><topic>Density functional theory</topic><topic>Fluorine</topic><topic>free radical</topic><topic>Initiation (polymerization)</topic><topic>Kinetics</topic><topic>Molecular weight</topic><topic>perfluoropolyether</topic><topic>Polymerization</topic><topic>Reaction kinetics</topic><topic>Scale (corrosion)</topic><topic>Termination (polymerization)</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Chen, Xin‐Tuo</creatorcontrib><creatorcontrib>Zhang, Liang‐Liang</creatorcontrib><creatorcontrib>Zhou, Li‐Yang</creatorcontrib><creatorcontrib>Wang, Shu‐Hua</creatorcontrib><creatorcontrib>Chen, Jian‐Feng</creatorcontrib><collection>CrossRef</collection><collection>Environment Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Environment Abstracts</collection><jtitle>AIChE journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Chen, Xin‐Tuo</au><au>Zhang, Liang‐Liang</au><au>Zhou, Li‐Yang</au><au>Wang, Shu‐Hua</au><au>Chen, Jian‐Feng</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene</atitle><jtitle>AIChE journal</jtitle><date>2024-11</date><risdate>2024</risdate><volume>70</volume><issue>11</issue><epage>n/a</epage><issn>0001-1541</issn><eissn>1547-5905</eissn><abstract>Chemically initiated oxidative polymerization stands out as the most suitable method for the large‐scale and controllable synthesis of perfluoropolyether (PFPE). However, the mechanism and related reaction kinetics of this synthesis reaction remain elusive. In this study, PFPE was synthesized through the copolymerization of hexafluoropropylene and oxygen, initiated by fluorine. Subsequently, the synthesis mechanism of this chemically initiated oxidative polymerization was first explored using density functional theory. Simulation results yielded a comprehensive reaction network of the synthesis process, including chain initiation, propagation, decomposition, transfer, and termination. Meanwhile, a detailed kinetic model was constructed based on theoretical reaction rates of relevant elementary reactions. The effects of reaction operating conditions on the molecular weight of PFPE were experimentally investigated, with results in good agreement with the kinetic model. This work stablishes a solid foundation for optimizing and controlling the PFPE synthesis process.</abstract><cop>Hoboken, USA</cop><pub>John Wiley & Sons, Inc</pub><doi>10.1002/aic.18534</doi><tpages>15</tpages><orcidid>https://orcid.org/0000-0002-6812-6860</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0001-1541 |
| ispartof | AIChE journal, 2024-11, Vol.70 (11), p.n/a |
| issn | 0001-1541 1547-5905 |
| language | eng |
| recordid | cdi_proquest_journals_3115757511 |
| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Chemical synthesis computational chemistry Controllability Copolymerization Decomposition reactions Density functional theory Fluorine free radical Initiation (polymerization) Kinetics Molecular weight perfluoropolyether Polymerization Reaction kinetics Scale (corrosion) Termination (polymerization) |
| title | Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-20T01%3A59%3A21IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Mechanism%20and%20kinetics%20study%20of%20the%20chemically%20initiated%20oxidative%20polymerization%20of%20hexafluoropropylene&rft.jtitle=AIChE%20journal&rft.au=Chen,%20Xin%E2%80%90Tuo&rft.date=2024-11&rft.volume=70&rft.issue=11&rft.epage=n/a&rft.issn=0001-1541&rft.eissn=1547-5905&rft_id=info:doi/10.1002/aic.18534&rft_dat=%3Cproquest_cross%3E3115757511%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=3115757511&rft_id=info:pmid/&rfr_iscdi=true |