Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1‐Vinylcyclohexene (VCH)
We report the first anionic polymerization of 1‐vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2‐disubstituted 1,3‐diene proceeded quantitatively in cyclohexane at 25 °C with sec‐butyllithium as an initiator...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2023-07, Vol.62 (28), p.e202302907-n/a |
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| creator | Hahn, Christoph Rauschenbach, Moritz Frey, Holger |
| description | We report the first anionic polymerization of 1‐vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2‐disubstituted 1,3‐diene proceeded quantitatively in cyclohexane at 25 °C with sec‐butyllithium as an initiator. The obtained polymers have well‐controlled molecular weights in the range of 5 to 142 kg mol−1, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ |
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Anionic living polymerization of 1‐vinylcyclohexene (VCH) with sec‐BuLi as an initiator in cyclohexane is possible. It is a key question whether the monomer acts as a 1,3‐diene or as a styrenic monomer. The cyclic structure of the 1,2‐substituted monomer shows extraordinary consequences on copolymerization behavior, microstructure and thermal behavior, compared to other conventional linear dienes (e.g. butadiene, isoprene).</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202302907</identifier><identifier>PMID: 37186346</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>1,3-Dienes ; Anionic polymerization ; Butyllithium ; Copolymerization Kinetics ; Copolymers ; Cyclohexane ; Dienes ; Glass transition temperature ; Initiators ; Living Anionic Polymerization ; Microstructure ; Molecular weight ; Molecular weight distribution ; Monomers ; NMR ; Nuclear magnetic resonance ; Polyisoprene ; Polymerization ; Polymers ; Polystyrene ; Styrene ; Styrenes ; Transition temperatures</subject><ispartof>Angewandte Chemie International Edition, 2023-07, Vol.62 (28), p.e202302907-n/a</ispartof><rights>2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH</rights><rights>2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><rights>2023. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4137-bf5130cbe1158ca375cee9ff94ae7e2b1299dea69df121901bec437f876afd2b3</citedby><cites>FETCH-LOGICAL-c4137-bf5130cbe1158ca375cee9ff94ae7e2b1299dea69df121901bec437f876afd2b3</cites><orcidid>0000-0002-9916-3103</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%2Fanie.202302907$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.202302907$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37186346$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Hahn, Christoph</creatorcontrib><creatorcontrib>Rauschenbach, Moritz</creatorcontrib><creatorcontrib>Frey, Holger</creatorcontrib><title>Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1‐Vinylcyclohexene (VCH)</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>We report the first anionic polymerization of 1‐vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2‐disubstituted 1,3‐diene proceeded quantitatively in cyclohexane at 25 °C with sec‐butyllithium as an initiator. The obtained polymers have well‐controlled molecular weights in the range of 5 to 142 kg mol−1, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ<1.07–1.20). In situ 1H NMR kinetic characterization revealed a weak gradient structure for the copolymers of styrene and VCH, (rSty=2.55, rVCH=0.39). P(VCH) obtained in cyclohexane with sec‐BuLi as an initiator showed both 1,4‐ and 3,4‐incorporation mode (ratio: 64 : 36). It was demonstrated that the microstructure of the resulting P(VCH) can be altered by the addition of a modifier (THF), resulting in increasing 3,4‐microstructure (up to 78 %) and elevated glass‐transition temperature up to 89 °C. Thus, the monomer VCH polymerizes carbanionically like a diene, however leading to rigid polymers with high glass transition temperature, which provides interesting options for combination with other dienes to well‐defined polymer architectures and materials.
Anionic living polymerization of 1‐vinylcyclohexene (VCH) with sec‐BuLi as an initiator in cyclohexane is possible. It is a key question whether the monomer acts as a 1,3‐diene or as a styrenic monomer. The cyclic structure of the 1,2‐substituted monomer shows extraordinary consequences on copolymerization behavior, microstructure and thermal behavior, compared to other conventional linear dienes (e.g. butadiene, isoprene).</description><subject>1,3-Dienes</subject><subject>Anionic polymerization</subject><subject>Butyllithium</subject><subject>Copolymerization Kinetics</subject><subject>Copolymers</subject><subject>Cyclohexane</subject><subject>Dienes</subject><subject>Glass transition temperature</subject><subject>Initiators</subject><subject>Living Anionic Polymerization</subject><subject>Microstructure</subject><subject>Molecular weight</subject><subject>Molecular weight distribution</subject><subject>Monomers</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Polyisoprene</subject><subject>Polymerization</subject><subject>Polymers</subject><subject>Polystyrene</subject><subject>Styrene</subject><subject>Styrenes</subject><subject>Transition temperatures</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkctO3DAUhq2qqFzaLUtkqRtYZPAlie3uRlMoSEAr0bKNHOeYGmVsaidqw4pH4Bn7JHgYSqVuuvKxz3c-WedHaJeSGSWEHWrvYMYI44QpIl6hLVoxWnAh-Otcl5wXQlZ0E22ndJN5KUn9Bm1yQWXNy3oL9ecQr52_xpfDFMED1r7DH92quhziaIYxQsJDwBovJtM7s25-wHPvgs_XL6GflhDdnR7yAw4W09_3D1fOT73JA-E7_FrJ9q8WJwdv0YbVfYJ3z-cO-nZ89HVxUpx9_nS6mJ8VpqRcFK2tKCemBUoraTQXlQFQ1qpSgwDWUqZUB7pWnaWMKkJbMCUXVopa2461fAftr723MfwYIQ3N0iUDfa89hDE1TNKyYqosZUbf_4PehDH6_LtMcVYzJp-o2ZoyMaQUwTa30S11nBpKmlUOzSqH5iWHPLD3rB3bJXQv-J_FZ0CtgZ-uh-k_umZ-cXr0V_4IlT2VHA</recordid><startdate>20230710</startdate><enddate>20230710</enddate><creator>Hahn, Christoph</creator><creator>Rauschenbach, Moritz</creator><creator>Frey, Holger</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-9916-3103</orcidid></search><sort><creationdate>20230710</creationdate><title>Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1‐Vinylcyclohexene (VCH)</title><author>Hahn, Christoph ; Rauschenbach, Moritz ; Frey, Holger</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4137-bf5130cbe1158ca375cee9ff94ae7e2b1299dea69df121901bec437f876afd2b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>1,3-Dienes</topic><topic>Anionic polymerization</topic><topic>Butyllithium</topic><topic>Copolymerization Kinetics</topic><topic>Copolymers</topic><topic>Cyclohexane</topic><topic>Dienes</topic><topic>Glass transition temperature</topic><topic>Initiators</topic><topic>Living Anionic Polymerization</topic><topic>Microstructure</topic><topic>Molecular weight</topic><topic>Molecular weight distribution</topic><topic>Monomers</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Polyisoprene</topic><topic>Polymerization</topic><topic>Polymers</topic><topic>Polystyrene</topic><topic>Styrene</topic><topic>Styrenes</topic><topic>Transition temperatures</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hahn, Christoph</creatorcontrib><creatorcontrib>Rauschenbach, Moritz</creatorcontrib><creatorcontrib>Frey, Holger</creatorcontrib><collection>Wiley-Blackwell Open Access Collection</collection><collection>Wiley Online Library Free Content</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hahn, Christoph</au><au>Rauschenbach, Moritz</au><au>Frey, Holger</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1‐Vinylcyclohexene (VCH)</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2023-07-10</date><risdate>2023</risdate><volume>62</volume><issue>28</issue><spage>e202302907</spage><epage>n/a</epage><pages>e202302907-n/a</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>We report the first anionic polymerization of 1‐vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2‐disubstituted 1,3‐diene proceeded quantitatively in cyclohexane at 25 °C with sec‐butyllithium as an initiator. The obtained polymers have well‐controlled molecular weights in the range of 5 to 142 kg mol−1, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ<1.07–1.20). In situ 1H NMR kinetic characterization revealed a weak gradient structure for the copolymers of styrene and VCH, (rSty=2.55, rVCH=0.39). P(VCH) obtained in cyclohexane with sec‐BuLi as an initiator showed both 1,4‐ and 3,4‐incorporation mode (ratio: 64 : 36). It was demonstrated that the microstructure of the resulting P(VCH) can be altered by the addition of a modifier (THF), resulting in increasing 3,4‐microstructure (up to 78 %) and elevated glass‐transition temperature up to 89 °C. Thus, the monomer VCH polymerizes carbanionically like a diene, however leading to rigid polymers with high glass transition temperature, which provides interesting options for combination with other dienes to well‐defined polymer architectures and materials.
Anionic living polymerization of 1‐vinylcyclohexene (VCH) with sec‐BuLi as an initiator in cyclohexane is possible. It is a key question whether the monomer acts as a 1,3‐diene or as a styrenic monomer. The cyclic structure of the 1,2‐substituted monomer shows extraordinary consequences on copolymerization behavior, microstructure and thermal behavior, compared to other conventional linear dienes (e.g. butadiene, isoprene).</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>37186346</pmid><doi>10.1002/anie.202302907</doi><tpages>6</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-9916-3103</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | 1,3-Dienes Anionic polymerization Butyllithium Copolymerization Kinetics Copolymers Cyclohexane Dienes Glass transition temperature Initiators Living Anionic Polymerization Microstructure Molecular weight Molecular weight distribution Monomers NMR Nuclear magnetic resonance Polyisoprene Polymerization Polymers Polystyrene Styrene Styrenes Transition temperatures |
| title | Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1‐Vinylcyclohexene (VCH) |
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