Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts
The ring-opening polymerization (ROP) of trans -1,4-cyclohexadiene carbonate (CHDC) has been investigated computationally and experimentally. DFT computations indicate that ring-opening of CHDC is thermodynamically possible, yet to a lesser extent than that of trans -cyclohexene carbonate (CHC). Eff...
Gespeichert in:
| Veröffentlicht in: | Polymer chemistry 2015-01, Vol.6 (11), p.1961-1971 |
|---|---|
| Hauptverfasser: | , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 1971 |
|---|---|
| container_issue | 11 |
| container_start_page | 1961 |
| container_title | Polymer chemistry |
| container_volume | 6 |
| creator | Diallo, Abdou Khadri Kirillov, Evgueni Slawinski, Martine Brusson, Jean-Michel Guillaume, Sophie M. Carpentier, Jean-François |
| description | The ring-opening polymerization (ROP) of
trans
-1,4-cyclohexadiene carbonate (CHDC) has been investigated computationally and experimentally. DFT computations indicate that ring-opening of CHDC is thermodynamically possible, yet to a lesser extent than that of
trans
-cyclohexene carbonate (CHC). Effective homopolymerizations of
rac
-CHDC and simultaneous or sequential copolymerizations of
rac
-CHDC with
rac
-CHC and
l
-LA were achieved with a diaminophenolate zinc-based complex ([(NNO)ZnEt]) or a guanidine (TBD) associated with an alcohol. These ROP reactions, which confirmed the lower reactivity of
rac
-CHDC
vs. rac
-CHC, especially in homopolymerization, proceeded without any decarboxylation. Quite uniquely, highly syndiotactic PCHDC was obtained from ROP of
rac
-CHDC with both the zinc- and TBD-based catalysts, as revealed by
13
C{
1
H} NMR studies. The prepared homopolymers and block or random copolymers were characterized by
1
H,
13
C{
1
H} NMR, MALDI-ToF MS, SEC and DSC techniques. |
| doi_str_mv | 10.1039/C4PY01713G |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_hal_p</sourceid><recordid>TN_cdi_hal_primary_oai_HAL_hal_01115003v1</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1677905993</sourcerecordid><originalsourceid>FETCH-LOGICAL-c400t-41ef43d74b59e4fae55761c536b5a683ca716c4b2010804867e18e77ac3afdee3</originalsourceid><addsrcrecordid>eNpdkcFqGzEQhpeSQk3iS55Ax7ZEicaSVt5jMEkcMLTQ9pDTMqudtVVkyZXWIZsH6fNmXZcEMpd_-Pj4DzNFcQ7iEoSsrhbq-4MAA_LuQzEBoyteVeXs5HXX6lMxzfm3GEeCmslyUvz9MYTWxUyebO8eiSUX1jzuKIzJdtEPW0ruGXsXA8PQMhvfwdixPmHIHC4Ut4P1cUNP2DoKxCymJgbsiW2pdWO2rBkY2o1L6EfWo-f_WmNaY4jc4kiG3Oez4mOHPtP0f54Wv25vfi6WfPXt7n5xveJWCdFzBdQp2RrV6IpUh6S1KcFqWTYay7m0aKC0qpkJEHOh5qUhmJMxaCV2LZE8Lb4cezfo611yW0xDHdHVy-tVfWACAPR4rkcY3c9Hd5finz3lvt66bMl7DBT3uYbSmEroqpKj-vWo2hRzTtS9doOoD7-q334lXwBOOok9</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1677905993</pqid></control><display><type>article</type><title>Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Diallo, Abdou Khadri ; Kirillov, Evgueni ; Slawinski, Martine ; Brusson, Jean-Michel ; Guillaume, Sophie M. ; Carpentier, Jean-François</creator><creatorcontrib>Diallo, Abdou Khadri ; Kirillov, Evgueni ; Slawinski, Martine ; Brusson, Jean-Michel ; Guillaume, Sophie M. ; Carpentier, Jean-François</creatorcontrib><description>The ring-opening polymerization (ROP) of
trans
-1,4-cyclohexadiene carbonate (CHDC) has been investigated computationally and experimentally. DFT computations indicate that ring-opening of CHDC is thermodynamically possible, yet to a lesser extent than that of
trans
-cyclohexene carbonate (CHC). Effective homopolymerizations of
rac
-CHDC and simultaneous or sequential copolymerizations of
rac
-CHDC with
rac
-CHC and
l
-LA were achieved with a diaminophenolate zinc-based complex ([(NNO)ZnEt]) or a guanidine (TBD) associated with an alcohol. These ROP reactions, which confirmed the lower reactivity of
rac
-CHDC
vs. rac
-CHC, especially in homopolymerization, proceeded without any decarboxylation. Quite uniquely, highly syndiotactic PCHDC was obtained from ROP of
rac
-CHDC with both the zinc- and TBD-based catalysts, as revealed by
13
C{
1
H} NMR studies. The prepared homopolymers and block or random copolymers were characterized by
1
H,
13
C{
1
H} NMR, MALDI-ToF MS, SEC and DSC techniques.</description><identifier>ISSN: 1759-9954</identifier><identifier>EISSN: 1759-9962</identifier><identifier>DOI: 10.1039/C4PY01713G</identifier><language>eng</language><publisher>Royal Society of Chemistry - RSC</publisher><subject>Carbonates ; Chemical Sciences ; Computation ; Copolymerization ; Copolymers ; Decarboxylation ; Differential scanning calorimetry ; Nuclear magnetic resonance ; Polymerization</subject><ispartof>Polymer chemistry, 2015-01, Vol.6 (11), p.1961-1971</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c400t-41ef43d74b59e4fae55761c536b5a683ca716c4b2010804867e18e77ac3afdee3</citedby><cites>FETCH-LOGICAL-c400t-41ef43d74b59e4fae55761c536b5a683ca716c4b2010804867e18e77ac3afdee3</cites><orcidid>0000-0003-2917-8657</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27901,27902</link.rule.ids><backlink>$$Uhttps://univ-rennes.hal.science/hal-01115003$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Diallo, Abdou Khadri</creatorcontrib><creatorcontrib>Kirillov, Evgueni</creatorcontrib><creatorcontrib>Slawinski, Martine</creatorcontrib><creatorcontrib>Brusson, Jean-Michel</creatorcontrib><creatorcontrib>Guillaume, Sophie M.</creatorcontrib><creatorcontrib>Carpentier, Jean-François</creatorcontrib><title>Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts</title><title>Polymer chemistry</title><description>The ring-opening polymerization (ROP) of
trans
-1,4-cyclohexadiene carbonate (CHDC) has been investigated computationally and experimentally. DFT computations indicate that ring-opening of CHDC is thermodynamically possible, yet to a lesser extent than that of
trans
-cyclohexene carbonate (CHC). Effective homopolymerizations of
rac
-CHDC and simultaneous or sequential copolymerizations of
rac
-CHDC with
rac
-CHC and
l
-LA were achieved with a diaminophenolate zinc-based complex ([(NNO)ZnEt]) or a guanidine (TBD) associated with an alcohol. These ROP reactions, which confirmed the lower reactivity of
rac
-CHDC
vs. rac
-CHC, especially in homopolymerization, proceeded without any decarboxylation. Quite uniquely, highly syndiotactic PCHDC was obtained from ROP of
rac
-CHDC with both the zinc- and TBD-based catalysts, as revealed by
13
C{
1
H} NMR studies. The prepared homopolymers and block or random copolymers were characterized by
1
H,
13
C{
1
H} NMR, MALDI-ToF MS, SEC and DSC techniques.</description><subject>Carbonates</subject><subject>Chemical Sciences</subject><subject>Computation</subject><subject>Copolymerization</subject><subject>Copolymers</subject><subject>Decarboxylation</subject><subject>Differential scanning calorimetry</subject><subject>Nuclear magnetic resonance</subject><subject>Polymerization</subject><issn>1759-9954</issn><issn>1759-9962</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNpdkcFqGzEQhpeSQk3iS55Ax7ZEicaSVt5jMEkcMLTQ9pDTMqudtVVkyZXWIZsH6fNmXZcEMpd_-Pj4DzNFcQ7iEoSsrhbq-4MAA_LuQzEBoyteVeXs5HXX6lMxzfm3GEeCmslyUvz9MYTWxUyebO8eiSUX1jzuKIzJdtEPW0ruGXsXA8PQMhvfwdixPmHIHC4Ut4P1cUNP2DoKxCymJgbsiW2pdWO2rBkY2o1L6EfWo-f_WmNaY4jc4kiG3Oez4mOHPtP0f54Wv25vfi6WfPXt7n5xveJWCdFzBdQp2RrV6IpUh6S1KcFqWTYay7m0aKC0qpkJEHOh5qUhmJMxaCV2LZE8Lb4cezfo611yW0xDHdHVy-tVfWACAPR4rkcY3c9Hd5finz3lvt66bMl7DBT3uYbSmEroqpKj-vWo2hRzTtS9doOoD7-q334lXwBOOok9</recordid><startdate>20150101</startdate><enddate>20150101</enddate><creator>Diallo, Abdou Khadri</creator><creator>Kirillov, Evgueni</creator><creator>Slawinski, Martine</creator><creator>Brusson, Jean-Michel</creator><creator>Guillaume, Sophie M.</creator><creator>Carpentier, Jean-François</creator><general>Royal Society of Chemistry - RSC</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope><scope>1XC</scope><scope>VOOES</scope><orcidid>https://orcid.org/0000-0003-2917-8657</orcidid></search><sort><creationdate>20150101</creationdate><title>Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts</title><author>Diallo, Abdou Khadri ; Kirillov, Evgueni ; Slawinski, Martine ; Brusson, Jean-Michel ; Guillaume, Sophie M. ; Carpentier, Jean-François</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c400t-41ef43d74b59e4fae55761c536b5a683ca716c4b2010804867e18e77ac3afdee3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Carbonates</topic><topic>Chemical Sciences</topic><topic>Computation</topic><topic>Copolymerization</topic><topic>Copolymers</topic><topic>Decarboxylation</topic><topic>Differential scanning calorimetry</topic><topic>Nuclear magnetic resonance</topic><topic>Polymerization</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Diallo, Abdou Khadri</creatorcontrib><creatorcontrib>Kirillov, Evgueni</creatorcontrib><creatorcontrib>Slawinski, Martine</creatorcontrib><creatorcontrib>Brusson, Jean-Michel</creatorcontrib><creatorcontrib>Guillaume, Sophie M.</creatorcontrib><creatorcontrib>Carpentier, Jean-François</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</collection><jtitle>Polymer chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Diallo, Abdou Khadri</au><au>Kirillov, Evgueni</au><au>Slawinski, Martine</au><au>Brusson, Jean-Michel</au><au>Guillaume, Sophie M.</au><au>Carpentier, Jean-François</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts</atitle><jtitle>Polymer chemistry</jtitle><date>2015-01-01</date><risdate>2015</risdate><volume>6</volume><issue>11</issue><spage>1961</spage><epage>1971</epage><pages>1961-1971</pages><issn>1759-9954</issn><eissn>1759-9962</eissn><abstract>The ring-opening polymerization (ROP) of
trans
-1,4-cyclohexadiene carbonate (CHDC) has been investigated computationally and experimentally. DFT computations indicate that ring-opening of CHDC is thermodynamically possible, yet to a lesser extent than that of
trans
-cyclohexene carbonate (CHC). Effective homopolymerizations of
rac
-CHDC and simultaneous or sequential copolymerizations of
rac
-CHDC with
rac
-CHC and
l
-LA were achieved with a diaminophenolate zinc-based complex ([(NNO)ZnEt]) or a guanidine (TBD) associated with an alcohol. These ROP reactions, which confirmed the lower reactivity of
rac
-CHDC
vs. rac
-CHC, especially in homopolymerization, proceeded without any decarboxylation. Quite uniquely, highly syndiotactic PCHDC was obtained from ROP of
rac
-CHDC with both the zinc- and TBD-based catalysts, as revealed by
13
C{
1
H} NMR studies. The prepared homopolymers and block or random copolymers were characterized by
1
H,
13
C{
1
H} NMR, MALDI-ToF MS, SEC and DSC techniques.</abstract><pub>Royal Society of Chemistry - RSC</pub><doi>10.1039/C4PY01713G</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0003-2917-8657</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1759-9954 |
| ispartof | Polymer chemistry, 2015-01, Vol.6 (11), p.1961-1971 |
| issn | 1759-9954 1759-9962 |
| language | eng |
| recordid | cdi_hal_primary_oai_HAL_hal_01115003v1 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Carbonates Chemical Sciences Computation Copolymerization Copolymers Decarboxylation Differential scanning calorimetry Nuclear magnetic resonance Polymerization |
| title | Syndioselective ring-opening polymerization and copolymerization of trans-1,4-cyclohexadiene carbonate mediated by achiral metal- and organo-catalysts |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-13T08%3A12%3A30IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_hal_p&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Syndioselective%20ring-opening%20polymerization%20and%20copolymerization%20of%20trans-1,4-cyclohexadiene%20carbonate%20mediated%20by%20achiral%20metal-%20and%20organo-catalysts&rft.jtitle=Polymer%20chemistry&rft.au=Diallo,%20Abdou%20Khadri&rft.date=2015-01-01&rft.volume=6&rft.issue=11&rft.spage=1961&rft.epage=1971&rft.pages=1961-1971&rft.issn=1759-9954&rft.eissn=1759-9962&rft_id=info:doi/10.1039/C4PY01713G&rft_dat=%3Cproquest_hal_p%3E1677905993%3C/proquest_hal_p%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1677905993&rft_id=info:pmid/&rfr_iscdi=true |