Polythioethers bearing side groups for efficient degradation by E1cB reaction: reaction design for polymerization and main-chain scission
We have previously reported the polycondensation by the tandem reactions of dithiols and α-(bromomethyl)acrylates, consisting of conjugate substitution (S N 2′ reaction) and conjugate addition (Michael addition) reactions. The resulting polythioethers underwent a main-chain scission (MCS) by E1cB re...
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description | We have previously reported the polycondensation by the tandem reactions of dithiols and α-(bromomethyl)acrylates, consisting of conjugate substitution (S
N
2′ reaction) and conjugate addition (Michael addition) reactions. The resulting polythioethers underwent a main-chain scission (MCS) by E1cB reaction, which is the reverse reaction of conjugate addition, although it was not quantitative due to the equilibrium. Herein, the modification of the structures of polythioethers led to irreversible MCS, whereby the β-positions of ester moieties were substituted with a phenyl group. This slight modification in the polymer structure influenced the monomer structures and polymerization mechanisms. The understanding of reaction mechanisms by model reactions was required to obtain high molecular weights of polythioethers. It was clarified that the consequent additions of 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and PBu
3
were effective to achieve high molecular weight. The resulting polythioethers decomposed by irreversible MCS
via
E1cB reaction with DBU.
A pendant group led to the irreversible main chain scission of polythioether by E1cB reaction. The pendant group also led to divergent polymerization paths according to catalysts, and the optimization by understanding the mechanism was required. |
doi_str_mv | 10.1039/d3ra03751g |
format | Article |
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N
2′ reaction) and conjugate addition (Michael addition) reactions. The resulting polythioethers underwent a main-chain scission (MCS) by E1cB reaction, which is the reverse reaction of conjugate addition, although it was not quantitative due to the equilibrium. Herein, the modification of the structures of polythioethers led to irreversible MCS, whereby the β-positions of ester moieties were substituted with a phenyl group. This slight modification in the polymer structure influenced the monomer structures and polymerization mechanisms. The understanding of reaction mechanisms by model reactions was required to obtain high molecular weights of polythioethers. It was clarified that the consequent additions of 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and PBu
3
were effective to achieve high molecular weight. The resulting polythioethers decomposed by irreversible MCS
via
E1cB reaction with DBU.
A pendant group led to the irreversible main chain scission of polythioether by E1cB reaction. The pendant group also led to divergent polymerization paths according to catalysts, and the optimization by understanding the mechanism was required.</description><identifier>ISSN: 2046-2069</identifier><identifier>EISSN: 2046-2069</identifier><identifier>DOI: 10.1039/d3ra03751g</identifier><identifier>PMID: 37435381</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Acrylates ; Cascade chemical reactions ; Chain scission ; Chemistry ; Conjugates ; Decomposition reactions ; Molecular weight ; Polymerization ; Reaction mechanisms ; Substitution reactions</subject><ispartof>RSC advances, 2023-07, Vol.13 (3), p.2782-2786</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2023</rights><rights>This journal is © The Royal Society of Chemistry 2023 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c473t-65b8cd1d99fdc8d020f9c871794961289f8eee893c384c420a81195c9687e35e3</citedby><cites>FETCH-LOGICAL-c473t-65b8cd1d99fdc8d020f9c871794961289f8eee893c384c420a81195c9687e35e3</cites><orcidid>0000-0003-1449-3347 ; 0000-0001-9833-0929</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC10332248/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC10332248/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,860,881,27901,27902,53766,53768</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37435381$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kawatani, Ryo</creatorcontrib><creatorcontrib>Hagiwara, Keito</creatorcontrib><creatorcontrib>Tanaka, Anri</creatorcontrib><creatorcontrib>Kohsaka, Yasuhiro</creatorcontrib><title>Polythioethers bearing side groups for efficient degradation by E1cB reaction: reaction design for polymerization and main-chain scission</title><title>RSC advances</title><addtitle>RSC Adv</addtitle><description>We have previously reported the polycondensation by the tandem reactions of dithiols and α-(bromomethyl)acrylates, consisting of conjugate substitution (S
N
2′ reaction) and conjugate addition (Michael addition) reactions. The resulting polythioethers underwent a main-chain scission (MCS) by E1cB reaction, which is the reverse reaction of conjugate addition, although it was not quantitative due to the equilibrium. Herein, the modification of the structures of polythioethers led to irreversible MCS, whereby the β-positions of ester moieties were substituted with a phenyl group. This slight modification in the polymer structure influenced the monomer structures and polymerization mechanisms. The understanding of reaction mechanisms by model reactions was required to obtain high molecular weights of polythioethers. It was clarified that the consequent additions of 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and PBu
3
were effective to achieve high molecular weight. The resulting polythioethers decomposed by irreversible MCS
via
E1cB reaction with DBU.
A pendant group led to the irreversible main chain scission of polythioether by E1cB reaction. The pendant group also led to divergent polymerization paths according to catalysts, and the optimization by understanding the mechanism was required.</description><subject>Acrylates</subject><subject>Cascade chemical reactions</subject><subject>Chain scission</subject><subject>Chemistry</subject><subject>Conjugates</subject><subject>Decomposition reactions</subject><subject>Molecular weight</subject><subject>Polymerization</subject><subject>Reaction mechanisms</subject><subject>Substitution reactions</subject><issn>2046-2069</issn><issn>2046-2069</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNpdkktP3DAQgC1UVBBw6R1kqReEFOpH4ti9VLwKlZBaVe058tqTrFFib-0EafkH_Gu8LF1ofRiPZr55eYzQB0pOKeHqk-VRE15XtNtCu4yUomBEqHdv9B10kNIdyUdUlAn6Hu3wuuQVl3QXPf4I_XKcuwDjHGLCM9DR-Q4nZwF3MUyLhNsQMbStMw78iC10UVs9uuDxbImvqDnHEbRZGT5vtIwl1_nn2EUuMUB0D-sg7S0etPOFmWeJk3EpZfs-2m51n-Dg5d5Dv79e_bq4KW6_X3-7OLstTFnzsRDVTBpLrVKtNdISRlplZE1rVSpBmVStBACpuOGyNCUjWlKqKqOErIFXwPfQl3XexTQbwJo8U9R9s4hu0HHZBO2afz3ezZsu3Df5uTljpcwZjl8yxPBngjQ2g0sG-l57CFNqmOSCqVXZjH78D70LU_R5vhWVe1KCsEydrCkTQ0oR2k03lKzKquaS_zx73vJ1ho_e9r9B_-40A4drICaz8b5-E_4EAQCubA</recordid><startdate>20230710</startdate><enddate>20230710</enddate><creator>Kawatani, Ryo</creator><creator>Hagiwara, Keito</creator><creator>Tanaka, Anri</creator><creator>Kohsaka, Yasuhiro</creator><general>Royal Society of Chemistry</general><general>The Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-1449-3347</orcidid><orcidid>https://orcid.org/0000-0001-9833-0929</orcidid></search><sort><creationdate>20230710</creationdate><title>Polythioethers bearing side groups for efficient degradation by E1cB reaction: reaction design for polymerization and main-chain scission</title><author>Kawatani, Ryo ; Hagiwara, Keito ; Tanaka, Anri ; Kohsaka, Yasuhiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c473t-65b8cd1d99fdc8d020f9c871794961289f8eee893c384c420a81195c9687e35e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Acrylates</topic><topic>Cascade chemical reactions</topic><topic>Chain scission</topic><topic>Chemistry</topic><topic>Conjugates</topic><topic>Decomposition reactions</topic><topic>Molecular weight</topic><topic>Polymerization</topic><topic>Reaction mechanisms</topic><topic>Substitution reactions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kawatani, Ryo</creatorcontrib><creatorcontrib>Hagiwara, Keito</creatorcontrib><creatorcontrib>Tanaka, Anri</creatorcontrib><creatorcontrib>Kohsaka, Yasuhiro</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>RSC advances</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kawatani, Ryo</au><au>Hagiwara, Keito</au><au>Tanaka, Anri</au><au>Kohsaka, Yasuhiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Polythioethers bearing side groups for efficient degradation by E1cB reaction: reaction design for polymerization and main-chain scission</atitle><jtitle>RSC advances</jtitle><addtitle>RSC Adv</addtitle><date>2023-07-10</date><risdate>2023</risdate><volume>13</volume><issue>3</issue><spage>2782</spage><epage>2786</epage><pages>2782-2786</pages><issn>2046-2069</issn><eissn>2046-2069</eissn><abstract>We have previously reported the polycondensation by the tandem reactions of dithiols and α-(bromomethyl)acrylates, consisting of conjugate substitution (S
N
2′ reaction) and conjugate addition (Michael addition) reactions. The resulting polythioethers underwent a main-chain scission (MCS) by E1cB reaction, which is the reverse reaction of conjugate addition, although it was not quantitative due to the equilibrium. Herein, the modification of the structures of polythioethers led to irreversible MCS, whereby the β-positions of ester moieties were substituted with a phenyl group. This slight modification in the polymer structure influenced the monomer structures and polymerization mechanisms. The understanding of reaction mechanisms by model reactions was required to obtain high molecular weights of polythioethers. It was clarified that the consequent additions of 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and PBu
3
were effective to achieve high molecular weight. The resulting polythioethers decomposed by irreversible MCS
via
E1cB reaction with DBU.
A pendant group led to the irreversible main chain scission of polythioether by E1cB reaction. The pendant group also led to divergent polymerization paths according to catalysts, and the optimization by understanding the mechanism was required.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>37435381</pmid><doi>10.1039/d3ra03751g</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0003-1449-3347</orcidid><orcidid>https://orcid.org/0000-0001-9833-0929</orcidid><oa>free_for_read</oa></addata></record> |
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source | DOAJ Directory of Open Access Journals; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; PubMed Central; PubMed Central Open Access |
subjects | Acrylates Cascade chemical reactions Chain scission Chemistry Conjugates Decomposition reactions Molecular weight Polymerization Reaction mechanisms Substitution reactions |
title | Polythioethers bearing side groups for efficient degradation by E1cB reaction: reaction design for polymerization and main-chain scission |
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