Thermoreversible gelation with ion-binding cross-links of variable multiplicity
Thermoreversible gelation and liquid-liquid phase separation are theoretically studied for the gels of polyfunctional molecules (polymers) whose network junctions are formed by complexation of functional groups on the polymer chains with added metal ions. Phase diagrams on the polymer/ion/solvent co...
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| Veröffentlicht in: | The Journal of chemical physics 2019-05, Vol.150 (17), p.174904-174904 |
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| container_title | The Journal of chemical physics |
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| creator | Tanaka, Fumihiko Nakagawa, Yoshiyuki Ohta, Seiichi Ito, Taichi |
| description | Thermoreversible gelation and liquid-liquid phase separation are theoretically studied for the gels of polyfunctional molecules (polymers) whose network junctions are formed by complexation of functional groups on the polymer chains with added metal ions. Phase diagrams on the polymer/ion/solvent concentration plane, including both sol-gel transition lines and liquid-liquid phase separation lines (spinodals), are derived as functions of the polymer functionality, molecular weight, maximum coordination number of ions, and temperature. Binding isotherms of ions are also calculated as functions of the ion concentration. Results of the calculated sol-gel transition lines are compared with our recent experimental data on gelation of star block and telechelic, acrylic copolymers cross-linked by iron ions. It is shown that, owing to reaction stoichiometry, there is an optimal ion concentration at which the solution gels for the lowest polymer concentration and also that a re-entrant sol phase appears in the ion concentrations higher than the optimal one. The effect of stepwise complex formation constants on the re-entrant phase is studied in detail. |
| doi_str_mv | 10.1063/1.5096546 |
| format | Article |
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Phase diagrams on the polymer/ion/solvent concentration plane, including both sol-gel transition lines and liquid-liquid phase separation lines (spinodals), are derived as functions of the polymer functionality, molecular weight, maximum coordination number of ions, and temperature. Binding isotherms of ions are also calculated as functions of the ion concentration. Results of the calculated sol-gel transition lines are compared with our recent experimental data on gelation of star block and telechelic, acrylic copolymers cross-linked by iron ions. It is shown that, owing to reaction stoichiometry, there is an optimal ion concentration at which the solution gels for the lowest polymer concentration and also that a re-entrant sol phase appears in the ion concentrations higher than the optimal one. 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The effect of stepwise complex formation constants on the re-entrant phase is studied in detail.</description><subject>Binding</subject><subject>Block copolymers</subject><subject>Complex formation</subject><subject>Coordination numbers</subject><subject>Crosslinking</subject><subject>Functional groups</subject><subject>Gelation</subject><subject>Gels</subject><subject>Ion concentration</subject><subject>Ions</subject><subject>Liquid phases</subject><subject>Mathematical analysis</subject><subject>Phase diagrams</subject><subject>Phase separation</subject><subject>Phase transitions</subject><subject>Polymers</subject><subject>Sol-gel processes</subject><subject>Stoichiometry</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNp90F1LwzAUBuAgipvTC_-AFLxRofOcpk2aSxl-gbCbeV3SNt0y-2XSTvbvzT5UEPQqgTznJecl5BxhjMDoLY4jECwK2QEZIsTC50zAIRkCBOgLBmxATqxdAgDyIDwmA-rGuIBwSKazhTJVY9RKGavTUnlzVcpON7X3obuF5y5-qutc13MvM421fqnrN-s1hbeSRsvNRNWXnW5LnelufUqOClladbY_R-T14X42efJfpo_Pk7sXPwsx7vw0KiiNo5jGRYhZkasMMy7SEHMFKJl74iwLKRNSgoxTjCJGFc_jWOWcowjoiFztclvTvPfKdkmlbabKUtaq6W0SBBQFBcrR0ctfdNn0pna_cyqAMAogok5d79R2S6OKpDW6kmadICSblhNM9i07e7FP7NNK5d_yq1YHbnbAuk62bf6b9ideNeYHJm1e0E_F3JJz</recordid><startdate>20190507</startdate><enddate>20190507</enddate><creator>Tanaka, Fumihiko</creator><creator>Nakagawa, Yoshiyuki</creator><creator>Ohta, Seiichi</creator><creator>Ito, Taichi</creator><general>American Institute of Physics</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>8FD</scope><scope>H8D</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-5852-1202</orcidid><orcidid>https://orcid.org/0000000158521202</orcidid></search><sort><creationdate>20190507</creationdate><title>Thermoreversible gelation with ion-binding cross-links of variable multiplicity</title><author>Tanaka, Fumihiko ; Nakagawa, Yoshiyuki ; Ohta, Seiichi ; Ito, Taichi</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c418t-b5f3385838f41cfdec1c79b41de01a638576c4369aa0a8b15563e7d88ed771923</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Binding</topic><topic>Block copolymers</topic><topic>Complex formation</topic><topic>Coordination numbers</topic><topic>Crosslinking</topic><topic>Functional groups</topic><topic>Gelation</topic><topic>Gels</topic><topic>Ion concentration</topic><topic>Ions</topic><topic>Liquid phases</topic><topic>Mathematical analysis</topic><topic>Phase diagrams</topic><topic>Phase separation</topic><topic>Phase transitions</topic><topic>Polymers</topic><topic>Sol-gel processes</topic><topic>Stoichiometry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tanaka, Fumihiko</creatorcontrib><creatorcontrib>Nakagawa, Yoshiyuki</creatorcontrib><creatorcontrib>Ohta, Seiichi</creatorcontrib><creatorcontrib>Ito, Taichi</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Technology Research Database</collection><collection>Aerospace Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tanaka, Fumihiko</au><au>Nakagawa, Yoshiyuki</au><au>Ohta, Seiichi</au><au>Ito, Taichi</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Thermoreversible gelation with ion-binding cross-links of variable multiplicity</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2019-05-07</date><risdate>2019</risdate><volume>150</volume><issue>17</issue><spage>174904</spage><epage>174904</epage><pages>174904-174904</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><coden>JCPSA6</coden><abstract>Thermoreversible gelation and liquid-liquid phase separation are theoretically studied for the gels of polyfunctional molecules (polymers) whose network junctions are formed by complexation of functional groups on the polymer chains with added metal ions. 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| ispartof | The Journal of chemical physics, 2019-05, Vol.150 (17), p.174904-174904 |
| issn | 0021-9606 1089-7690 |
| language | eng |
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| source | AIP Journals Complete; Alma/SFX Local Collection |
| subjects | Binding Block copolymers Complex formation Coordination numbers Crosslinking Functional groups Gelation Gels Ion concentration Ions Liquid phases Mathematical analysis Phase diagrams Phase separation Phase transitions Polymers Sol-gel processes Stoichiometry |
| title | Thermoreversible gelation with ion-binding cross-links of variable multiplicity |
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