Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistry
Vinyl polymer tacticity is critical for regulating the thermal and physical properties of materials. Stereoselective cationic polymerization of vinyl ethers has gained significant progress in recent years, while monomer scope beyond simple alkyl vinyl ethers to access functionalized isotactic polyme...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2023-06-01
|
| Series: | Giant |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666542523000139 |
| _version_ | 1797801717990948864 |
|---|---|
| author | Hui Zhu Yu Jiang Zan Yang Xun Zhang Saihu Liao |
| author_facet | Hui Zhu Yu Jiang Zan Yang Xun Zhang Saihu Liao |
| author_sort | Hui Zhu |
| collection | DOAJ |
| description | Vinyl polymer tacticity is critical for regulating the thermal and physical properties of materials. Stereoselective cationic polymerization of vinyl ethers has gained significant progress in recent years, while monomer scope beyond simple alkyl vinyl ethers to access functionalized isotactic polymer materials remains to be explored but highly desirable. Herein, we report the successful development of a stereoselective cationic polymerization of alkenyl vinyl ethers by employing confined Brønsted acid organocatalysis. This organocatalytic system shows high efficiency and stereoselectivity in the polymerization of several alkenyl vinyl ethers, as well as good compatibility to the diolefinic monomers without touching the C=C bonds in the alkenyl part during the cationic polymerization, thus allowing for further modification on these C-C double bonds after polymerization to construct functionalized, isotactic polymer materials. Further, a series of thermoplastic copolymers with tunable properties and variable and predictable contents of side-chain C=C bonds can be synthesized through the corresponding stereoselective copolymerization. Sequential post-polymerization modification of both isotactic homopolymers and copolymers by combining thiol-ene and sulfur(VI) fluoride exchange (SuFEx) click reactions is also demonstrated. |
| first_indexed | 2024-03-13T04:54:44Z |
| format | Article |
| id | doaj.art-8dc48524f81c428f9eaa3b2851dd3e00 |
| institution | Directory Open Access Journal |
| issn | 2666-5425 |
| language | English |
| last_indexed | 2024-03-13T04:54:44Z |
| publishDate | 2023-06-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Giant |
| spelling | doaj.art-8dc48524f81c428f9eaa3b2851dd3e002023-06-18T05:03:27ZengElsevierGiant2666-54252023-06-0114100151Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistryHui Zhu0Yu Jiang1Zan Yang2Xun Zhang3Saihu Liao4Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350116, ChinaKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350116, ChinaKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350116, ChinaKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350116, China; State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Lingling Lu, Shanghai, 200032, China; Corresponding authors.Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350116, China; State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China; Beijing National Laboratory of Molecular Science (BNLMS), Beijing 100190, China; Corresponding authors.Vinyl polymer tacticity is critical for regulating the thermal and physical properties of materials. Stereoselective cationic polymerization of vinyl ethers has gained significant progress in recent years, while monomer scope beyond simple alkyl vinyl ethers to access functionalized isotactic polymer materials remains to be explored but highly desirable. Herein, we report the successful development of a stereoselective cationic polymerization of alkenyl vinyl ethers by employing confined Brønsted acid organocatalysis. This organocatalytic system shows high efficiency and stereoselectivity in the polymerization of several alkenyl vinyl ethers, as well as good compatibility to the diolefinic monomers without touching the C=C bonds in the alkenyl part during the cationic polymerization, thus allowing for further modification on these C-C double bonds after polymerization to construct functionalized, isotactic polymer materials. Further, a series of thermoplastic copolymers with tunable properties and variable and predictable contents of side-chain C=C bonds can be synthesized through the corresponding stereoselective copolymerization. Sequential post-polymerization modification of both isotactic homopolymers and copolymers by combining thiol-ene and sulfur(VI) fluoride exchange (SuFEx) click reactions is also demonstrated.http://www.sciencedirect.com/science/article/pii/S2666542523000139Stereoselective polymerizationCationic polymerizationVinyl ethersTacticityClick reactions |
| spellingShingle | Hui Zhu Yu Jiang Zan Yang Xun Zhang Saihu Liao Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistry Giant Stereoselective polymerization Cationic polymerization Vinyl ethers Tacticity Click reactions |
| title | Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistry |
| title_full | Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistry |
| title_fullStr | Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistry |
| title_full_unstemmed | Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistry |
| title_short | Organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post-functionalization via click chemistry |
| title_sort | organocatalytic stereoselective cationic polymerization of alkenyl vinyl ethers and post functionalization via click chemistry |
| topic | Stereoselective polymerization Cationic polymerization Vinyl ethers Tacticity Click reactions |
| url | http://www.sciencedirect.com/science/article/pii/S2666542523000139 |
| work_keys_str_mv | AT huizhu organocatalyticstereoselectivecationicpolymerizationofalkenylvinylethersandpostfunctionalizationviaclickchemistry AT yujiang organocatalyticstereoselectivecationicpolymerizationofalkenylvinylethersandpostfunctionalizationviaclickchemistry AT zanyang organocatalyticstereoselectivecationicpolymerizationofalkenylvinylethersandpostfunctionalizationviaclickchemistry AT xunzhang organocatalyticstereoselectivecationicpolymerizationofalkenylvinylethersandpostfunctionalizationviaclickchemistry AT saihuliao organocatalyticstereoselectivecationicpolymerizationofalkenylvinylethersandpostfunctionalizationviaclickchemistry |