Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune properties
Dehydrogenation and subsequent chemical modification of polyolefins emerges as a promising polymer-to-polymer upcycling pathway. We report the functionalization of polycyclooctene (PCOE), a model for dehydrogenated polyethylene, by thiol-ene click chemistry to install carboxylic acid (COOH) terminat...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2024-03-01
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| Series: | Giant |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666542523000930 |
| _version_ | 1797248281250627584 |
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| author | Eli Fastow Roshni John Chethalen E. Bryan Coughlin Karen I. Winey |
| author_facet | Eli Fastow Roshni John Chethalen E. Bryan Coughlin Karen I. Winey |
| author_sort | Eli Fastow |
| collection | DOAJ |
| description | Dehydrogenation and subsequent chemical modification of polyolefins emerges as a promising polymer-to-polymer upcycling pathway. We report the functionalization of polycyclooctene (PCOE), a model for dehydrogenated polyethylene, by thiol-ene click chemistry to install carboxylic acid (COOH) terminated alkane pendant groups. This functionalization approach attached three pendants of different alkane spacer length: thioglycolic acid, mercaptopropionic acid, and mercaptooctanoic acid. Functionalization attached pendants to 3–22 mol% of the ethylene monomeric units, was well controlled by varying reaction stoichiometry and time, and did not require acid groups protections. Greater than 95% of the COOH groups participated in secondary bonding, forming aggregates detectable in X-ray scattering at high COOH mass fractions. Crystallinity and melting temperature decreased with increasing COOH mass fraction. Dynamic mechanical analysis (DMA) reveals both COOH mass fraction and pendant architecture tunes the rubbery plateau moduli, which is well described by the molar mass per backbone bond. This functionalized polymer exhibits commensurate surface and mechanical properties to commercial poly(ethylene-co-acrylic acid). |
| first_indexed | 2024-03-08T15:52:47Z |
| format | Article |
| id | doaj.art-7c1b5798ec3b4e77ba8ba9336f634ae6 |
| institution | Directory Open Access Journal |
| issn | 2666-5425 |
| language | English |
| last_indexed | 2024-04-24T20:12:06Z |
| publishDate | 2024-03-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Giant |
| spelling | doaj.art-7c1b5798ec3b4e77ba8ba9336f634ae62024-03-23T06:26:09ZengElsevierGiant2666-54252024-03-0117100231Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune propertiesEli Fastow0Roshni John Chethalen1E. Bryan Coughlin2Karen I. Winey3Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA 19104, United StatesDepartment of Polymer Science and Engineering, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United StatesDepartment of Polymer Science and Engineering, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United States; Corresponding authors.Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA 19104, United States; Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States; Corresponding authors.Dehydrogenation and subsequent chemical modification of polyolefins emerges as a promising polymer-to-polymer upcycling pathway. We report the functionalization of polycyclooctene (PCOE), a model for dehydrogenated polyethylene, by thiol-ene click chemistry to install carboxylic acid (COOH) terminated alkane pendant groups. This functionalization approach attached three pendants of different alkane spacer length: thioglycolic acid, mercaptopropionic acid, and mercaptooctanoic acid. Functionalization attached pendants to 3–22 mol% of the ethylene monomeric units, was well controlled by varying reaction stoichiometry and time, and did not require acid groups protections. Greater than 95% of the COOH groups participated in secondary bonding, forming aggregates detectable in X-ray scattering at high COOH mass fractions. Crystallinity and melting temperature decreased with increasing COOH mass fraction. Dynamic mechanical analysis (DMA) reveals both COOH mass fraction and pendant architecture tunes the rubbery plateau moduli, which is well described by the molar mass per backbone bond. This functionalized polymer exhibits commensurate surface and mechanical properties to commercial poly(ethylene-co-acrylic acid).http://www.sciencedirect.com/science/article/pii/S2666542523000930Polymer upcyclingThiol-ene click chemistryPolycycloocteneAssociating polymerFunctionalizationDynamic mechanical analysis |
| spellingShingle | Eli Fastow Roshni John Chethalen E. Bryan Coughlin Karen I. Winey Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune properties Giant Polymer upcycling Thiol-ene click chemistry Polycyclooctene Associating polymer Functionalization Dynamic mechanical analysis |
| title | Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune properties |
| title_full | Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune properties |
| title_fullStr | Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune properties |
| title_full_unstemmed | Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune properties |
| title_short | Thiol-ene click chemistry incorporates carboxylic acid-terminated alkane pendants on polycyclooctene to tune properties |
| title_sort | thiol ene click chemistry incorporates carboxylic acid terminated alkane pendants on polycyclooctene to tune properties |
| topic | Polymer upcycling Thiol-ene click chemistry Polycyclooctene Associating polymer Functionalization Dynamic mechanical analysis |
| url | http://www.sciencedirect.com/science/article/pii/S2666542523000930 |
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