Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina
Bio-based platform molecules such as itaconic, fumaric, and muconic acid offer much promise in the formation of sustainable unsaturated polyester resins upon reaction with suitable diols and polyols. The C=C bonds present in these polyester chains allows for post-polymerization modification and such...
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ftunivgenova:oai:iris.unige.it:11567/1062443 2024-04-14T08:04:49+00:00 Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina Oliver B Moore Polly-Ann Hanson James William Comerford Pellis A T J Farmer Oliver, B Moore Polly-Ann, Hanson James William, Comerford Pellis, A T, J Farmer 2019 ELETTRONICO https://hdl.handle.net/11567/1062443 https://doi.org/10.3389/fchem.2019.00501 eng eng info:eu-repo/semantics/altIdentifier/wos/WOS:000475433700001 volume:7 firstpage:501 lastpage:501 numberofpages:1 journal:FRONTIERS IN CHEMISTRY https://hdl.handle.net/11567/1062443 doi:10.3389/fchem.2019.00501 info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-85074030753 info:eu-repo/semantics/article 2019 ftunivgenova https://doi.org/10.3389/fchem.2019.00501 2024-03-21T02:37:55Z Bio-based platform molecules such as itaconic, fumaric, and muconic acid offer much promise in the formation of sustainable unsaturated polyester resins upon reaction with suitable diols and polyols. The C=C bonds present in these polyester chains allows for post-polymerization modification and such moieties are conventionally utilized in curing processes during the manufacture of coatings. The C=C modification sites can also act as points to add useful pendants which can alter the polymers final properties such as glass transition temperature, biodegradability, hardness, polarity, and strength. A commonly observed modification is the addition of secondary amines via an aza-Michael addition. Conventional procedures for the addition of amines onto itaconate polyesters require reaction times of several days as a result of undesired side reactions, in particular, the formation of the less reactive mesaconate regioisomer. The slow reversion of the mesaconate back to itaconate, followed by subsequent amine addition, is the primary reason for such extended reaction times. Herein we report our efforts toward finding a suitable catalyst for the aza-Michael addition of diethylamine onto a model substrate, dimethyl itaconate, with the aim of being able to add amine onto the itaconate units without excessive regioisomerization to the inactive mesaconate. A catalyst screen showed that iodine on acidic alumina results in an effective, heterogeneous, reusable catalyst for the investigated aza-Michael addition. Extending the study further, itaconate polyester was prepared by Candida Antartica Lipase B (CaL-B) via enzymatic polytranesterification and subsequently modified with diethylamine using the iodine on acidic alumina catalyst, dramatically reducing the required length of reaction (>70% addition after 4 h). The approach represents a multidisciplinary example whereby biocatalytic polymerization is combined with chemocatalytic modification of the resultant polyester for the formation of useful bio-based polyesters. Article in Journal/Newspaper antartic* Università degli Studi di Genova: CINECA IRIS Frontiers in Chemistry 7 |
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Università degli Studi di Genova: CINECA IRIS |
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ftunivgenova |
language |
English |
description |
Bio-based platform molecules such as itaconic, fumaric, and muconic acid offer much promise in the formation of sustainable unsaturated polyester resins upon reaction with suitable diols and polyols. The C=C bonds present in these polyester chains allows for post-polymerization modification and such moieties are conventionally utilized in curing processes during the manufacture of coatings. The C=C modification sites can also act as points to add useful pendants which can alter the polymers final properties such as glass transition temperature, biodegradability, hardness, polarity, and strength. A commonly observed modification is the addition of secondary amines via an aza-Michael addition. Conventional procedures for the addition of amines onto itaconate polyesters require reaction times of several days as a result of undesired side reactions, in particular, the formation of the less reactive mesaconate regioisomer. The slow reversion of the mesaconate back to itaconate, followed by subsequent amine addition, is the primary reason for such extended reaction times. Herein we report our efforts toward finding a suitable catalyst for the aza-Michael addition of diethylamine onto a model substrate, dimethyl itaconate, with the aim of being able to add amine onto the itaconate units without excessive regioisomerization to the inactive mesaconate. A catalyst screen showed that iodine on acidic alumina results in an effective, heterogeneous, reusable catalyst for the investigated aza-Michael addition. Extending the study further, itaconate polyester was prepared by Candida Antartica Lipase B (CaL-B) via enzymatic polytranesterification and subsequently modified with diethylamine using the iodine on acidic alumina catalyst, dramatically reducing the required length of reaction (>70% addition after 4 h). The approach represents a multidisciplinary example whereby biocatalytic polymerization is combined with chemocatalytic modification of the resultant polyester for the formation of useful bio-based polyesters. |
author2 |
Oliver, B Moore Polly-Ann, Hanson James William, Comerford Pellis, A T, J Farmer |
format |
Article in Journal/Newspaper |
author |
Oliver B Moore Polly-Ann Hanson James William Comerford Pellis A T J Farmer |
spellingShingle |
Oliver B Moore Polly-Ann Hanson James William Comerford Pellis A T J Farmer Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina |
author_facet |
Oliver B Moore Polly-Ann Hanson James William Comerford Pellis A T J Farmer |
author_sort |
Oliver B Moore |
title |
Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina |
title_short |
Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina |
title_full |
Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina |
title_fullStr |
Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina |
title_full_unstemmed |
Improving the Post-Polymerisation Modification of Bio-based Itaconate Unsaturated Polyesters: Catalysing Aza-Michael Additions with Reusable Iodine on Acidic Alumina |
title_sort |
improving the post-polymerisation modification of bio-based itaconate unsaturated polyesters: catalysing aza-michael additions with reusable iodine on acidic alumina |
publishDate |
2019 |
url |
https://hdl.handle.net/11567/1062443 https://doi.org/10.3389/fchem.2019.00501 |
genre |
antartic* |
genre_facet |
antartic* |
op_relation |
info:eu-repo/semantics/altIdentifier/wos/WOS:000475433700001 volume:7 firstpage:501 lastpage:501 numberofpages:1 journal:FRONTIERS IN CHEMISTRY https://hdl.handle.net/11567/1062443 doi:10.3389/fchem.2019.00501 info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-85074030753 |
op_doi |
https://doi.org/10.3389/fchem.2019.00501 |
container_title |
Frontiers in Chemistry |
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7 |
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