Thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate]
•The thermal degradation of P(3HB-co-16 mol%−4HB) was investigated by its pyrolyzates and kinetics approaches.•The thermal degradation of P(3HB-co-16 mol%−4HB) proceeded at least in two steps.•Thermal degradation behavior of P(3HB-co-16 mol%−4HB) changed in time and/or temperature•Random degradation...
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| Veröffentlicht in: | Polymer degradation and stability 2021-01, Vol.183, p.109460, Article 109460 |
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| container_title | Polymer degradation and stability |
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| creator | Omura, Taku Goto, Tatsuya Maehara, Akira Kimura, Satoshi Abe, Hideki Iwata, Tadahisa |
| description | •The thermal degradation of P(3HB-co-16 mol%−4HB) was investigated by its pyrolyzates and kinetics approaches.•The thermal degradation of P(3HB-co-16 mol%−4HB) proceeded at least in two steps.•Thermal degradation behavior of P(3HB-co-16 mol%−4HB) changed in time and/or temperature•Random degradation in the initial period changes to subsequent 0th-order weight loss meaning unzipping degradation of 3HB units.•The unzipping degradation of 3HB unit from the chain end may stop at the 4HB unit randomly present in the copolymer.
The thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-16 mol%-4-hydroxybutyrate] (P(3HB-co-16 mol%-4HB)) was investigated based on spectroscopic analysis of its pyrolyzates and two kinetic modeling approaches. Pyrolyzate analysis revealed that trans-crotonic acid, cis-crotonic acid, γ-butyrolactone, and their oligomers (dimers and trimers) were produced following thermal degradation of P(3HB-co-16 mol%-4HB). The kinetic analyses confirmed that the thermal degradation behavior of this copolymer changed depending on the time and/or temperature parameters. Specifically, this degradation process proceeded in at least two steps, (i) initial random degradation and (ii) subsequent 0th-order weight loss, which indicated unzipping degradation of the 3HB units. Based on 13C NMR and two-dimensional NMR methods, it was determined that the unzipping degradation of 3HB units starting from the chain end may stop or volatilize an oligomer when the reaction reaches a 4HB unit randomly present in the copolymer. |
| doi_str_mv | 10.1016/j.polymdegradstab.2020.109460 |
| format | Article |
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The thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-16 mol%-4-hydroxybutyrate] (P(3HB-co-16 mol%-4HB)) was investigated based on spectroscopic analysis of its pyrolyzates and two kinetic modeling approaches. Pyrolyzate analysis revealed that trans-crotonic acid, cis-crotonic acid, γ-butyrolactone, and their oligomers (dimers and trimers) were produced following thermal degradation of P(3HB-co-16 mol%-4HB). The kinetic analyses confirmed that the thermal degradation behavior of this copolymer changed depending on the time and/or temperature parameters. Specifically, this degradation process proceeded in at least two steps, (i) initial random degradation and (ii) subsequent 0th-order weight loss, which indicated unzipping degradation of the 3HB units. Based on 13C NMR and two-dimensional NMR methods, it was determined that the unzipping degradation of 3HB units starting from the chain end may stop or volatilize an oligomer when the reaction reaches a 4HB unit randomly present in the copolymer.</description><identifier>ISSN: 0141-3910</identifier><identifier>EISSN: 1873-2321</identifier><identifier>DOI: 10.1016/j.polymdegradstab.2020.109460</identifier><language>eng</language><publisher>London: Elsevier Ltd</publisher><subject>Biodegradation ; Butyrolactone ; Copolymers ; Degradation mechanism ; Dimers ; Heat conductivity ; Kinetic analysis ; Microbial copolyester ; NMR ; Nuclear magnetic resonance ; Oligomers ; P(3HB-co-4HB) ; Polyhydroxyalkanoate ; Process parameters ; Reaction kinetics ; Temperature ; Temperature effects ; Thermal cycling ; Thermal degradation ; Trimers ; Unzipping reaction ; Weight loss ; β-elimination</subject><ispartof>Polymer degradation and stability, 2021-01, Vol.183, p.109460, Article 109460</ispartof><rights>2020</rights><rights>Copyright Elsevier BV Jan 2021</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c482t-134fcafe277cf75996d9250448602de0d0c23eb8706236365a6944279b96f4fe3</citedby><cites>FETCH-LOGICAL-c482t-134fcafe277cf75996d9250448602de0d0c23eb8706236365a6944279b96f4fe3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S014139102030389X$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,776,780,3537,27901,27902,65306</link.rule.ids></links><search><creatorcontrib>Omura, Taku</creatorcontrib><creatorcontrib>Goto, Tatsuya</creatorcontrib><creatorcontrib>Maehara, Akira</creatorcontrib><creatorcontrib>Kimura, Satoshi</creatorcontrib><creatorcontrib>Abe, Hideki</creatorcontrib><creatorcontrib>Iwata, Tadahisa</creatorcontrib><title>Thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate]</title><title>Polymer degradation and stability</title><description>•The thermal degradation of P(3HB-co-16 mol%−4HB) was investigated by its pyrolyzates and kinetics approaches.•The thermal degradation of P(3HB-co-16 mol%−4HB) proceeded at least in two steps.•Thermal degradation behavior of P(3HB-co-16 mol%−4HB) changed in time and/or temperature•Random degradation in the initial period changes to subsequent 0th-order weight loss meaning unzipping degradation of 3HB units.•The unzipping degradation of 3HB unit from the chain end may stop at the 4HB unit randomly present in the copolymer.
The thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-16 mol%-4-hydroxybutyrate] (P(3HB-co-16 mol%-4HB)) was investigated based on spectroscopic analysis of its pyrolyzates and two kinetic modeling approaches. Pyrolyzate analysis revealed that trans-crotonic acid, cis-crotonic acid, γ-butyrolactone, and their oligomers (dimers and trimers) were produced following thermal degradation of P(3HB-co-16 mol%-4HB). The kinetic analyses confirmed that the thermal degradation behavior of this copolymer changed depending on the time and/or temperature parameters. Specifically, this degradation process proceeded in at least two steps, (i) initial random degradation and (ii) subsequent 0th-order weight loss, which indicated unzipping degradation of the 3HB units. Based on 13C NMR and two-dimensional NMR methods, it was determined that the unzipping degradation of 3HB units starting from the chain end may stop or volatilize an oligomer when the reaction reaches a 4HB unit randomly present in the copolymer.</description><subject>Biodegradation</subject><subject>Butyrolactone</subject><subject>Copolymers</subject><subject>Degradation mechanism</subject><subject>Dimers</subject><subject>Heat conductivity</subject><subject>Kinetic analysis</subject><subject>Microbial copolyester</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Oligomers</subject><subject>P(3HB-co-4HB)</subject><subject>Polyhydroxyalkanoate</subject><subject>Process parameters</subject><subject>Reaction kinetics</subject><subject>Temperature</subject><subject>Temperature effects</subject><subject>Thermal cycling</subject><subject>Thermal degradation</subject><subject>Trimers</subject><subject>Unzipping reaction</subject><subject>Weight loss</subject><subject>β-elimination</subject><issn>0141-3910</issn><issn>1873-2321</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNqNkE9Lw0AQxRdRsFa_Q0AEPWzdf9lkDx6kaBUKitSTyLLZzNqEtlt302K-vQnx1JNzGZh58x7zQ-iKkgklVN7Wk61ftesSvoIpY2OKCSOs3ykhyREa0TzjmHFGj9GIUEExV5ScorMYa9KVSOkIvS6WENZmlQwupqn8JilgafaVD4l3SR_xcf12gzletmXwP22xa9pgGsDWY3E4_DxHJ86sIlz89TF6f3xYTJ_w_GX2PL2fYyty1mDKhbPGAcsy67JUKVkqlhIhcklYCaQklnEo8oxIxiWXqZFKCJapQkknHPAxuhx8t8F_7yA2uva7sOkiNROKqowqIjrV3aCywccYwOltqNYmtJoS3UPUtT6AqHuIeoDY3c-Ge-he2VcQdLQVbCyUVQDb6NJX_3T6BSLphBA</recordid><startdate>202101</startdate><enddate>202101</enddate><creator>Omura, Taku</creator><creator>Goto, Tatsuya</creator><creator>Maehara, Akira</creator><creator>Kimura, Satoshi</creator><creator>Abe, Hideki</creator><creator>Iwata, Tadahisa</creator><general>Elsevier Ltd</general><general>Elsevier BV</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>202101</creationdate><title>Thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate]</title><author>Omura, Taku ; Goto, Tatsuya ; Maehara, Akira ; Kimura, Satoshi ; Abe, Hideki ; Iwata, Tadahisa</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c482t-134fcafe277cf75996d9250448602de0d0c23eb8706236365a6944279b96f4fe3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Biodegradation</topic><topic>Butyrolactone</topic><topic>Copolymers</topic><topic>Degradation mechanism</topic><topic>Dimers</topic><topic>Heat conductivity</topic><topic>Kinetic analysis</topic><topic>Microbial copolyester</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Oligomers</topic><topic>P(3HB-co-4HB)</topic><topic>Polyhydroxyalkanoate</topic><topic>Process parameters</topic><topic>Reaction kinetics</topic><topic>Temperature</topic><topic>Temperature effects</topic><topic>Thermal cycling</topic><topic>Thermal degradation</topic><topic>Trimers</topic><topic>Unzipping reaction</topic><topic>Weight loss</topic><topic>β-elimination</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Omura, Taku</creatorcontrib><creatorcontrib>Goto, Tatsuya</creatorcontrib><creatorcontrib>Maehara, Akira</creatorcontrib><creatorcontrib>Kimura, Satoshi</creatorcontrib><creatorcontrib>Abe, Hideki</creatorcontrib><creatorcontrib>Iwata, Tadahisa</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Polymer degradation and stability</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Omura, Taku</au><au>Goto, Tatsuya</au><au>Maehara, Akira</au><au>Kimura, Satoshi</au><au>Abe, Hideki</au><au>Iwata, Tadahisa</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate]</atitle><jtitle>Polymer degradation and stability</jtitle><date>2021-01</date><risdate>2021</risdate><volume>183</volume><spage>109460</spage><pages>109460-</pages><artnum>109460</artnum><issn>0141-3910</issn><eissn>1873-2321</eissn><abstract>•The thermal degradation of P(3HB-co-16 mol%−4HB) was investigated by its pyrolyzates and kinetics approaches.•The thermal degradation of P(3HB-co-16 mol%−4HB) proceeded at least in two steps.•Thermal degradation behavior of P(3HB-co-16 mol%−4HB) changed in time and/or temperature•Random degradation in the initial period changes to subsequent 0th-order weight loss meaning unzipping degradation of 3HB units.•The unzipping degradation of 3HB unit from the chain end may stop at the 4HB unit randomly present in the copolymer.
The thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-16 mol%-4-hydroxybutyrate] (P(3HB-co-16 mol%-4HB)) was investigated based on spectroscopic analysis of its pyrolyzates and two kinetic modeling approaches. Pyrolyzate analysis revealed that trans-crotonic acid, cis-crotonic acid, γ-butyrolactone, and their oligomers (dimers and trimers) were produced following thermal degradation of P(3HB-co-16 mol%-4HB). The kinetic analyses confirmed that the thermal degradation behavior of this copolymer changed depending on the time and/or temperature parameters. Specifically, this degradation process proceeded in at least two steps, (i) initial random degradation and (ii) subsequent 0th-order weight loss, which indicated unzipping degradation of the 3HB units. Based on 13C NMR and two-dimensional NMR methods, it was determined that the unzipping degradation of 3HB units starting from the chain end may stop or volatilize an oligomer when the reaction reaches a 4HB unit randomly present in the copolymer.</abstract><cop>London</cop><pub>Elsevier Ltd</pub><doi>10.1016/j.polymdegradstab.2020.109460</doi><oa>free_for_read</oa></addata></record> |
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| subjects | Biodegradation Butyrolactone Copolymers Degradation mechanism Dimers Heat conductivity Kinetic analysis Microbial copolyester NMR Nuclear magnetic resonance Oligomers P(3HB-co-4HB) Polyhydroxyalkanoate Process parameters Reaction kinetics Temperature Temperature effects Thermal cycling Thermal degradation Trimers Unzipping reaction Weight loss β-elimination |
| title | Thermal degradation behavior of poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate] |
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