Matrix matters: Hyperbranched flame retardants in aliphatic and aromatic epoxy resins
We synthesized a library of phosphorus-based flame retardants (phosphates and phosphoramides of low and high molar mass) and investigated their behavior in two epoxy resins (one aliphatic and one aromatic). The pyrolytic and burning behavior of the two resins (via TGA, TG-FTIR, Hot stage FTIR, Py-GC...
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Veröffentlicht in: | Polymer degradation and stability 2019-12, Vol.170, p.108986, Article 108986 |
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description | We synthesized a library of phosphorus-based flame retardants (phosphates and phosphoramides of low and high molar mass) and investigated their behavior in two epoxy resins (one aliphatic and one aromatic). The pyrolytic and burning behavior of the two resins (via TGA, TG-FTIR, Hot stage FTIR, Py-GC/MS, PCFC, DSC, LOI, UL-94, Cone calorimeter) are analyzed and compared to the results of flame retardant (FR)-containing composites. A decomposition pathway incorporating the identified modes of action and known chemical mechanisms is proposed. The overlap of decomposition temperature (Tdec) ranges of matrix and FR determines the efficacy of the system. Low molar mass FRs strongly impact material properties like Tg but are very reactive, and high molar mass variants are more thermally stable. Varying P–O and P–N content of the FR affects decomposition, but the chemical structure of the matrix also guides FR behavior. Thus, phosphates afford lower fire load and heat release in aliphatic epoxy resins, and phosphoramides can act as additives in an aromatic matrix or a reactive FRs in aliphatic ones. The chemical structure and the structure-property relationship of both FR and matrix are central to FR performance and must be viewed not as two separate but as one codependent system.
•The decomposition pathway of an aliphatic epoxy resin is elucidated via multi-methodical approach.•Phosphates and phosphoramides as low or high molar mass and hyperbranched polymer are added as FRs.•Phosphates: phosphorylation/ flame poisoning. Phosphoramides: additives in aromatic matrix but reactive in aliphatic matrix.•Chemical reactions crucial to FR modes of action require that FR and matrix decompose in proximate temperature ranges.•Flame retardancy is high when overlap is high. Chemical structure and polymerization influence decomposition temperature. |
doi_str_mv | 10.1016/j.polymdegradstab.2019.108986 |
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•The decomposition pathway of an aliphatic epoxy resin is elucidated via multi-methodical approach.•Phosphates and phosphoramides as low or high molar mass and hyperbranched polymer are added as FRs.•Phosphates: phosphorylation/ flame poisoning. Phosphoramides: additives in aromatic matrix but reactive in aliphatic matrix.•Chemical reactions crucial to FR modes of action require that FR and matrix decompose in proximate temperature ranges.•Flame retardancy is high when overlap is high. Chemical structure and polymerization influence decomposition temperature.</description><identifier>ISSN: 0141-3910</identifier><identifier>EISSN: 1873-2321</identifier><identifier>DOI: 10.1016/j.polymdegradstab.2019.108986</identifier><language>eng</language><publisher>London: Elsevier Ltd</publisher><subject>Additives ; Aliphatic compounds ; Cone calorimeters ; Decomposition ; Epoxy resin ; Epoxy resins ; Fire load ; Flame retardant ; Flame retardants ; Hyperbranched polymer ; Material properties ; Organic chemistry ; Phosphate ; Phosphates ; Phosphoramide ; Phosphorus ; Polymers ; Protective clothing ; Resins ; Thermal stability</subject><ispartof>Polymer degradation and stability, 2019-12, Vol.170, p.108986, Article 108986</ispartof><rights>2019 Elsevier Ltd</rights><rights>Copyright Elsevier BV Dec 2019</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c398t-2f3175177c651e41ed17d793e1fe2d53a1724a7a77e1aba1a6baf8e18fc329513</citedby><cites>FETCH-LOGICAL-c398t-2f3175177c651e41ed17d793e1fe2d53a1724a7a77e1aba1a6baf8e18fc329513</cites><orcidid>0000-0002-9461-1368 ; 0000-0001-5726-9754</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S0141391019303143$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,776,780,3537,27901,27902,65306</link.rule.ids></links><search><creatorcontrib>Battig, Alexander</creatorcontrib><creatorcontrib>Markwart, Jens C.</creatorcontrib><creatorcontrib>Wurm, Frederik R.</creatorcontrib><creatorcontrib>Schartel, Bernhard</creatorcontrib><title>Matrix matters: Hyperbranched flame retardants in aliphatic and aromatic epoxy resins</title><title>Polymer degradation and stability</title><description>We synthesized a library of phosphorus-based flame retardants (phosphates and phosphoramides of low and high molar mass) and investigated their behavior in two epoxy resins (one aliphatic and one aromatic). The pyrolytic and burning behavior of the two resins (via TGA, TG-FTIR, Hot stage FTIR, Py-GC/MS, PCFC, DSC, LOI, UL-94, Cone calorimeter) are analyzed and compared to the results of flame retardant (FR)-containing composites. A decomposition pathway incorporating the identified modes of action and known chemical mechanisms is proposed. The overlap of decomposition temperature (Tdec) ranges of matrix and FR determines the efficacy of the system. Low molar mass FRs strongly impact material properties like Tg but are very reactive, and high molar mass variants are more thermally stable. Varying P–O and P–N content of the FR affects decomposition, but the chemical structure of the matrix also guides FR behavior. Thus, phosphates afford lower fire load and heat release in aliphatic epoxy resins, and phosphoramides can act as additives in an aromatic matrix or a reactive FRs in aliphatic ones. The chemical structure and the structure-property relationship of both FR and matrix are central to FR performance and must be viewed not as two separate but as one codependent system.
•The decomposition pathway of an aliphatic epoxy resin is elucidated via multi-methodical approach.•Phosphates and phosphoramides as low or high molar mass and hyperbranched polymer are added as FRs.•Phosphates: phosphorylation/ flame poisoning. Phosphoramides: additives in aromatic matrix but reactive in aliphatic matrix.•Chemical reactions crucial to FR modes of action require that FR and matrix decompose in proximate temperature ranges.•Flame retardancy is high when overlap is high. Chemical structure and polymerization influence decomposition temperature.</description><subject>Additives</subject><subject>Aliphatic compounds</subject><subject>Cone calorimeters</subject><subject>Decomposition</subject><subject>Epoxy resin</subject><subject>Epoxy resins</subject><subject>Fire load</subject><subject>Flame retardant</subject><subject>Flame retardants</subject><subject>Hyperbranched polymer</subject><subject>Material properties</subject><subject>Organic chemistry</subject><subject>Phosphate</subject><subject>Phosphates</subject><subject>Phosphoramide</subject><subject>Phosphorus</subject><subject>Polymers</subject><subject>Protective clothing</subject><subject>Resins</subject><subject>Thermal stability</subject><issn>0141-3910</issn><issn>1873-2321</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqNkE1LAzEQhoMoWD_-w4J43JpJdje7ggcp2goVL_YcpsmsTel-mKTS_nu31pMn5zIM877vMA9jt8DHwKG4W4_7brNvLH14tCHiciw4VMOurMrihI2gVDIVUsApG3HIIJUV8HN2EcKaD5XlMGKLV4ze7ZIGYyQf7pPZvie_9NiaFdmk3mBDiaeI3mIbQ-LaBDeuX2F0JsHWJui75megvtvtB2lwbbhiZzVuAl3_9ku2eH56n8zS-dv0ZfI4T42sypiKWoLKQSlT5EAZkAVlVSUJahI2lwhKZKhQKQJcImCxxLokKGsjRZWDvGQ3x9zed59bClGvu61vh5NaSMm5kEqKQfVwVBnfheCp1r13Dfq9Bq4PJPVa_yGpDyT1keTgnx79NLzy5cjrYBy1hqzzZKK2nftn0jcTlYcP</recordid><startdate>20191201</startdate><enddate>20191201</enddate><creator>Battig, Alexander</creator><creator>Markwart, Jens C.</creator><creator>Wurm, Frederik R.</creator><creator>Schartel, Bernhard</creator><general>Elsevier Ltd</general><general>Elsevier BV</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0002-9461-1368</orcidid><orcidid>https://orcid.org/0000-0001-5726-9754</orcidid></search><sort><creationdate>20191201</creationdate><title>Matrix matters: Hyperbranched flame retardants in aliphatic and aromatic epoxy resins</title><author>Battig, Alexander ; Markwart, Jens C. ; Wurm, Frederik R. ; Schartel, Bernhard</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c398t-2f3175177c651e41ed17d793e1fe2d53a1724a7a77e1aba1a6baf8e18fc329513</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Additives</topic><topic>Aliphatic compounds</topic><topic>Cone calorimeters</topic><topic>Decomposition</topic><topic>Epoxy resin</topic><topic>Epoxy resins</topic><topic>Fire load</topic><topic>Flame retardant</topic><topic>Flame retardants</topic><topic>Hyperbranched polymer</topic><topic>Material properties</topic><topic>Organic chemistry</topic><topic>Phosphate</topic><topic>Phosphates</topic><topic>Phosphoramide</topic><topic>Phosphorus</topic><topic>Polymers</topic><topic>Protective clothing</topic><topic>Resins</topic><topic>Thermal stability</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Battig, Alexander</creatorcontrib><creatorcontrib>Markwart, Jens C.</creatorcontrib><creatorcontrib>Wurm, Frederik R.</creatorcontrib><creatorcontrib>Schartel, Bernhard</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>Battig, Alexander</au><au>Markwart, Jens C.</au><au>Wurm, Frederik R.</au><au>Schartel, Bernhard</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Matrix matters: Hyperbranched flame retardants in aliphatic and aromatic epoxy resins</atitle><jtitle>Polymer degradation and stability</jtitle><date>2019-12-01</date><risdate>2019</risdate><volume>170</volume><spage>108986</spage><pages>108986-</pages><artnum>108986</artnum><issn>0141-3910</issn><eissn>1873-2321</eissn><abstract>We synthesized a library of phosphorus-based flame retardants (phosphates and phosphoramides of low and high molar mass) and investigated their behavior in two epoxy resins (one aliphatic and one aromatic). The pyrolytic and burning behavior of the two resins (via TGA, TG-FTIR, Hot stage FTIR, Py-GC/MS, PCFC, DSC, LOI, UL-94, Cone calorimeter) are analyzed and compared to the results of flame retardant (FR)-containing composites. A decomposition pathway incorporating the identified modes of action and known chemical mechanisms is proposed. The overlap of decomposition temperature (Tdec) ranges of matrix and FR determines the efficacy of the system. Low molar mass FRs strongly impact material properties like Tg but are very reactive, and high molar mass variants are more thermally stable. Varying P–O and P–N content of the FR affects decomposition, but the chemical structure of the matrix also guides FR behavior. Thus, phosphates afford lower fire load and heat release in aliphatic epoxy resins, and phosphoramides can act as additives in an aromatic matrix or a reactive FRs in aliphatic ones. The chemical structure and the structure-property relationship of both FR and matrix are central to FR performance and must be viewed not as two separate but as one codependent system.
•The decomposition pathway of an aliphatic epoxy resin is elucidated via multi-methodical approach.•Phosphates and phosphoramides as low or high molar mass and hyperbranched polymer are added as FRs.•Phosphates: phosphorylation/ flame poisoning. Phosphoramides: additives in aromatic matrix but reactive in aliphatic matrix.•Chemical reactions crucial to FR modes of action require that FR and matrix decompose in proximate temperature ranges.•Flame retardancy is high when overlap is high. Chemical structure and polymerization influence decomposition temperature.</abstract><cop>London</cop><pub>Elsevier Ltd</pub><doi>10.1016/j.polymdegradstab.2019.108986</doi><orcidid>https://orcid.org/0000-0002-9461-1368</orcidid><orcidid>https://orcid.org/0000-0001-5726-9754</orcidid></addata></record> |
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subjects | Additives Aliphatic compounds Cone calorimeters Decomposition Epoxy resin Epoxy resins Fire load Flame retardant Flame retardants Hyperbranched polymer Material properties Organic chemistry Phosphate Phosphates Phosphoramide Phosphorus Polymers Protective clothing Resins Thermal stability |
title | Matrix matters: Hyperbranched flame retardants in aliphatic and aromatic epoxy resins |
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