{"title":"通过硼酸桥作为交联剂,探索硼烷增强酚醛树脂热稳定性的潜力,以及碳质材料中硼种形成的机理:综合研究","authors":"","doi":"10.1016/j.polymdegradstab.2024.110983","DOIUrl":null,"url":null,"abstract":"<div><p>In advanced material science, we explore the potential of boratrane, a promising agent for enhancing thermal stability. By combining rigorous Density Functional Theory (DFT) calculations with groundbreaking experimental analyses, we reveal the intricate interplay of radical intermediates and mechanisms underlying the thermal evolution of boratrane-infused materials. Our innovative approach illuminates dynamic structural transformations and elucidates boratrane's pivotal role in fortifying thermal resilience. The DFT calculations identify radical intermediates and mechanisms of thermal degradation, highlighting the role of borate bridges in delocalizing π-electrons in aromatic rings through Gibbs free energy (∆G<sub>RXN</sub>), Highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO), and electrostatic potential (ESP) analyses. Fukui function analysis provides insights into the reactivity of these structures towards free radical attacks. Our findings demonstrate that boratrane-modified resins exhibit a stable BO<sub>4</sub><sup>-</sup> structure, which prevents self-condensation of boratrane to B<sub>2</sub>O<sub>3</sub> and enhances the thermal stability of oxygenated resins. This improvement is due to the formation of intramolecular hydrogen bonds, contributing to helix-like structures that strengthen the resin. The mechanism by which the BO<sub>4</sub><sup>-</sup> structure terminates radical agents and transforms into carbonaceous material is elucidated through thermodynamic values, revealing the plausible reactions and chemical structure of boron in the resulting material.</p></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":null,"pages":null},"PeriodicalIF":6.3000,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Exploring boratrane's potential to enhance the thermal stability of phenol-formaldehyde resins by borate bridge as a crosslinker and the mechanistic formation of boron species in carbonaceous materials: A comprehensive study\",\"authors\":\"\",\"doi\":\"10.1016/j.polymdegradstab.2024.110983\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In advanced material science, we explore the potential of boratrane, a promising agent for enhancing thermal stability. By combining rigorous Density Functional Theory (DFT) calculations with groundbreaking experimental analyses, we reveal the intricate interplay of radical intermediates and mechanisms underlying the thermal evolution of boratrane-infused materials. Our innovative approach illuminates dynamic structural transformations and elucidates boratrane's pivotal role in fortifying thermal resilience. The DFT calculations identify radical intermediates and mechanisms of thermal degradation, highlighting the role of borate bridges in delocalizing π-electrons in aromatic rings through Gibbs free energy (∆G<sub>RXN</sub>), Highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO), and electrostatic potential (ESP) analyses. Fukui function analysis provides insights into the reactivity of these structures towards free radical attacks. Our findings demonstrate that boratrane-modified resins exhibit a stable BO<sub>4</sub><sup>-</sup> structure, which prevents self-condensation of boratrane to B<sub>2</sub>O<sub>3</sub> and enhances the thermal stability of oxygenated resins. This improvement is due to the formation of intramolecular hydrogen bonds, contributing to helix-like structures that strengthen the resin. The mechanism by which the BO<sub>4</sub><sup>-</sup> structure terminates radical agents and transforms into carbonaceous material is elucidated through thermodynamic values, revealing the plausible reactions and chemical structure of boron in the resulting material.</p></div>\",\"PeriodicalId\":406,\"journal\":{\"name\":\"Polymer Degradation and Stability\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.3000,\"publicationDate\":\"2024-08-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Degradation and Stability\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0141391024003276\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Degradation and Stability","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0141391024003276","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Exploring boratrane's potential to enhance the thermal stability of phenol-formaldehyde resins by borate bridge as a crosslinker and the mechanistic formation of boron species in carbonaceous materials: A comprehensive study
In advanced material science, we explore the potential of boratrane, a promising agent for enhancing thermal stability. By combining rigorous Density Functional Theory (DFT) calculations with groundbreaking experimental analyses, we reveal the intricate interplay of radical intermediates and mechanisms underlying the thermal evolution of boratrane-infused materials. Our innovative approach illuminates dynamic structural transformations and elucidates boratrane's pivotal role in fortifying thermal resilience. The DFT calculations identify radical intermediates and mechanisms of thermal degradation, highlighting the role of borate bridges in delocalizing π-electrons in aromatic rings through Gibbs free energy (∆GRXN), Highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO), and electrostatic potential (ESP) analyses. Fukui function analysis provides insights into the reactivity of these structures towards free radical attacks. Our findings demonstrate that boratrane-modified resins exhibit a stable BO4- structure, which prevents self-condensation of boratrane to B2O3 and enhances the thermal stability of oxygenated resins. This improvement is due to the formation of intramolecular hydrogen bonds, contributing to helix-like structures that strengthen the resin. The mechanism by which the BO4- structure terminates radical agents and transforms into carbonaceous material is elucidated through thermodynamic values, revealing the plausible reactions and chemical structure of boron in the resulting material.
期刊介绍:
Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology.
Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal.
However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.