{"title":"用含 N/Cl 的芳香烃制备高性能合成沥青","authors":"Yu-kun Zhang, Xiong-chao Lin, Hong-feng Gao, Wen-shuai Xi, Cai-hong Wang, Yong-gang Wang","doi":"10.1016/S1872-5805(24)60864-4","DOIUrl":null,"url":null,"abstract":"<div><p>The preparation of a synthetic pitch from aromatic monomers could easily regulate structure orientation at the molecular level, which would be useful in fabrication. An isotropic synthetic pitch was prepared by a chlorine- and/or nitrogen-induced substitution polymerization reaction method using aromatic hydrocarbon precursors containing Cl and N, which for this study were chloromethyl naphthalene and quinoline. This method was verified by investigating the structural changes under different synthesis conditions, and the synthesis mechanism induced by aromatics containing Cl was also probed. The result shows that the pyridinic N in quinoline contains a lone pair of electrons, and is an effective active site to induce the polymerization reaction by coupling with aromatic hydrocarbons containing Cl. The reaction between such free radicals causes strong homopolymerization and oligomerization. A higher reaction temperature and longer reaction time significantly increased the degree of polymerization and thus increased the softening point of the pitch. A linear molecular structure was formed by the Cl substitution reaction, which produced a highly spinnable pitch with a softening point of 258.6 °C, and carbon fibers with a tensile strength of 1 163.82 MPa were obtained. This study provides a relatively simple and safe method for the preparation of high-quality spinnable pitch.</p></div>","PeriodicalId":19719,"journal":{"name":"New Carbon Materials","volume":"39 4","pages":"Pages 655-667"},"PeriodicalIF":5.7000,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Preparation of a high-performance synthetic pitch from aromatic hydrocarbons containing N/Cl\",\"authors\":\"Yu-kun Zhang, Xiong-chao Lin, Hong-feng Gao, Wen-shuai Xi, Cai-hong Wang, Yong-gang Wang\",\"doi\":\"10.1016/S1872-5805(24)60864-4\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The preparation of a synthetic pitch from aromatic monomers could easily regulate structure orientation at the molecular level, which would be useful in fabrication. An isotropic synthetic pitch was prepared by a chlorine- and/or nitrogen-induced substitution polymerization reaction method using aromatic hydrocarbon precursors containing Cl and N, which for this study were chloromethyl naphthalene and quinoline. This method was verified by investigating the structural changes under different synthesis conditions, and the synthesis mechanism induced by aromatics containing Cl was also probed. The result shows that the pyridinic N in quinoline contains a lone pair of electrons, and is an effective active site to induce the polymerization reaction by coupling with aromatic hydrocarbons containing Cl. The reaction between such free radicals causes strong homopolymerization and oligomerization. A higher reaction temperature and longer reaction time significantly increased the degree of polymerization and thus increased the softening point of the pitch. A linear molecular structure was formed by the Cl substitution reaction, which produced a highly spinnable pitch with a softening point of 258.6 °C, and carbon fibers with a tensile strength of 1 163.82 MPa were obtained. This study provides a relatively simple and safe method for the preparation of high-quality spinnable pitch.</p></div>\",\"PeriodicalId\":19719,\"journal\":{\"name\":\"New Carbon Materials\",\"volume\":\"39 4\",\"pages\":\"Pages 655-667\"},\"PeriodicalIF\":5.7000,\"publicationDate\":\"2024-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"New Carbon Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1872580524608644\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"Materials Science\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"New Carbon Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1872580524608644","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"Materials Science","Score":null,"Total":0}
引用次数: 0
摘要
用芳香族单体制备合成沥青可以在分子水平上轻松调节结构取向,这在制造过程中非常有用。本研究采用氯和/或氮诱导的取代聚合反应方法,使用含 Cl 和 N 的芳香烃前体(本研究使用的是氯甲基萘和喹啉)制备了各向同性合成沥青。通过研究不同合成条件下的结构变化,验证了该方法的有效性,并探究了含 Cl 芳烃诱导的合成机理。结果表明,喹啉中的吡啶 N 含有一对孤对电子,是与含 Cl 的芳香烃偶联诱导聚合反应的有效活性位点。这种自由基之间的反应会引起强烈的均聚和低聚作用。较高的反应温度和较长的反应时间可显著提高聚合度,从而提高沥青的软化点。通过 Cl 取代反应形成了线性分子结构,产生了软化点为 258.6 °C 的高可纺性沥青,并获得了拉伸强度为 1 163.82 MPa 的碳纤维。这项研究为制备高质量可纺沥青提供了一种相对简单和安全的方法。
Preparation of a high-performance synthetic pitch from aromatic hydrocarbons containing N/Cl
The preparation of a synthetic pitch from aromatic monomers could easily regulate structure orientation at the molecular level, which would be useful in fabrication. An isotropic synthetic pitch was prepared by a chlorine- and/or nitrogen-induced substitution polymerization reaction method using aromatic hydrocarbon precursors containing Cl and N, which for this study were chloromethyl naphthalene and quinoline. This method was verified by investigating the structural changes under different synthesis conditions, and the synthesis mechanism induced by aromatics containing Cl was also probed. The result shows that the pyridinic N in quinoline contains a lone pair of electrons, and is an effective active site to induce the polymerization reaction by coupling with aromatic hydrocarbons containing Cl. The reaction between such free radicals causes strong homopolymerization and oligomerization. A higher reaction temperature and longer reaction time significantly increased the degree of polymerization and thus increased the softening point of the pitch. A linear molecular structure was formed by the Cl substitution reaction, which produced a highly spinnable pitch with a softening point of 258.6 °C, and carbon fibers with a tensile strength of 1 163.82 MPa were obtained. This study provides a relatively simple and safe method for the preparation of high-quality spinnable pitch.
期刊介绍:
New Carbon Materials is a scholarly journal that publishes original research papers focusing on the physics, chemistry, and technology of organic substances that serve as precursors for creating carbonaceous solids with aromatic or tetrahedral bonding. The scope of materials covered by the journal extends from diamond and graphite to a variety of forms including chars, semicokes, mesophase substances, carbons, carbon fibers, carbynes, fullerenes, and carbon nanotubes. The journal's objective is to showcase the latest research findings and advancements in the areas of formation, structure, properties, behaviors, and technological applications of carbon materials. Additionally, the journal includes papers on the secondary production of new carbon and composite materials, such as carbon-carbon composites, derived from the aforementioned carbons. Research papers on organic substances will be considered for publication only if they have a direct relevance to the resulting carbon materials.