线型酚醛树脂结构改性的研究进展  

Research Progress on Structural Modification of Novolac Resin

作　　者：陈双 雷子萱 徐力 李嘉玄 陈栋梁 强军锋[1] 刘育红[2] CHEN Shuang;LEI Zixuan;XU Li;LI Jiaxuan;CHEN Dongliang;QIANG Junfeng;LIU Yuhong(College of Materials Science and Engineering,Xi an University of Science and Technology,Xi'an 710054,China;School of Chemical Engineering and Technology,Xi'an Jiaotong University,Xi'an 710049,China)

机构地区：[1]西安科技大学材料科学与工程学院,西安710054 [2]西安交通大学化学工程与技术学院,西安710049

出　　处：《材料导报》2023年第23期205-214,共10页Materials Reports

基　　金：陕西省重点研发计划-两链融合(2021GXLH-Z-020);国家自然科学基金-中物院联合基金(U193010027);国家自然科学基金(51873171)。

摘　　要：酚醛树脂具有良好的力学性能和耐高温性,被广泛应用于航天、建筑等多个领域,尤其作为高性能碳/碳复合材料或碳/酚醛耐烧蚀材料的基体树脂。传统酚醛树脂固化过程释放挥发分,固化后交联结构存在不足,如紧密堆砌的刚性芳环导致其脆性高,易氧化的酚羟基与亚甲基降低了其耐热性和残炭率。传统酚醛的多层次结构设计和改性是满足酚醛树脂在新型复合材料成型工艺和高性能热防护领域应用的关键,例如在线型酚醛分子结构中引入可加成官能团,如炔丙基、烯丙基等,借助此类基团之间的热聚合实现酚醛树脂的加成固化,还可以对酚醛树脂进行结构设计改性,如羟基醚化、环氧化或引进钼、硼、有机硅等组分,通过化学键接和物理缠结实现对分子结构的调控。这类新型酚醛树脂从本质上避免了固化过程中小分子的逸出,更易于制备出高质量的复合材料。鉴于此,本文着重叙述了几种典型的结构改性线型酚醛树脂及其在烧蚀防护领域的研究和应用进展。Phenolic resin has excellent mechanical properties and high temperature resistance,and is widely used in aerospace,architecture and other fields as the matrix resin of high-performance carbon/carbon composites or carbon/phenolic ablation resistant materials.The traditional phenolic resin releases volatiles during curing process,and its cross-linking structure after curing is deficient.For example,the tightly stacked rigid aromatic rings cause its high brittleness,the easily oxidized phenolic hydroxyl groups and methylene groups reduce its heat resistance and carbon residue rate.The multi-level structure design and modification of traditional phenolic resin is the key to satisfy its application in the field of new composite molding process and high-performance thermal protection.For example,the introduction of additive functional groups like propargyl groups and allyl groups into the novolac resin can achieve additive curing by thermal polymerization process.Through hydroxyl etherification reaction,epoxidation reaction or the introduction of molybdenum,boron,silicone and other components into the resin matrix,the molecular structure of resin can be regulated through chemical bonding and physical entanglement,then the structural design modification of phenolic resin can be achieved.This type of new phenolic resin essentially avoids the escape of small molecules during the curing process,and is easier to prepare high-quality composites.In summary,this paper focuses on several typical structural modified novolac resins and their research progress in the field of ablation protection.

关 键 词：酚醛树脂 结构改性 加成固化 耐热 复合材料 

分 类 号：TQ323.1[化学工程—合成树脂塑料工业]