主链含芳基均三嗪环结构氮杂环聚芳醚及其C纤维复合材料  

Thermosetting poly(aryl ether)s bearing phthalazinone and phenyl-s-triazine units in backbones and their C fiber composites

作　　者：宗立率[1,2] 邬祚强 王锦艳[1,2] 蹇锡高[1,2] 

机构地区：[1]辽宁省高性能树脂工程技术研究中心,大连116012 [2]大连理工大学化工学院高分子材料系,大连116024

出　　处：《复合材料学报》2013年第S1期59-64,共6页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(21074017)

摘　　要：本文以4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)与4-二(4-氟苯基)-6-苯基-1,3,5-三嗪(BFPT)进行亲核取代,进而使用4-硝基邻苯二甲腈(NPH)对其封端,得到双邻苯二甲腈封端的齐聚物(PBD-Ph)。在少量固化剂二氨基二苯砜(DAS)存在下,在一定固化工艺条件下,固化形成含三芳基均三嗪环结构热固型树脂(Th-PBD)。红外光谱和1 H-核磁共振法对合成出的齐聚物进行结构表征,证实产物分子结构与目标产物一致。利用示差量热扫描法(DSC)及流变测试树脂的熔融及固化粘度行为变化曲线。加入5%固化剂DAS时,经Kissinger方程计算固化反应活化能为60.06kJ/mol。流变测试表明PBD-Phs均可在低于450℃时发生熔融转变,加入固化剂后体系粘度随温度呈先上升后下降趋势。热失重测试(TGA)表明在氮气氛围下固化物的5%热失重温度均在500℃以上,900℃残碳率均高于60%。采用热压法制备Th-PBD1的C纤维复合材料。动态机械性能分析(DMA)表明Th-PBD1的400℃残余储能模量约9Gpa,玻璃化转变温度(Tg)高于400℃;SEM测试表明,复合材料挂胶量较高,与C纤维结合紧密。Novel oligomeric poly(aryl ether)phthalonitriles(PBD-Phs)were prepared by utilizing a nucleophilic displacement reaction between 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ)and 4-bis(4- fluophenyl)-6-phenyl-1,3,5-triazine(BFPT)under alkaline conditions through shifting the stoichiometric ratio of each monomer.Then 4-nitrophthalonitrile was added to get oligmers with phthalonitrile end unites on both sides.And all of them could be cured to the thermosetting materials bearing phenyl-s-triazine structure(Th-PBD)in the presence of a small amount of the curing additive—4,4'-aminophenyl sulfone in definite curing procedure.1 H- NMR and FT-IR have been used to confirm and monitor the structures of the products,which was proved to be in accordance with the molecule design.DSC and Rheology tests were carried to investigate the thermosetting properties of PBD-Ph1including melting points and the curing viscosity shifting curves.Additionally,the reaction activation energy was calculated 60.06kJ/mol by Kissinger equation via different heating rate in DSC scanning. Rheology tests demonstrate the series of PBD-Ph oligmers could all be melted below 450℃.However,the viscosity of each polymer expressed a increasing-then-decreasing tendency in the presence of 4,4'-aminophenyl sulfone, which has provided a new processing method.The result of TGA shows that the cured products have good heat resistance.The temperature for 5% weight loss of Th-PBD-Ph1tested by TGA in nitrogen is beyond 513℃. Additionally,the char yield of them in 900 ℃ is more than 60%,indicating their outstanding thermal stability. DMA was used to analyses the thermo mechanical properties of the C fiber composite of Th-PBD-Ph1with storage modulus being about 9GPa at 400℃and Tg surpassing 400℃.SEM indicate that the hang quantity of cement of C fiber composites was high,and the resins adhere to fibers closely.

关 键 词：杂萘联苯 邻苯二甲腈 聚芳醚 三芳基均三嗪环 

分 类 号：TB332[一般工业技术—材料科学与工程]