新型生物基苯并噁嗪的合成及性能  

Synthesis and Properties of a Novel Bio-based Benzoxazine

作　　者：殷平 闫红强[1] 程捷[1] 方征平[1] YIN Ping;YAN Hongqiang;CHENG Jie;FANG Zhengping(Laboratory of Polymer Material and Engineering, Ningbo Institute of Technology, Zhejiang University, Ningbo 315100, China;Chemical Engineering and Bioengineering, Zhejiang University, Hangzhou 310027, China)

机构地区：[1]浙江大学宁波理工学院高分子材料与共混实验室,宁波315100 [2]浙江大学化学工程与生物工程学院,杭州310027

出　　处：《高等学校化学学报》2019年第5期1071-1079,共9页Chemical Journal of Chinese Universities

基　　金：浙江省自然科学基金(批准号:LY19E030004);宁波市自然科学基金(批准号:2018A610184);宁波市工业重大专项(批准号:2015B11005)资助~~

摘　　要：以生物基糠胺、酚酞和多聚甲醛为原料,制备了一种新型生物基苯并噁嗪树脂——酚酞糠胺型苯并嗪树脂(PPTL-F-BOZ),采用FTIR,1H NMR和13C NMR等手段对其单体PTL-F-BOZ的结构进行了表征,并对其固化反应、耐热和阻燃性能进行分析.结果表明,与传统的化石基双酚型苯并噁嗪——双酚A苯胺型苯并噁嗪(BPA-A-BOZ)相比,PTL-F-BOZ显示出较低的固化反应温度,且糠胺中呋喃环的存在会增加聚合物的交联密度,并减缓苯氧结构向苯酚结构的重排反应,致使其在DSC曲线中出现了2个固化峰. PPTL-FBOZ树脂具有较高的T5%(质量损失5%的温度)和800℃的残炭率,其极限氧指数(LOI)高达36. 2%,在垂直燃烧中达到V-0等级,表现出优异的热稳定性和阻燃性能.A novel bio-based benzoxazine resin(phenolphthalein-furfuramine-benzoxazine,PTL-F-BOZ),used bio-based furfurylamine,phenolphthalein,and paraformaldehyde as raw materials,was synthesized and characterized by Fourier transform infrared spectroscopy(FTIR),nuclear magnetic resonance(1 H NMR and13 C NMR). The curing, thermal and flame retardant properties were analyzed by differential scanning calorimetric(DSC),thermogravimetric analyzer(TG),limiting oxygen index(LOI),vertical burning test,microscale combustion calorimetry(MCC),cone calorimeter(Cone) and scanning electron microscope(SEM).The DSC curve of PTL-F-BOZ showed a two-stage curing with two maxima at 224 and 251 ℃ respectively,and had lower curing temperature than that of the traditional fossil-based bisphenol benzoxazine bisphenol A-aniline benzoxazine(bisphenol A-aniline-benzoxazine, BPA-A-BOZ). The presence of the furan ring in the furfurylamine increased the cross-linking density of polymer,retarded the rearrangement reaction from the phenoxy structure to the phenol structure,and resulted in two curing peaks in the DSC curve of PTL-F-BOZ. Under nitrogen and air atmospheres,the temperatures of 5% mass loss(T5%) for PPTL-F-BOZ resin were 380 and 370 ℃,respectively and the residual chars at 800 ℃ were 63. 0% and 10. 5%,respectively. Compared with PBPA-A-BOZ resin,PPTL-F-BOZ resin both possessed higher T5%and residual char of 800 ℃. From the DTG curve,the maximum mass loss rates of two decomposition stage(Peak 1 and Peak 2 values) of PPTL-FBOZ resin were 0. 67%/min and 3. 28%/min,which were only 7. 38% and 63. 44% of PBPA-A-BOZ(9. 07%/min and 5. 17%/min) under nitrogen atmosphere,and those were also the same under air atmosphere. LOI of PPTL-F-BOZ resin was 36. 2%,which was higher than that of PBPA-A-BOZ resin. Meanwhile,in the UL-94 test,PPTL-F-BOZ resin extinguished quickly and released less smoke during combustion process,and the original morphology was kept well and a stable carbon layer was formed after burning. Its first ignition time(t1) and sec

关 键 词：生物基苯并噁嗪 酚酞糠胺型苯并噁嗪树脂 固化反应 耐热性能 阻燃性能 

分 类 号：O631[理学—高分子化学]