苯基苯酚改性酚醛树脂的裂解性能研究

复合材料科学与工程 ›› 2014, Vol. 0 ›› Issue (10): 11-15.

苯基苯酚改性酚醛树脂的裂解性能研究

秦小婷, 刘育建^*, 张衍, 方俊

华东理工大学材料科学与工程学院,特种功能高分子材料及相关技术教育部重点实验室,上海200237

收稿日期:2014-04-10 出版日期:2014-10-28 发布日期:2021-09-16
通讯作者: 刘育建(1964-),男,硕士,副研究员,主要从事特种复合材料树脂基体研究,yjliu@ecust.edu.cn。
作者简介:秦小婷(1988-),女,硕士,主要从事耐高温树脂基体研。
基金资助:
国家自然科学基金资助项目(51303054);国家重点基础研究发展计划(973项目)(2013CB035505);上海市重点学科资助项目(B502)

STUDY ON THE PYROLYSIS PERFORMANCE OF PHENYL-PHENOL MODIFIED PHENOLIC RESIN

QIN Xiao-ting, LIU Yu-jian^*, ZHANG Yan, FANG Jun

Key Laboratory for Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, School of Materials Science and Engineering, Ecust China University of Science and Technology,Shanghai 200237,China

Received:2014-04-10 Online:2014-10-28 Published:2021-09-16

摘要/Abstract

摘要： 采用热重分析(TGA)、裂解气质联用(Py-GC-MS)和傅里叶变换红外光谱(FT-IR)等手段对苯基苯酚改性酚醛树脂的裂解机理进行了研究。结果表明,苯基苯酚改性酚醛树脂中的亚甲基反应活性较高,450℃条件下即开始断裂,同时亚甲基与酚羟基发生反应,产生酚类、苯环类及其甲基衍生物。在更高的温度下树脂发生结构重排形成蒽、菲类物质,并进一步发生脱氢炭化反应。裂解气质联用分析证明,在相同的裂解条件下,苯基苯酚改性酚醛树脂的裂解挥发份明显少于普通酚醛树脂。论文通过对树脂微观结构随温度演变的过程进行研究,对苯基苯酚改性酚醛树脂具有优良耐热性的根本原因进行了诠释。

关键词: 酚醛树脂, 裂解, 苯基苯酚, 机理

Abstract: The pyrolysis mechanism of the phenyl-phenol modified phenolic resin (PPR)is investigated by using thermogravimetic analysis (TGA), pyrolysis-gas chromatogram-mass spectrum (Py-GC-MS) and fourier transform infrared spectrum (FT-IR). The results indicate that methylene has higher activity than other groups in the resins, which tends to break and further react with phenolic hydroxyl, accompanying with the release of phenols, benzodiazepines and methyl derivatives at 450℃. At higher temperature,the structural rearrange reactions take place, and the structure transforms into anthracene, phenanthrene or amorphous carbon through further dehydrogenation coking reaction. According to the results of Py-GC-MS, the amount of volatile released from the phenyl-phenol modified PF is less than that from the ordinary PF under the same condition,which demonstrate better thermal stability of PPR.

Key words: phenolic resin, pyrolysis, phenyl-phenol , mechanism

中图分类号:

TB332

秦小婷, 刘育建, 张衍, 方俊. 苯基苯酚改性酚醛树脂的裂解性能研究[J]. 复合材料科学与工程, 2014, 0(10): 11-15.

QIN Xiao-ting, LIU Yu-jian, ZHANG Yan, FANG Jun. STUDY ON THE PYROLYSIS PERFORMANCE OF PHENYL-PHENOL MODIFIED PHENOLIC RESIN[J]. COMPOSITES SCIENCE AND ENGINEERING, 2014, 0(10): 11-15.

参考文献

[1] 黄发荣,焦杨声. 酚醛树脂及其应用[M]. 北京:化学工业出版社,2003.
[2] Knop A,Pilato L A. Phenolic Resins:Chemistry,Application and Performance,Future Directions[M]. Heidelberg:Springer,1985.
[3] Reghunadhan Nair C P,Bindu R L,Ninan K N. Thermal characteristics of addition-cure phenolic resins[J]. Polymer Degradation and Stability,2001,73(2):251.
[4] 朱永茂. 国外酚醛树脂及其塑料发展动向[J]. 热固性树脂,2003,18 (6):28-30.
[5] 刘晓蓓,王晓洁,惠雪梅. 耐高温环氧树脂研究进展[J]. 玻璃钢/复合材料,2013,(3):118-121.
[6] 宋超,刘胜平,徐世爱. 硼改性酚醛树脂固化反应动力学的研究[J]. 玻璃钢/复合材料,2010,(6):45-47.
[7] 茆凌峰,刘坐镇. 耐高温耐腐蚀酚醛环氧乙烯基酯树脂[J]. 玻璃钢/复合材料,2012,(2):64-66.
[8] 蒋海云. 酚醛树脂高温结构、性能演变特性及耐热改性研究[D]. 南京:东南大学,2010.
[9] Trick K A,Saliba T E. Mechanism of the pyrolysis of phenolic resin in carbon /phenolic composite [J]. Carbon,1995,33(11):1509-1515.
[10] 蒋海云,王继刚,等. 酚醛树脂的高温裂解色谱质谱分析[J]. 功能材料,2008,6(39):1024 - 1026.
[11] 张衍,刘育建,王井岗,等. 苯基苯酚型酚醛树脂中羟甲基邻/对位异构的核磁共振分析及性能影响[J]. 华东理工大学学报,2008,34(1):81-85.
[12] 张衍,王井岗,刘育建. 红外光谱对苯基苯酚改性酚醛树脂的研究[J]. 玻璃钢/复合材料,2003,(6):27-29.
[13] Bab H,Aizenshtat Z. Phenol-formaldehyde resins as a link to the understanding of the isothermal kinetic behavior of geopolimers (kerogens and coals) [J]. Journal of Analytical and Applied Pyrolysis,1991,19(7):265-277.
[14] 李琳,李步广,刘洪波,等. 酚醛树脂为原料制备双电层电容器用电极材料的工艺研究[J]. 炭素技术,2004, 23(4):1-6.
[15] Wang J G,Jiang H Y,Jiang N. Study on the pyrolysis of phenol-formaldehyde(PF) resin and modified PF resin[J]. Thermochemical Acta,2009,496(1-2):136-142.