以对氨基苯丙炔醚(APPE)、炔丙胺与苯酚、双酚A、间甲酚和多聚甲醛在无溶剂下通过Mannich反应合成了5种含炔丙基型苯并噁嗪，并对5种含炔丙基型苯并噁嗪及其固化树脂分别进行了结构表征和热稳定性测试。结果表明：室温下粘度较小的树脂有更宽的加工窗口，炔丙基醚型苯并噁嗪比N-炔丙基型苯并噁嗪的固化温度高，噁嗪环开环的同时炔丙基发生了交联。炔丙基醚型聚苯并噁嗪比N-炔丙基型聚苯并噁嗪有更好的热稳定性，聚苯并噁嗪树脂的裂解挥发分主要是苯酚及甲基衍生物。
Five kinds of benzoxazine precursor containing propargyl group(P-appe、B-appe、P-pla、B-pla and M-pla) were synthesized by Mannich condensation reaction among p-aminophenyl propargyl ether(appe) or propargylamine, phenol or bisphenol A or m-cresol and paraformaldehyde without solvent, and the struc-ture of the five kinds of benzoxazine were characterized and the thermal stability of their curing resin tested were tested. The results show that the benzoxazine resin with low viscosity has wider processing window. The curing temperature of the benzoxazine containing propargyl ether is higher than that of the benzoxazine containing N-propargyl. The ring-opening polymerization of benzoxazine and cross-linking reac-tion of the propargyl groups take place simultaneously. The polybenzoxazine containing propargyl ether shows better thermal stability than polybenzoxazine containing N-propargyl. The thermal decomposition products of the polybenzoxazine resin are mainly phenol and its derivatives.
参考文献
| [1] | Baris Kiskan;Narendra Nath Ghosh;Yusuf Yagci .Polybenzoxazine-based composites as high-performance materials[J].Polymer international,2011(2):167-177. |
| [2] | Hyun Jin Kim;Zdenka Brunovska;Hatsuo Ishida .Molecular characterization of the polymerization of acetylene-functional benzoxazine resins[J].Polymer: The International Journal for the Science and Technology of Polymers,1999(7):1815-1822. |
| [3] | H. J. Kim;Z. Brunovska;H. Ishida .Synthesis and thermal characterization of polybenzoxazines based on acetylene-functional monomers[J].Polymer: The International Journal for the Science and Technology of Polymers,1999(23):6565-6573. |
| [4] | 顾宜.苯并噁嗪树脂--一类新型热固性工程塑料[J].热固性树脂,2002(02):31-34,39. |
| [5] | Tarek Agag;Tsutomu Takeichi .Novel Benzoxazine Monomers Containing p-Phenyl Propargyl Ether: Polymerization of Monomers and Properties of Polybenzoxazines[J].Macromolecules,2001(21):7257-7263. |
| [6] | Agag T.;Takeichi T. .Synthesis and characterization of novel benzoxazine monomers containing allyl groups and their high performance thermosets[J].Macromolecules,2003(16):6010-6017. |
| [7] | 余鼎声;徐日炜;丁雪佳 等.含N-烯丙基的苯并噁嗪中间体和组合物及其制备方法[P].中国,l472205A,2004-02-04. |
| [8] | 郭颖,顾奕,袁荞龙,黄发荣.低粘度苯并（噁）嗪树脂的制备与固化[J].绝缘材料,2011(02):13-16. |
| [9] | Baris Kiskan;Yusuf Yagci .Synthesis and characterization of thermally curable polyacetylenes by polymerization of propargyl benzoxazine using rhodium catalyst[J].Polymer: The International Journal for the Science and Technology of Polymers,2008(10):2455-2460. |
| [10] | Ishida H .Process for Preparation of Benzoxazine Com-pounds in Solventless Systems[P].US,5543516,1996-08-06. |
| [11] | Agag, T.;Geiger, S.;Alhassan, S.M.;Qutubuddin, S.;Ishida, H. .Low-viscosity polyether-based main-chain benzoxazine polymers: Precursors for flexible thermosetting polymers[J].Macromolecules,2010(17):7122-7127. |
| [12] | Hemvichian, K;Kim, HD;Ishida, H .Identification of volatile products and determination of thermal degradation mechanisms of polybenzoxazine model oligomers by GC-MS[J].Polymer Degradation and Stability,2005(2):213-224. |
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