为了提高苯并噁嗪的热稳定性,以对碘苯胺、3-氨基苯乙炔、苯酚及多聚甲醛为原料合成了新型的含炔基苯并噁嗪(PA-an-ba),并通过傅里叶变换红外光谱仪和核磁共振仪(1H-NMR,13C-NMR)对其结构进行表征,通过差示扫描量热仪和热重分析仪对其固化行为和热性能进行了测试。结果表明:炔基的引入能显著提高聚苯并噁嗪的耐热性,其失重率为5%和10%时的温度分别为437℃和464℃,800℃的残炭率为73%,比传统苯并噁嗪提高了40%。
In order to improve the thermal stability of benzoxazine,alkynyl-containing benzoxazine was synthesized from p-Iodoaniline,3-Aminophenylacetylene,phenol,paraformaldehyde and characterized by fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (1H-NMR,13C-NMR).The cure behavior and thermal stability of the benzoxazine with alkynyl groups were tested by differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA).The results showed that the thermal stability was improved significantly with the introducing alkynyl groups.The 5% and 10% decomposition temperatures were 437℃ and 464℃ respectively,and the char yield at 800℃ was as high as 73% under nitrogen environment which was 40% higher than traditional benzoxazine.
[1] Holly F W,Cope A C.Condensation products of aldehydes and ketones with o-aminobenzyl alcohol and o-hydroxybenzylamine[J].Journal of the American Chemical Society,1944,66(11):1875-1879.
[2] 曾明,王洛礼,刘景民.苯并噁嗪树脂的合成及应用[J].化工新型材料,2000,28(5):14.
[3] Ning X,Ishida H.Phenolic materials via ring-opening polymerization:symthesis and characterization of bisphenol-a based benzoxazines and their polymers[J].Journal of Polymer Science,Part A:Polymer Chemistry,1994,32:1121-1129.
[4] Ishida H,Houglas I A.Physical and mechanical characterization of near-zero shrinkage polybenzoxazines[J].Journal of Polymer Science:Part B,1996,34:1019-1030.
[5] Ishida H,Hong Y L.A study on the volumetric expansion of benzoxazine-based phenolic resin[J].Macromolecular,1997,30:1099-1106.
[6] 朱国敏,沈学宁,黄发荣.二乙烯基硅氧烷-双苯并环丁烯树脂的制备与性能研究[J].玻璃钢/复合材料,2005,34(4):16-19.
[7] 虞莲雯,王耀先,陈兴旺.改性双马来酞亚胺-氰酸酷树脂固化工艺的研究[J].玻璃钢/复合材料,2008,37(2):35-37.
[8] Zhang Y,Gao J,Shen X,et al.The preparation,characterization,and cure reactions of new bisbenzocyclobutene-terminated aromatic imides[J].Journal of Applied Polymer Science,2006,99(4):1705-1719.
[9] 张飞,牛慧君,赵立波,等.RTM用苯并噁嗪树脂基碳纤维复合材料的性能研究[J].化工新型材料,2011,39(11):60.
[10] 杜学峰,莫越奇.高性能苯并噁嗪基复合材料研究进展[J].化工新型材料,2007,35(9):32.
[11] Jin L,Agag T,Ishida H.Bis(benzoxzine-maleimide)s as a novel class of high performance resin:synthesis and properties[J].European Polymer Journal,2010,46:354-363.
[12] Liu Y L,Chou C I.High performent benzoxazine monomers and polymers containing furan group[J].Journal of Polymer Science:Part A:Polymer Chemistry,2005,43:5267-5282.
[13] Wang H,Wang J,Liu W B,et al.Synthesis of novel furan-containing tetrafunctional fluorine-based benzoxazine monomer and its high performance thermoset[J].RSC Advances,2014,4:64798.
[14] Chang H C,Lin C H,Tian Y W,et al.Synthesis of 9,9-bis(4-aminopheny ) fluorine-based benzoxazine and properties of its high-performance thermoset[J].Polymer Chemistry,2012,50:2201-2210.
[15] Zhang K,Zhuang Q X,Zhou Y C,et al.Preparation and properties of novel low dielectric constant benzoxazole-based polybenzoxazine[J].Polymer Chemistry,2012,50:5115-5123.
[16] Wu J Y.Mohamed M G,Kuo S W.Directly synthesized nitrogen-doped microporous carbons from polybenzoxazine resins for carbon dioxide capture[J].Polymer Chemistry,2017,8:5481.
[17] 潘光艳,任浩,齐汇民,等.氰基苯并噁嗪/环氧树脂共混体系的性能研究[J].化工新型材料,2008,36(11):81.
[18] Ran Q C,Tian Q,Li C,et al.Investigation of processing,thermal,and mechanical properties of a new composite matrix-benzoxazine containing aldehyde group[J].Polymers Advanced Technologies,2010,21:170-176.
[19] Xu Y,Ran Q C,Li C,et al.Study on the catalytic prepolymerization of an acetylene-functional benzoxazine and the thermal degradation of its cured product[J].RSC Advances,2015,5:82429.
[20] Kim H J,Brunovska Z,Ishida H.Molecular characterization of the polymerization of acetylene-functional benzoxazine resins[J].Polymer,1999,40:1815-1822.
基金资助
四川省高等学校油气田材料重点实验室资助项目(X151517KCL12);西南石油大学科研启航项目(2015QHZ017)
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