一种新型苯并噁嗪的合成及其固化行为的研究
摘要
本文综述了苯并噁嗪树脂的研究进展,针对苯并噁嗪树脂的固化温度高、交联密度低及韧性差等缺点,设计出一种新型的同时含有马来酰亚胺和羧基的苯并噁嗪,采用共混改性的方法,制备出加工温度低的高性能树脂。
以自制的HPM为原料,采用溶液法合成了具有新结构的苯并噁嗪单体3-(4-羧基)苯基-3,4-二氢-6-(N-马来酰亚胺)-1,3-苯并噁嗪(Mal-Bz-Co),并对它的合成条件及提纯进行了探讨。通过研究最终选用异丙醇为溶剂进行Mal-Bz-Co的合成,其产率高,产物纯度高,并发现合成产物中主要杂质为三嗪中间体及未完全反应的反应物,通过溶解性试验找到了以异丙醇和二氧六环两种溶剂对粗产物进行了分离和提纯的新方法,得到了较为纯净的Mal-Bz-Co,并用核磁及红外检测方法确认了它的结构。
通过DSC法对Mal-Bz-Co的固化行为及其与两种环氧树脂共混物的固化行为进行了研究。结果发现Mal-Bz-Co的固化温度仍然较高,其固化峰值温度为238.3℃，但其与双酚A酚醛环氧树脂(DGEBA)、邻甲酚醛环氧树脂(o-CFER)共混后却具有很低的固化温度,其中Mal-Bz-Co/o-CFER(1:2)和Mal-Bz-Co/DGEBA(1:2)两种共混体系的固化峰值温度分别为148.6℃和141.3℃,其固化温度远低于纯Mal-Bz-Co的固化温度,在目前所研究的苯并噁嗪与环氧树脂共混体系中如此低的固化温度还鲜有报道。通过对不同配比的Mal-Bz-Co与o-CFER共混物的固化行为进行研究,发现当Mal-Bz-Co与o-CFER的配比为1：1时,共混物的固化温度较低,其固化峰值温度为141.5℃。
通过TGA测量了Mal-Bz-Co树脂及Mal-Bz-Co/o-CFER树脂的热性能,结果表明：Mal-Bz-Co的固化产物降解10%的温度为371℃,800℃的残碳率为45%,Mal-Bz-Co/o-CFER(1:1)的固化产物降解10%的温度为380℃,800℃的残碳率为43.4%。这些数据表明Mal-Bz-Co树脂及其与环氧树脂的共混树脂具有优良的热性能。此外,Mal-Bz-Co与环氧树脂共聚物的初始降解温度较纯Mal-Bz-Co树脂有所提高,表明环氧树脂的引入提高了Mal-Bz-Co的交联密度,改善了其热性能。
以上研究表明,所合成的新结构苯并噁嗪与环氧树脂共混后具有很低的固化温度,其较低的加工温度及其优良的热性能预示了它良好的应用前景。
In this paper, the progress of benzoxazine resin was reviewed. Aiming at the disadvantages of benzoxazine resin such as high curing temperature、low crosslink densities and poor toughness, a novel benzoxazine containing maleimide and carboxyl moieties was synthesized. Furthermore, blending modification was used in the research and high performance resin with low processing temperature was obtained.
The novel benzoxazine 1-[3-(4-carboxylphenyl)-3,4-dihydro-2H-benzo[e][1,3]-oxazin-6-yl] maleimide (Mal-Bz-Co) was synthesized by solution method with self-made HPM as raw material, and the synthesized condition and purification was researched. By the research, isopropanol was selected to synthesis Mal-Bz-Co, which showed high yield and high purity of the products. And the research showed that main impurity in the primary products was triazine intermediate and un-reacted reagents. A new separation and purification method used isopropanol and dioxane was found by solubility test. The structure of Mal-Bz-Co was characterized with Fourier transform infrared spectra (FTIR) and Proton nuclear magnetic resonance spectra (1H NMR).
The curing behavior of Mal-Bz-Co and the cocuring behavior of Mal-Bz-Co with two kind of epoxy resins were researched by Differential scanning calorimetry (DSC). The results showed that the curing temperature of Mal-Bz-Co was still high and the maximum curing temperature (Tp) was 238.3℃. However, the curing temperature of Mal-Bz-Co becomes very low when cocured with o-Cresol formaldehyde epoxy resin (o-CFER) or Diglycidyl ether of bisphenol A (DGEBA). The Tp of Mal-Bz-Co/o-CFER (1:2) and Mal-Bz-Co/DGEBA (1:1) were 148.6℃and 141.3℃respectively, which were not only much lower than that of pure Mal-Bz-Co, but also much lower than that of the reported benzoxazine/epoxy system. The effect of the ratio of Mal-Bz-Co and o-CFER on the curing behavior was researched in this paper. And the results showed that the curing temperature of the blending system was relative low (Tp about 141.5℃) when the ratio of Mal-Bz-Co and o-CFER was 1:1.
The thermal properties of pure Mal-Bz-Co resin and Mal-Bz-Co/o-CFER resin was researched by Thermogravimetric analysis (TGA). The results showed that T10 (degradation temperature of loss 10wt%) of pure Mal-Bz-Co resin was 371℃and Yc (char yield at 800) of pure Mal-Bz-Co resin was 45%. And T10 and Yc of Mal-Bz-Co/o-CFER (1:1) resin were 380℃and 43.4% respectively. The TGA results indicated good thermal properties of pure Mal-Bz-Co resin and Mal-Bz-Co/o-CFER resin. Additionally, the higher initial degradation temperature of Mal-Bz-Co/o-CFER than pure Mal-Bz-Co resin indicated that the addition of epoxy could increase the crosslink density and improve the thermal property.
The research showed that the curing temperature of the novel benzoxazine/epoxy blend was very low. The low processing temperature and the excellent thermal property indicated its good application prospect.
以自制的HPM为原料,采用溶液法合成了具有新结构的苯并噁嗪单体3-(4-羧基)苯基-3,4-二氢-6-(N-马来酰亚胺)-1,3-苯并噁嗪(Mal-Bz-Co),并对它的合成条件及提纯进行了探讨。通过研究最终选用异丙醇为溶剂进行Mal-Bz-Co的合成,其产率高,产物纯度高,并发现合成产物中主要杂质为三嗪中间体及未完全反应的反应物,通过溶解性试验找到了以异丙醇和二氧六环两种溶剂对粗产物进行了分离和提纯的新方法,得到了较为纯净的Mal-Bz-Co,并用核磁及红外检测方法确认了它的结构。
通过DSC法对Mal-Bz-Co的固化行为及其与两种环氧树脂共混物的固化行为进行了研究。结果发现Mal-Bz-Co的固化温度仍然较高,其固化峰值温度为238.3℃，但其与双酚A酚醛环氧树脂(DGEBA)、邻甲酚醛环氧树脂(o-CFER)共混后却具有很低的固化温度,其中Mal-Bz-Co/o-CFER(1:2)和Mal-Bz-Co/DGEBA(1:2)两种共混体系的固化峰值温度分别为148.6℃和141.3℃,其固化温度远低于纯Mal-Bz-Co的固化温度,在目前所研究的苯并噁嗪与环氧树脂共混体系中如此低的固化温度还鲜有报道。通过对不同配比的Mal-Bz-Co与o-CFER共混物的固化行为进行研究,发现当Mal-Bz-Co与o-CFER的配比为1：1时,共混物的固化温度较低,其固化峰值温度为141.5℃。
通过TGA测量了Mal-Bz-Co树脂及Mal-Bz-Co/o-CFER树脂的热性能,结果表明：Mal-Bz-Co的固化产物降解10%的温度为371℃,800℃的残碳率为45%,Mal-Bz-Co/o-CFER(1:1)的固化产物降解10%的温度为380℃,800℃的残碳率为43.4%。这些数据表明Mal-Bz-Co树脂及其与环氧树脂的共混树脂具有优良的热性能。此外,Mal-Bz-Co与环氧树脂共聚物的初始降解温度较纯Mal-Bz-Co树脂有所提高,表明环氧树脂的引入提高了Mal-Bz-Co的交联密度,改善了其热性能。
以上研究表明,所合成的新结构苯并噁嗪与环氧树脂共混后具有很低的固化温度,其较低的加工温度及其优良的热性能预示了它良好的应用前景。
In this paper, the progress of benzoxazine resin was reviewed. Aiming at the disadvantages of benzoxazine resin such as high curing temperature、low crosslink densities and poor toughness, a novel benzoxazine containing maleimide and carboxyl moieties was synthesized. Furthermore, blending modification was used in the research and high performance resin with low processing temperature was obtained.
The novel benzoxazine 1-[3-(4-carboxylphenyl)-3,4-dihydro-2H-benzo[e][1,3]-oxazin-6-yl] maleimide (Mal-Bz-Co) was synthesized by solution method with self-made HPM as raw material, and the synthesized condition and purification was researched. By the research, isopropanol was selected to synthesis Mal-Bz-Co, which showed high yield and high purity of the products. And the research showed that main impurity in the primary products was triazine intermediate and un-reacted reagents. A new separation and purification method used isopropanol and dioxane was found by solubility test. The structure of Mal-Bz-Co was characterized with Fourier transform infrared spectra (FTIR) and Proton nuclear magnetic resonance spectra (1H NMR).
The curing behavior of Mal-Bz-Co and the cocuring behavior of Mal-Bz-Co with two kind of epoxy resins were researched by Differential scanning calorimetry (DSC). The results showed that the curing temperature of Mal-Bz-Co was still high and the maximum curing temperature (Tp) was 238.3℃. However, the curing temperature of Mal-Bz-Co becomes very low when cocured with o-Cresol formaldehyde epoxy resin (o-CFER) or Diglycidyl ether of bisphenol A (DGEBA). The Tp of Mal-Bz-Co/o-CFER (1:2) and Mal-Bz-Co/DGEBA (1:1) were 148.6℃and 141.3℃respectively, which were not only much lower than that of pure Mal-Bz-Co, but also much lower than that of the reported benzoxazine/epoxy system. The effect of the ratio of Mal-Bz-Co and o-CFER on the curing behavior was researched in this paper. And the results showed that the curing temperature of the blending system was relative low (Tp about 141.5℃) when the ratio of Mal-Bz-Co and o-CFER was 1:1.
The thermal properties of pure Mal-Bz-Co resin and Mal-Bz-Co/o-CFER resin was researched by Thermogravimetric analysis (TGA). The results showed that T10 (degradation temperature of loss 10wt%) of pure Mal-Bz-Co resin was 371℃and Yc (char yield at 800) of pure Mal-Bz-Co resin was 45%. And T10 and Yc of Mal-Bz-Co/o-CFER (1:1) resin were 380℃and 43.4% respectively. The TGA results indicated good thermal properties of pure Mal-Bz-Co resin and Mal-Bz-Co/o-CFER resin. Additionally, the higher initial degradation temperature of Mal-Bz-Co/o-CFER than pure Mal-Bz-Co resin indicated that the addition of epoxy could increase the crosslink density and improve the thermal property.
The research showed that the curing temperature of the novel benzoxazine/epoxy blend was very low. The low processing temperature and the excellent thermal property indicated its good application prospect.
引文
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