【作者】 赵庆来；

【导师】 杨刚；

【作者基本信息】 四川大学 ， 材料学， 2007， 硕士

【摘要】 含马来酰亚胺和烯丙基醚苯并嗯嗪中间体是由马来酰亚胺化合物、烯丙基醚化合物与多聚甲醛脱水缩合反应而成。研究该化合物的合成及固化性能的原因是它的分子结构中含有马来酰亚胺、烯丙基醚和噁嗪环三类活性反应官能基团，自身可以作为高性能树脂基体，还可以作为低分子量的改性剂。本文首先对烯丙氧基苯胺类化合物的合成进行了探索。在实验中，我们详细研究了各种合成条件对产率的影响，发现邻位、对位烯丙氧基苯胺采用由邻硝基酚、对硝基酚为初始原料接烯丙基的合成路线，然后经过硝基还原得到苯胺类单体，这是一条经济合理的合成反应路线；而间烯丙氧基苯胺则可由间氨基酚为原料采用氨基保护/解保护路线得到。以自制的N-（4-羟基苯基）马来酰亚胺（4-HPM）为酚源，苯胺和4-烯丙氧基苯胺为胺源，合成了马来酰亚胺苯并噁嗪中间体3-苯基-3,4-二氢-（N-马来酰亚胺）-1，3-苯并噁嗪（MIB）和3-（4-烯丙氧基）苯基-3,4-二氢-6-（N-马来酰亚胺）-1，3-苯并噁嗪（AMB），利用傅立叶红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）、元素分析（EA）等对产物进行了表征。实验发现MIB和AMB可溶于丙酮、甲醇、氯仿、四氢呋喃等普通有机溶剂，AMB熔点129.5℃。用差示扫描量热分析（DSC）和热失重分析（TGA）技术对AMB和MIB的热聚合行为进行了比较研究，结果表明，马来酰亚胺引入噁嗪化合物后可以明显提高聚合产物的热性能；烯丙基醚官能团引入后的AMB比MIB的熔点更低，且使传统噁嗪化合物的热性能得到非常显著的提高；AMB可以在更低的温度下聚合（150～200℃），在150℃的热处理可以明显降低预聚物的固化反应温度，且热处理后的产物T₅（5%热失重温度）为449℃，800℃下残碳率达到65%。此外，AMB存在有三种不同的固化机理，烯丙基醚的Claisen重排反应、烯丙基和马来酰亚胺基团发生ene反应与嗯嗪环固化反应，三种反应的放热峰发生了重叠；烯丙基醚Claisen重排后生成的酚羟基对噁嗪开环聚合反应起了催化促进作用。通过非等温DSC法对AMB自催化固化行为进行了分析。采用Kissinger方程和差减微分法分析了在升温速度为5℃～20℃/min之间的AMB非等温固化行为。差减微分法表明，固化反应活化能和反应级数随着升温速度的增大而减小。更多还原

【Abstract】 Benzoxazine with maleimde and allyloxy groups is synthesized by the reaction of allyloxy compounds, maleimide compounds and peraformaldehyde. The reason to research it is that there are three kinds of reactive functional groups, maleimide, allyloxy and benzoxazine ring in its molecular structure. In practice, it can be used as high-performance resin matrix, as well as a low molecular weight modifier.Firstly, this paper has probed into the synthesis of allyloxy aniline compounds. During the experiment, we have carefully researched the synthetic conditions’ influence on the final rate of production. Two ways of synthesizing of 2-allyloxyaniline and 4-allyloxyaniline are given and compared, the aniline protection / deprotection way and the reduction of nitro group from nitro-phenol as initial raw material. The result shows the latter one is better. It is suitable to synthesize 3-allyloxyaniline for the former.Two benzoxazines, compounded with maleimide group, 3-phenyl-3, 4-dihydro-2H-6- （N-maleimido）-1, 3-benzoxazine（MIB）, 3-（4-allyloxy）phenyl-3, 4-dihydro-2H-6-（N-maleimido）-1, 3-benzoxazine（AMB）, were synthesized from N-（4-hydroxyphenyl） maleimide, paraformaldehyde, aniline and 4-（allyloxy）-benzene amine. Structures of AMB were confirmed by FT-IR and ¹H NMR as well as elemental analysis. MIB and AMB were found to readily soluble in common organic solvents, such as acetone, methanol, chloroform, tetrahydrofuran et al. The only minor difference in structure between them is that AMB has a flexible and thermally reactive allyloxy group in molecular structure. AMB have a melting point of 129.5℃. Using differential scanning calorimeter （DSC） and thermogravimetric analysis （TGA） technology, thermal properties of AMB were studied comparing with that of MIB. It was found that, AMB could be cured at relatively lower temperatures （150～200℃）. After thermal self-polymerization of AMB at 150℃for 20 min., the product showed a five percent weight temperature（T₅） of 449℃and a char yield of 65% at 800℃respectively, much higher than that ofMIB （T₅: 375℃; char yield: 56% at 800℃）. In addition, AMB has three different kinds of curing mechanisms: the Claisen rearrangement reaction of allyoxy, the ene reaction of allyl and maleimide groups and curing reaction of benzoxazine ring. The three exothermic reactions overlap each other. The phenol hydroxy from Claisen rearrangement reaction of allyloxy catalyse the ring opening reaction of benzoxazine.The curing behaviors of AMB have been studied in details by non-isothermal and dynamic differential scanning calorimetry （DSC）. Kissinger equation and Freeman-Carroll equation has been introduced to deal with the data of DSC analysis. Freeman-Carroll equation shows that the activation energy and the order of the reaction decrease with the increase of calefactive speed.更多还原