6-甲基-3-甲基丙烯酰氧乙基-3，4-2H-1，3-苯并噁嗪及其共聚物的合成  

Synthesis of 6-Methyl-3-methacryloxyethyl-3,4-dihydro-2H-benzo[e][1,3]oxazine and Its Copolymer

作　　者：张文利[1] 朱春莉[1] 王登霞[2] 姚丙建[1] 李晓娜[1] 鲁在君[1] 

机构地区：[1]山东大学化学与化工学院,特种功能聚集体材料教育部重点实验室,济南250100 [2]中国兵器工业集团第五三研究所,济南250031

出　　处：《高等学校化学学报》2013年第7期1794-1800,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21074067)资助

摘　　要：以6-甲基-3-羟乙基-3,4-2H-1,3-苯并噁嗪(MB-OH)和甲基丙烯酰氯为原料,通过酯化反应合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪(MBEM).采用自由基溶液聚合法,以偶氮二异丁腈(AIBN)为引发剂,以甲苯为溶剂,以MBEM与N-苯基马来酰亚胺(NPMI)为单体,合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪-co-N-苯基马来酰亚胺共聚物[P(MBEM-co-NPMI)].分别对MB-OH,MBEM,P(MBEM-co-NPMI)进行加热固化,得到相应的交联聚合物PMB-OH,PMBEM和P[P(MBEM-co-NPMI)].对其结构、分子量和热性能进行了表征.结果表明,PMB-OH,PMBEM,P[P(MBEM-co-NPMI)]的最大损耗因子tanδmax对应的玻璃化转变温度(Tg)分别为92,129和181℃,最大损耗模量G″max对应的Tg分别为56,91和156℃.在N2气氛围下,PMB-OH,PMBEM,P[P(MBEM-co-NPMI)]失重5%的温度分别为257,244和260℃;失重10%的温度分别为280,266和284℃;800℃的残炭率分别为23.2%,17.8%和14.0%.表明P[P(MBEM-co-NPMI)]具有优异的耐热性能.6-Methyl-3-methacryloxyethyl-3,4-dihydro-2H-benzo[e][1,3]oxazine（MEBM） was synthesized by simple esterification reaction of 2-（6-methyl-4H-benzo[e][1,3]oxazin-3-yl）-ethanol（MB-OH） with methacryloyl chloride. MBEM/N-Phenylmaleimide copolymer[P（MBEM-co-NPMI）] was synthesized with N-phenylmaleimide（NPMI） and MBEM by free radical solution polymerization using azodiisobutyronitrile（AIBN） as initiator and toluene as solvent. The corresponding polymers of PMB-OH, PMBEM and P[P（MBEM-co-NPMI）] were obtained by thermal cross-linking of MB-OH, MBEM and P（MBEM-co-NPMI）, respectively. The molecular weight of the resulting copolymer was determined by gel permeation chromatography（GPC）. The structure and chemical composition of MBEM and P（MBEM-co-NPMI） were characterized by Fourier transform infrared spectroscopy（FTIR） and nuclear magnetic resonance spectroscopy（1H NMR, 13C NMR）. The curing behavior of all substances was also studied by differential scanning calorimetry（DSC） and FTIR. Thermal properties of the cross-linking polymers of PMB-OH, PMBEM and P[P（MBEM-co-NPMI）] were investigated by dynamic mechanical analysis（DMA） and thermal gravime-tric analysis（TGA）. The results show that the temperatures in maximum loss factor of the cross-linking polymers of PMB-OH, PMBEM, and P[P（MBEM-co-NPMI）] are 92, 129, and 181℃, respectively. The temperatures in maximum loss modulus of the cross-linking polymers of PMB-OH, PMBEM and P[P（MBEM-co-NPMI）] are 56, 91 and 156℃, respectively. Under N2, the temperatures of the cross-linking polymers of PMB-OH, PMBEM and P[P（MBEM-co-NPMI）] at 5% mass loss are 257, 244 and 260℃, respectively, and the temperatures at 10% mass loss are 280, 266, 284℃, respectively. Their ultimate char yields are 23.2%, 17.8% and 14.0% at 800℃, respectively. These results suggest that P[P（MBEM-co-NPMI）] has excellent heat resistant performance.

关 键 词：苯并噁嗪 甲基丙烯酰氯 N-苯基马来酰亚胺 热性能 

分 类 号：O631[理学—高分子化学]