高等学校化学学报

高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (7): 1794.doi: 10.7503/cjcu20120981

• 高分子化学 • 上一篇    

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

张文利1, 朱春莉1, 王登霞2, 姚丙建1, 李晓娜1, 鲁在君1   

  1. 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
  • 收稿日期:2012-10-30 出版日期:2013-07-10 发布日期:2013-06-21
  • 通讯作者: 鲁在君, 男, 教授, 主要从事苯并噁嗪复合材料及阴离子聚合研究. E-mail: z.lu@sdu.edu.cn E-mail:z.lu@sdu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 21074067)资助.

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

ZHANG Wen-Li1, ZHU Chun-Li1, WANG Deng-Xia2, YAO Bing-Jian1, LI Xiao-Na1, LU Zai-Jun1   

  1. 1. Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China;
    2. Fifty-three Institute of China North Industries Group Corporation, Jinan 250031, China
  • Received:2012-10-30 Online:2013-07-10 Published:2013-06-21
  • Contact: Zaijun LU E-mail:z.lu@sdu.edu.cn

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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.

关键词: 苯并噁嗪, 甲基丙烯酰氯, N-苯基马来酰亚胺, 热性能

Abstract:

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.

Key words: Benzoxazine, Methacryloyl chloride, N-Phenylmaleimide, Thermal property

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