【作者】 唐锐；

【导师】 王跃川；

【作者基本信息】 四川大学 ， 高分子材料， 2003， 硕士

【摘要】 本文是关于N—烷基马来酰亚胺（MI）的合成以及其作为光引发剂的应用研究。合成了六种N—烷基MI，考察了它们在丙烯酸酯类的光固化体系中，与树脂、单体以及光敏助剂的相互作用和影响；探索了MI对聚乙烯醇和聚苯乙烯树脂的紫外光辐射老化，以及MI的光反应产物对光固化涂层的光稳定性的影响。 尝试了四种合成MI的方法，其中二甲苯脱水一步反应的方法效果最好，所得MI纯度高，收率在25-55％。IR和¹HNMR表征了所合成六种MI的结构。测定了其紫外光谱、熔点以及折射率。 采用凝胶转化率曲线法和表干时间法，从MI的结构和浓度、活性稀释剂、助剂和树脂等方面对MI引发的光固化进行了研究。结果表明：光固化速度随着MI扩散能力的增加而增加，且与MI浓度的平方根呈线性关系。单官能活性稀释剂醋酸乙烯酯的自由基活性低，不利于光固化。苯乙烯的紫外吸收峰将MI在212和232cm^-1的两个主要吸收峰掩盖，使得MI不能有效的引发反应。双官能活性稀释剂1，6己二醇二丙烯酸（HDDA）比三羟甲基丙烷三丙烯酸酯（TPGDA）更有利于光固化。叔胺能敏化MI，提高MI的引发效率，从而提高光固化速度。其中甲基二乙醇胺的敏化作用最强，二乙醇胺次之，三乙胺最低。含丙烯酸酯的叔胺在低浓度时，对光固化有一定促进作用。氯乙酸及氯乙酸乙酯能通过链转移的方式有效地提高光固化速度，且光固化速度随浓度增加而增加。乙烯基醚在低浓度下也能提高光固化速度。以MI为光引发剂时，脂肪族丙烯酸酯树脂的光固化速度比丙烯酸化环氧树脂的快，且与MI的结构有关。 研究了MI及其反应产物对聚合物光稳定性的影响。结果表明：经相同辐照时间后，加入MI的PVA-1799和PVA-1788的分子量及分子量分布的变化比没有加MI的要小；MI的加入对PS影响较小。MI的光反应产物延长了脂肪族丙烯酸酯树脂固化膜的开裂时间。对于脂肪族丙烯酸酯树脂／丙烯酸酯环氧树脂（2／1）的固化膜，含MI光反应产物的固化膜颜色变化比不含的低一级，同时MI的加入对于固化膜硬度和热稳定性影响较小。更多还原

【Abstract】 This work is about the syntheses of N-alkyl maleimides and their applications as photoinitiators for photo polymerization and photo curing. Four synthesis methods for N-alkyl maleimides were compared. Among them the method using xylene to dehydrate by one-step reaction was found to be the best. Six N-alkyl maleimides were prepared with yield from 25% to 55% by this method. The structures and properties of these Mis were characterized by FTIR, 1H-NMR, UV spectra, melting point and refractive index.The effects of MI structure and concentration, reactive diluents, additives and resins on photo curing initiated by MI were studied by the gel conversion and photo-curing rate. The results showed that the photo-curing rate was proportional to the square root of Mi’s concentration. Vinyl acetate was not a reactive mono-functional diluent for the photo curing of difunctional acrylic aliphatic polyurethane initiated by MI. As the electronic absorption of Styrene covered the main range of absorbencies of MI in UV spectra, MI cannot initiate the photo polymerization for the system containing styrene. Compared with TPGDA, HDDA was found more reactive for the photo curing of acrylic aliphatic polyurethane. The photo curing was sensitized by tertiary amines. The effects of sensitization was found in the order: methyl diethanol amine > dimethyl ethanol amine > triethyl amine. At low concentration, the acrylate containing tertiary amine group can also enhance the photo curing reaction. Chloroacetic acid and ethyl chloroacetate were also found effective in increasing the photo-curing rate. Vinyl ether monomers* can also increase the photo-curing rate when their concentration was at relatively low level. The aliphatic difunctional acylated polyurethane was found more reactive than difunctional acrylated epoxy resin toward the photo initiation of MI.The effects of MI on the photo stability and ageing of PVA, PS and photo-curedfilm containing MI component were studied. The results showed that the molecular weight and their distribution of PVA-1788 and PS were not changed greatly by UV irradiation after addition of MI, while for PVA-1799, molecular weight increased after irradiation. MI also improved the anti-cracking and minimized the color changes of the cured film in the photo ageing experiments. At the same time, MI had little effect on the hardness and thermal stability of the cued film.更多还原