【作者】 于法暖；

【导师】 冯柏成；

【作者基本信息】 青岛科技大学 ， 化学工艺， 2010， 硕士

【摘要】 通过分析内酰胺的结构特征,根据原料来源及合成的难易程度本文筛选出丁内酰胺、戊内酰胺、己内酰胺和庚内酰胺四个内酰胺化合物。分别以环戊酮和环庚酮和盐酸羟胺反应合成相应的酮肟,然后和20%的发烟硫酸进行Beckmann重排合成了戊内酰胺和庚内酰胺,两步总收率分别为81%和77.5%,并且对影响反应的因素进行了讨论。四个内酰胺和S2Cl2分别进行缩合反应合成了相应的内酰胺二硫化物,此工艺的特征是以过量的内酰胺作为缚酸剂,避免了吡啶等其它缚酸剂对产品的污染,适合工业化生产。采用正交和单因素实验的方法获得了合成己内酰胺二硫化物(CLD)最优反应条件如下:反应温度60℃,己内酰胺和S2Cl2的摩尔比为5:1,反应时间2.5小时,使用碳11(高沸点烷烃)作为溶剂,后处理工艺简单,产品收率89.2%,较文献值高,乙酸乙酯重结晶后熔点129~130℃,液相色谱纯度大于99%。为了降低生产成本,设计了己内酰胺的回收工艺并对其循环利用进行了讨论。本文中相关的化合物均使用GC、HPLC进行了定量分析,使用了IR、1H NMR、GC-MS及LC-MS等进行了结构表征。用DTDM、丁内酰胺二硫化物(BLD)和CLD改变或部分改变天然橡胶NR和丁基橡胶IIR的配方中硫磺用量,在不同硫化温度下硫化并测试了老化前后的力学性能。BLD和CLD能够代替DTDM,并提高硫化胶的焦烧安全性和改善抗硫化返原能力。更多还原

【Abstract】 It is an object of this paper to provide a commercially feasible and economical process for producing nitrosamine-free lactam disulfide which has an application as sulfur donor in rubber vulcanization. According to the structure design, lactams were selected as the starting materials for the preparation of lactam disulfides. Due to the ease of synthesis and availability four lactams were screened and two of four lactams,γ-velerolactam andω-heptanolactam, were prepared firstly conversing cyclopentanone and cycloheptanone with hydroxylamine hydrochloride into cyclopentanone oxime and cycloheptanone oxime, then implying the Beckmann rearrangement of oxime with 20% oleum, in 81% and 77.5% overall yield, respectively. An improved process for preparation of lactam disulfides was investigated. It was charactered that excess of caprolactam was implied as acid acceptor so as to expel the contamination of other kinds of acid acceptor. Especially for the caprolactam disulfide, the optimum reaction conditions through orthogonal experiments were obtained as follows: the temperature 60℃, the mole ratio of caprolactam: S2Cl2 5:1, the reaction time 2.5h, under the conditions the reaction of caprolactam and S2Cl2 was carry out in a solvent of carbon 11(a high boiling point petroleum) and caprolactam disulfide was obtained with easy workup in 89.2% yield, recrystallized from ethyl acetate with a 129~130℃melting point and with HPLC purity more than 99%. For the purpose of lower cost, the process for recycling caprolactam hydrochloride was designed. The purity of related compounds were determined by GC or HPLC, structures confirmed by IR, 1H NMR and GC-MS, LC-MS.By addition of BLD, CLD and DTDM as sulfur donor to NR and IIR, the curing behaviour and the properties of vulcanizate before and after aging were investigated. DTDM can be substituted by BLD and CLD to improve the scorch safety and reversion resistance.更多还原