一种新催化剂的丁腈橡胶加氢动力学研究及丁腈橡胶乳液加氢的探索

【作者】 张云云；

【导师】 徐瑞清；

【作者基本信息】 北京化工大学 ， 材料学， 2000， 硕士

【摘要】 HNBR是耐热、耐老化、耐H₂S等综合性能优异的耐油橡胶。HNBR的市场需求量随着油田开采和汽车工业的发展在逐年增加。HNBR生产在国内尚属空白，急待开发。 本文首次以Rh-Ru双金属催化剂对NBR进行溶液均相加氢动力学研究，从加氢动力学数据求得各因素相应的反应级数和加氢速率常数k，导出该催化剂在115℃～145℃对NBR溶液均相加氢速率方程： -d[C=C]／dt=k[C=C]^1.68[P_H2]^1.07[Rh-Ru]^1.30 并求得相应的加氢反应活化能为13.68kJ／mol。同时研究了该催化剂对NBR均相加氢过程中工艺条件的影响，并求得较佳的工艺条件为：NBR浓度：7（g／100ml），催化剂浓度0.25％（干胶重），催化剂：配体L₂=1：6（Wt），氢气压力1.4MPa，温度145℃。 本文还分别以RhCl（PPh₃）₃和RuCl₂（PPh₃）₃为催化剂，在共溶剂条件下，初步考察了NBR乳液加氢的主要因素对加氢反应的影响，得到如下工艺条件： RhCl（PPh₃）₃为催化剂的NBR乳液加氢较佳工艺条件为：丙酮／氯苯作共溶剂，NBR浓度为1.81g／100ml，催化剂浓度0.25％干胶重，催化剂：配体L₂=1：6（Wt），反应温度90℃，氢气压力1.4MPa；反应12小时加氢度可达81.1％。 RuCl₂（PPh₃）₃为催化剂的NBR乳液加氢较佳工艺条件与RhCl（PPh₃）₃催化剂对NBR乳液加氢相似，其较佳反应温度为145℃；并且在体系中加入添加剂三乙胺，其用量为催化剂的2倍，以抑制凝胶生成，反应16小时加氢度达75.0％。更多还原

【Abstract】 HNBR(hydrogenated Nitrile Rubber) is a kind of oil resisting rubber with excellent properties such as aging resistance, heat resistance, H2S resistance, and so on .The demand of HNBR is increasing with the development in oil-field and automobile industry.The kinetic study of the homogeneous solution hydrogenation of NBR using Rh-Ru bimetallic complex catalyst, has been carried out for the first time. The effects of C=C concentration, catalyst concentration, hydrogen pressure as well as temperature, on both the rate and degree of hydrogenation have been studied.The reaction order of each factor was calculated, a rate law was obtained as follows:-d[C=C]/dt=k[C=C]’ 68[Ph2]1. 07[Rh-Ru]1. 30The apparent activation energy is 13.68 kJ/mol at the temperature from 115℃ tol45℃ . Optimum reaction conditions were developed: NBR concentration 7g/100ml, catalyst concentration 0.25%(dry rubber weight); catalyst:L2=l :6(Wt). hydrogen pressure 1.4MPa; temperature 145℃; 98% hydrogenation was achieved within 5 hours.The hydrogenation of the C=C bonds in NBR emulsion using oil-soluble catalyst (RhCl(PPh3)3 or RuCl2(PPh3)3) in an organic cosolvent was studied. The effects of main reaction factors on NBR hydrogenation were examined.In the presence of RhCl(PPh3)3 catalyst, 81.1% hydrogenation of NBR emulsion could be achieved within 12 hours under conditions: NBR concentration 1.81g/100ml,catalyst concentration 0.25%( dry rubber weight), catalyst:PPh3=l :6(Wt), hydrogen pressure 1.4MPa .temperature 90#, using acetone-cholobenzene as cosolvent.For the RuCl2(PPh3)3 catalyst, silimar preferred conditionswas obtained. The preferred temperature is 145 .Additive triethylamine ((C2H5N3)is added to prevent gel formation( catalyst: additive=l:2(Wt)), 75.0% hydrogenation can be achieved for 16 hours.更多还原