环氧环已烷的合成及应用

【作者】 蒋卫和；

【导师】 邓剑如； 刘小秦；

【作者基本信息】 湖南大学 ， 化学工程， 2003， 硕士

【摘要】 环氧环己烷是一种化学性质比较活泼的精细化工原料，应用范围十分广泛，具有良好的综合利用前景。国内外对其已有研究，合成方法可分为氧气催化氧化法、过氧化物催化氧化法、邻氯醇法、电氧化法及回收法。可在农药、医药、涂料等十余个行业得到广泛应用。 为解决因合成时成本高或污染大等导致环氧环己烷紧缺问题，作者在实验之前，进行了大量的调研工作。较全面地研究了环氧环己烷的合成方法以及应用。结合环己烯加成氯醇法与回收开环氯醇法技术，本论文提出了制备环氧环己烷新的工艺方法：双氯醇法。 在实验过程中，对氯醇化反应、皂化反应工艺条件进行了各种探索与选择，使环己烯氯醇法合成环氧环己烷的收率达到85％左右，含量可达99.5％。且连续化小试也取得了良好效果。其创新点主要如下： 1．无机相闭路循环，避免了一般氯醇法所带来的副产氯化氢处理问题和大量废水排放问题，减少了环境污染。 2．萃取剂伴生，环己烯反应选择性高。 3．轻质油同步分离，轻质油中主要组分环氧环己烷与正戊醇沸点相近，普通精馏无法分离，环氧环己烷生成邻氯环己醇后提高了相对挥发度，可用精馏实现进一步的分离。 除对双氯醇法合成环氧环己烷进行了研究外，还以环氧环己烷为原料合成了环己二醇二丙烯酸酯。 本实验借助单因素寻优等有关方法进行了合成工艺研究。考察了催化剂、带水剂、阻聚剂等对反应的影响。寻找了丙烯酸与环己二醇的较优摩尔配比为2.2：1。并对反应动力学特征进行了讨论，估算了该反应表观活化能大约为42.8kJ·mol^-1。现已确立了一条较合适的工业生产的工艺路线。 对于环氧环己烷应用于丙烯酸酯类的创新点在于环氧环己烷本身结构的特殊性：饱和的六元环比苯环性质更稳定，比直链刚性更强。而与丙烯酸反应生成多官能团的特种丙烯酸酯，其品质更优用途更广。更多还原

【Abstract】 Cyclohexene oxide (CHO) is very important fine chemical engineering raw material. Its chemical properties are reactive and its application is wide range. In a word, Cyclohexene oxide have good useful prospect. Cyclohexene oxide has been studied at home and abroad. Its synthetic methods were variety, including oxygen catalytic oxidation, peroxide catalytic oxidation, o-chloroalcohol synthesis, and electrochemical oxidation and recovery method. CHO was widely applied from agricultural, medication to coating and other fields.Many documents were reviewed in order to get proper method to produce CHO, to avoid high cost and great pollution in synthesis. The synthetic methods and application of CHO were investigated comprehensively. Combining method of cyclohexene addition product 2-chlorocyclohexanol with recovery method of ring-opening product 2-chlorocyclohexanol, this thesis built up a new technic method (i.e. double chloroalcohol method) to prepare CHO.In experiment process, the processing conditions of chloroalcohol reaction and saponification reaction were searched and selected carefully. The yield of cyclohexene chloroalcohol method to synthesize CHO up to 85% and the purification up to 99.5%. Furthermore, Good results were achieved in the continuous small-scale production test. Its new ideas and results are as follows:(1) By use of the adoption of inorganic phase closed-loop system, we can avoid to dispose by-product hydrochloride, discharge a great deal of exhausted water, and reduce environment pollution.(2) Co-production of extractant in reaction resulted in high selectivity of cyclohexene reaction.(3) The light oil were separated synchronically, because the main component in light oil are CHO and n-pentanol, and their boiling points are very close, common fractionation could not separate them. In reaction, CHO’s forming o-chloro cyclohexanol increased relative volatility. In this condition, further separation could be realized by fractionation.The author also studied the synthesis of acrylate in application except for above mentioned. In the stage, CHO was main starting material. Its hydrolyzed cyclohexanediol reacted with acrylic acid and formed cyclohexanedion diacrylate, which is very significant for meeting the growing needs of radiation curing acrylate.In our research, synthetic processing was studied at the aid of single factor superior-finding. The infiunces of catalyst, deaqueous agent, and inhibitor were examined in the reaction. The optimized molar ratio of acrylic acid to cyclohexanediol was 2.2 ! 1. The reaction kinetic characteristic was discussed and apparent activation energy was calculated about 42.8KJ mol-1. as a result, a processing route fitting for industrial production was established.The new idea of CHO’s application to acrylate lied in particular structure of CHO itself: cyclohexyl ring is more stable than phenyl ring in chemical properties and more strong than linear chain compounds in hardness, and CHO’s reaction with acrylic acid could formed polyfunctional special acrylate. Its quality is excellent and its use is wide.更多还原