2，2-二甲基-3-氯丙醇两步法制备新戊二醇研究
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摘要
新戊二醇用途广泛,不但用于聚酯的生产和芳烃、环烷烃的选择分离,而且在制药领域的应用也不断扩大。镇痛药布洛芬的制备过程中消耗大量的新戊二醇,并副产大量含2,2-二甲基-3-氯丙醇的废水,如果不有效回收和治理,将严重制约生产工艺的经济性和环保指标。本文对布洛芬生产过程中产生的2,2-二甲基-3-氯丙醇经环氧化、水解两步反应制备新戊二醇的工艺进行了研究。
本文研究了2,2-二甲基-3-氯丙醇在未加相转移催化剂和加入相转移催化剂下经环氧化生成2,2-二甲基-1,3-环氧丙烷,然后2,2-二甲基-1,3-环氧丙烷在不同催化剂下经水解生成新戊二醇的合成新工艺。通过考察相转移催化剂的种类及其用量、碱的种类及用量、碱浓度对环氧化反应的影响,得到了优化的环氧化反应工艺条件;通过考察水解催化剂的类型、催化剂用量、搅拌速度、反应温度、以及相转移催化剂对水解反应的影响,得到了水解反应的优化工艺条件。在优化的环氧化条件下对其动力学进行了研究,建立了环氧化反应的动力学模型,通过动力学实验,拟合确定了模型中的反应动力学参数并得到了环氧化反应的反应活化能。
实验考察结果得到的2,2-二甲基-3-氯丙醇在相转移催化作用下经环氧化反应制备2,2-二甲基-1,3-环氧丙烷的优化工艺条件为:采用表面活性剂S1为相转移催化剂,其用量为2,2-二甲基-3-氯丙醇量的3%,氢氧化钠用量与2,2-二甲基-3-氯丙醇用量比为nS:nA=1.4:1,氢氧化钠浓度为45%。在此优化工艺条件下环氧化反应的收率为91.16%。
宏观动力学实验结果表明环氧化反应为拟一级反应,活化能为0.99×104J/mol,指前因子为1.44×106min-1。两相间的传质为反应控制步骤,其反应机理为分子内SN2亲核取代反应。
建立了以1,3-丙二醇为内标适用于水基体系中新戊二醇的定量分析方法,拟合得到的线性回归方程为:y = 0.02786 x? 0.00627,回归系数R为0.9989,SD为0.0039,相对标准偏差为1.88%,检出限为2.0×10-3mg/ml。
2,2-二甲基-1,3-环氧丙烷水解生成新戊二醇的反应机理为酸性水解反应机理,得到的优化工艺条件为:采用表面活性剂S2为相转移催化剂,其用量为2,2-二甲基-1,3-环氧丙烷量的1%,采用硫酸浓度为3.5%,2,2-二甲基-1,3-环氧丙烷与水体积比为1:7,反应温度为55℃,搅拌速度大于40r/min。优化条件下的水解反应的平均收率为95.47%。
根据以上研究结果,对布洛芬生产过程产生的2,2-二甲基-3-氯丙醇经两步反应回收新戊二醇的工艺进行设计,确定了各设备的尺寸与材质,具有较大的工业指导价值,工业应用表明流程合理、工艺可行。
Neopentyl glycol has wide range of uses, not only in the production of polyester and aromatics, cycloalkanes choice of separation, but also in the field of pharmaceutical applications. As a condensing agent, a large amount of neopentyl glycol was consumed in the preparation of ibuprofen, at the same time, by-product waste contained 2,2-dimethyl-3-chloro-propanol. It would severely restrict the economic production process and environmental indicators, if not effective recovery and treatment. This article studied the preparation process of neopentyl glycol by cycliazation reaction and hydrolysis reaction from 2,2-dimethyl-3-chloro-propanol.
In this paper, 2,2-dimethyl-1,3-epoxy propane was prepared from 2,2-dimethyl-3-chloro-propanol by cycliazation under different catalysts; neopentyl glycol was generated from 2,2-dimethyl-1,3-epoxy propane by hydrolysis under different catalyst. The optimized cycliazation process conditions were obtained by studying the effects of different phase transfer catalysts and their dosage, different alkali, alkali dosage, alkali concentration. The optimized hydrolysis process conditions were also obtained by studying the effects of different hydrolysis catalyst, catalyst amount, stirring speed, reaction temperature, and phase transfer catalyst. The kinetic model of cycliazation reaction under the optimized cycliazation process conditions was established, the kinetic parameters and cycliazation reaction activation energy were obtained by fitting the kinetic experiments to the model.
The results of experimental show that the optimum conditions of the preaparation of 2,2 - dimethyl -1,3 - epoxy propane by the cycliazation of 2,2 - dimethyl -3 - chloro-propanol under phase transfer catalyst are: surfactant S1 as the phase transfer catalyst and the dosage of it is 3% of 2,2-dimethyl-3-chloro-propanol volume, the molar ratio of sodium hydroxide to 2,2 - dimethyl -3 - chloro-propanol = 1.4:1, the concentration of sodium hydroxide is 45%(wt).The cycliazation yield is 91.16% under this optimized cycliazation process conditions.
It was shown that the kinetics of cycliazation reaction under phase transfer catalysts is a pseudo first-order reaction, the activation energies evaluated is 0.99×104J/mol, the pre-exponential factor is 1.44×106min-1. Mass transfer of two phases is the controlling step for the reaction and the reaction mechanism is intramolecular SN2 nucleophilic substitution reaction.
The method for quantitative analysis of neopentyl glycol in water -based multicomponent system by gas chromatography internal standard curve using 1,3-propanediol as internal standard has been developed. The linear regression equation is y = 0.02786 x? 0.00627; regression coefficient is 0.9989; the relative standard deviation is 1.88% and the detection limit of this method is 2.0×10-6g/ml. The mechanism of 2,2 - dimethyl -1,3 - epoxy propane hydrolysis to generate neopentyl glycol is acid hydrolysis reaction mechanisms. The optimum conditions of the preparation of neopentyl glycol by the hydrolysis of 2,2 - dimethyl -1,3 - epoxy propane is: surfactant S2 as phase transfer catalyst and the dosage of it is 1% of 2,2 - dimethyl -1,3 - propylene of the amount; the concentration of sulfuric acid is 3.5%; the volume ratio of 2-2 Methyl-1,3-epoxy propylene to water is 1:7; the reaction temperature is 55℃and stirring speed is more than 40r/min. The average yield of hydrolysis reaction is 95.47% under the optimum conditions.
According to the above researching results,neopentyl glycol recovery process by the two-step reaction from waste contained 2,2 - dimethyl -3 - chloro-propanol in ibuprofen was designed. The sizes and materials of various equipments were determined as well.This design host great value of industrial guidance and industrial applications show that the process is reasonable and technology is feasible.
本文研究了2,2-二甲基-3-氯丙醇在未加相转移催化剂和加入相转移催化剂下经环氧化生成2,2-二甲基-1,3-环氧丙烷,然后2,2-二甲基-1,3-环氧丙烷在不同催化剂下经水解生成新戊二醇的合成新工艺。通过考察相转移催化剂的种类及其用量、碱的种类及用量、碱浓度对环氧化反应的影响,得到了优化的环氧化反应工艺条件;通过考察水解催化剂的类型、催化剂用量、搅拌速度、反应温度、以及相转移催化剂对水解反应的影响,得到了水解反应的优化工艺条件。在优化的环氧化条件下对其动力学进行了研究,建立了环氧化反应的动力学模型,通过动力学实验,拟合确定了模型中的反应动力学参数并得到了环氧化反应的反应活化能。
实验考察结果得到的2,2-二甲基-3-氯丙醇在相转移催化作用下经环氧化反应制备2,2-二甲基-1,3-环氧丙烷的优化工艺条件为:采用表面活性剂S1为相转移催化剂,其用量为2,2-二甲基-3-氯丙醇量的3%,氢氧化钠用量与2,2-二甲基-3-氯丙醇用量比为nS:nA=1.4:1,氢氧化钠浓度为45%。在此优化工艺条件下环氧化反应的收率为91.16%。
宏观动力学实验结果表明环氧化反应为拟一级反应,活化能为0.99×104J/mol,指前因子为1.44×106min-1。两相间的传质为反应控制步骤,其反应机理为分子内SN2亲核取代反应。
建立了以1,3-丙二醇为内标适用于水基体系中新戊二醇的定量分析方法,拟合得到的线性回归方程为:y = 0.02786 x? 0.00627,回归系数R为0.9989,SD为0.0039,相对标准偏差为1.88%,检出限为2.0×10-3mg/ml。
2,2-二甲基-1,3-环氧丙烷水解生成新戊二醇的反应机理为酸性水解反应机理,得到的优化工艺条件为:采用表面活性剂S2为相转移催化剂,其用量为2,2-二甲基-1,3-环氧丙烷量的1%,采用硫酸浓度为3.5%,2,2-二甲基-1,3-环氧丙烷与水体积比为1:7,反应温度为55℃,搅拌速度大于40r/min。优化条件下的水解反应的平均收率为95.47%。
根据以上研究结果,对布洛芬生产过程产生的2,2-二甲基-3-氯丙醇经两步反应回收新戊二醇的工艺进行设计,确定了各设备的尺寸与材质,具有较大的工业指导价值,工业应用表明流程合理、工艺可行。
Neopentyl glycol has wide range of uses, not only in the production of polyester and aromatics, cycloalkanes choice of separation, but also in the field of pharmaceutical applications. As a condensing agent, a large amount of neopentyl glycol was consumed in the preparation of ibuprofen, at the same time, by-product waste contained 2,2-dimethyl-3-chloro-propanol. It would severely restrict the economic production process and environmental indicators, if not effective recovery and treatment. This article studied the preparation process of neopentyl glycol by cycliazation reaction and hydrolysis reaction from 2,2-dimethyl-3-chloro-propanol.
In this paper, 2,2-dimethyl-1,3-epoxy propane was prepared from 2,2-dimethyl-3-chloro-propanol by cycliazation under different catalysts; neopentyl glycol was generated from 2,2-dimethyl-1,3-epoxy propane by hydrolysis under different catalyst. The optimized cycliazation process conditions were obtained by studying the effects of different phase transfer catalysts and their dosage, different alkali, alkali dosage, alkali concentration. The optimized hydrolysis process conditions were also obtained by studying the effects of different hydrolysis catalyst, catalyst amount, stirring speed, reaction temperature, and phase transfer catalyst. The kinetic model of cycliazation reaction under the optimized cycliazation process conditions was established, the kinetic parameters and cycliazation reaction activation energy were obtained by fitting the kinetic experiments to the model.
The results of experimental show that the optimum conditions of the preaparation of 2,2 - dimethyl -1,3 - epoxy propane by the cycliazation of 2,2 - dimethyl -3 - chloro-propanol under phase transfer catalyst are: surfactant S1 as the phase transfer catalyst and the dosage of it is 3% of 2,2-dimethyl-3-chloro-propanol volume, the molar ratio of sodium hydroxide to 2,2 - dimethyl -3 - chloro-propanol = 1.4:1, the concentration of sodium hydroxide is 45%(wt).The cycliazation yield is 91.16% under this optimized cycliazation process conditions.
It was shown that the kinetics of cycliazation reaction under phase transfer catalysts is a pseudo first-order reaction, the activation energies evaluated is 0.99×104J/mol, the pre-exponential factor is 1.44×106min-1. Mass transfer of two phases is the controlling step for the reaction and the reaction mechanism is intramolecular SN2 nucleophilic substitution reaction.
The method for quantitative analysis of neopentyl glycol in water -based multicomponent system by gas chromatography internal standard curve using 1,3-propanediol as internal standard has been developed. The linear regression equation is y = 0.02786 x? 0.00627; regression coefficient is 0.9989; the relative standard deviation is 1.88% and the detection limit of this method is 2.0×10-6g/ml. The mechanism of 2,2 - dimethyl -1,3 - epoxy propane hydrolysis to generate neopentyl glycol is acid hydrolysis reaction mechanisms. The optimum conditions of the preparation of neopentyl glycol by the hydrolysis of 2,2 - dimethyl -1,3 - epoxy propane is: surfactant S2 as phase transfer catalyst and the dosage of it is 1% of 2,2 - dimethyl -1,3 - propylene of the amount; the concentration of sulfuric acid is 3.5%; the volume ratio of 2-2 Methyl-1,3-epoxy propylene to water is 1:7; the reaction temperature is 55℃and stirring speed is more than 40r/min. The average yield of hydrolysis reaction is 95.47% under the optimum conditions.
According to the above researching results,neopentyl glycol recovery process by the two-step reaction from waste contained 2,2 - dimethyl -3 - chloro-propanol in ibuprofen was designed. The sizes and materials of various equipments were determined as well.This design host great value of industrial guidance and industrial applications show that the process is reasonable and technology is feasible.
引文
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