γ-十一内酯的合成与提纯研究
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摘要
γ-十一内酯是一种极其重要的内酯类香料,具有强烈的桃子香气,故又称为桃醛,可广泛应用于日化香精和食用香精,近年来其合成和提纯方法的研究受到广泛关注。本文系统研究了γ-十一内酯的制备和提纯工艺,为工业生产提供理论指导。
以正辛醇和丙烯酸甲酯为原料,在引发剂过氧化二特丁基的作用下,通过游离基加成反应合成了γ-十一内酯粗产品,通过气相色谱法实现了对反应进程的监控,系统考察了游离基加成反应的各影响因素。实验结果表明,最佳投料比为丙烯酸甲酯∶正辛醇=1∶7 ,催化剂用量为1%(相当于总质量),反应时间为8h,反应温度为180℃,使用恒压滴液漏斗加料2.5h,收率可达到78%(以丙烯酸甲酯为基准)。
提纯γ-十一内酯粗产品使用真空间歇精馏操作,在严格控制好其它操作条件的前提下,重点研究了回流比对产品纯度和收率的影响。采用变回流比操作时,采出初期设定回流比为8,采出后期设定回流比为12,产品纯度超过99%,收率超过50%。
本文还系统分析了游离基加成反应的副反应状况,采用添加催化助剂的方式提高了产品收率,并改善了其它工艺操作参数。催化助剂包括酸、卤化锌和无机盐。催化剂联用的效用包括:提高产品收率、缩短反应时间、降低反应温度、减少正辛醇用量以及降低重组分杂质含量。
γ-undecalactone is a very important kind of lactone perfumes. It is also named peach aldehyde since it has a strong fragrance of peach with it. The preparation and purification technology ofγ-undecalactone which are researched in this paper are highly interested recently due to its extensive application in daily chemical essence and edible essence. This paper will provide industrial production with theoretical guidance.
Via free radical addition reaction,γ-undecalactone’s crude product was prepared from n-butanol and methacrylate in the presence of di-tert-butyl peroxide initiator. Under the monitoring of the reaction process with gas chromatography, the influencing factors of the free radical addition reaction were systematically investigated. The experimental results indicate that the best inventory ratio of n-butanol and methacrylate is 1:7; catalyst amount is 1%( based on total mass of material); reaction time is 8h; reaction tempreture is 180℃; feeding time of constant pressure funnel is 2.5h; the yield based on methacrylate reaches 78%.
γ-undecalactone’s crude product was purified by vacuum batch distillation. On the premise of strict control of other conditions, the impact of reflux ratio on product purity and yield was focused on. Product purity would be more than 99% and yield 50% by introducing variable reflux ratios which was setted as 8 during the initial produced stage and as 12 during the late produced stage.
The side effects of free radical addition reaction were also studied in this paper. Adding catalytic promoters including acids, zinc halide and inorganic salts has improved the product yield and other process operation parameters.The combined catalysts can improve the product yield, shorten the reaction time, lower the reaction temperature, reduce the consumption of n-butanol and decrease the contents of impurity in heavy component.
以正辛醇和丙烯酸甲酯为原料,在引发剂过氧化二特丁基的作用下,通过游离基加成反应合成了γ-十一内酯粗产品,通过气相色谱法实现了对反应进程的监控,系统考察了游离基加成反应的各影响因素。实验结果表明,最佳投料比为丙烯酸甲酯∶正辛醇=1∶7 ,催化剂用量为1%(相当于总质量),反应时间为8h,反应温度为180℃,使用恒压滴液漏斗加料2.5h,收率可达到78%(以丙烯酸甲酯为基准)。
提纯γ-十一内酯粗产品使用真空间歇精馏操作,在严格控制好其它操作条件的前提下,重点研究了回流比对产品纯度和收率的影响。采用变回流比操作时,采出初期设定回流比为8,采出后期设定回流比为12,产品纯度超过99%,收率超过50%。
本文还系统分析了游离基加成反应的副反应状况,采用添加催化助剂的方式提高了产品收率,并改善了其它工艺操作参数。催化助剂包括酸、卤化锌和无机盐。催化剂联用的效用包括:提高产品收率、缩短反应时间、降低反应温度、减少正辛醇用量以及降低重组分杂质含量。
γ-undecalactone is a very important kind of lactone perfumes. It is also named peach aldehyde since it has a strong fragrance of peach with it. The preparation and purification technology ofγ-undecalactone which are researched in this paper are highly interested recently due to its extensive application in daily chemical essence and edible essence. This paper will provide industrial production with theoretical guidance.
Via free radical addition reaction,γ-undecalactone’s crude product was prepared from n-butanol and methacrylate in the presence of di-tert-butyl peroxide initiator. Under the monitoring of the reaction process with gas chromatography, the influencing factors of the free radical addition reaction were systematically investigated. The experimental results indicate that the best inventory ratio of n-butanol and methacrylate is 1:7; catalyst amount is 1%( based on total mass of material); reaction time is 8h; reaction tempreture is 180℃; feeding time of constant pressure funnel is 2.5h; the yield based on methacrylate reaches 78%.
γ-undecalactone’s crude product was purified by vacuum batch distillation. On the premise of strict control of other conditions, the impact of reflux ratio on product purity and yield was focused on. Product purity would be more than 99% and yield 50% by introducing variable reflux ratios which was setted as 8 during the initial produced stage and as 12 during the late produced stage.
The side effects of free radical addition reaction were also studied in this paper. Adding catalytic promoters including acids, zinc halide and inorganic salts has improved the product yield and other process operation parameters.The combined catalysts can improve the product yield, shorten the reaction time, lower the reaction temperature, reduce the consumption of n-butanol and decrease the contents of impurity in heavy component.
引文
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