CN104003871B - Butyl benzyl phthalate rectifying low-boiling-point substance is utilized to prepare the method for jasmal - Google Patents
Butyl benzyl phthalate rectifying low-boiling-point substance is utilized to prepare the method for jasmal Download PDFInfo
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- CN104003871B CN104003871B CN201410223385.8A CN201410223385A CN104003871B CN 104003871 B CN104003871 B CN 104003871B CN 201410223385 A CN201410223385 A CN 201410223385A CN 104003871 B CN104003871 B CN 104003871B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention discloses a kind of method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal, the method comprises the following steps: 1) drop in reactor by butyl benzyl phthalate rectifying low-boiling-point substance, acetic acid, the first catalyzer and water entrainer, be warming up to 90 ~ 130 DEG C of back flow reaction and point water, separate until phase splitter is anhydrous; 2) in reactor, add acetic anhydride and the second catalyzer again, continue to be warming up to 130 ~ 160 DEG C of back flow reaction, gas-chromatography is followed the tracks of, and stops heating when benzyl butyl ether residual in reaction mass is less than 0.2%; 3) reaction products therefrom is carried out rectification under vacuum removing impurity, then be washed till neutrality with the sodium carbonate solution that weight percentage is 15 ~ 25%, then obtain finished product ethyl ester benzyl ester through washing, rectifying.Facts have proved, the method is easy and simple to handle, efficiency is high, production cost is low, be suitable for suitability for industrialized production.
Description
Technical field
The invention belongs to chemical perfume preparing technical field, specifically refer to a kind of method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal.
Background technology
Butyl benzyl phthalate is a kind of softening agent, is mainly used in the course of processing of plastics, in order to improve plasticity, the mobility of resin, when coordinating with other softening agent, goods can be made to have the excellent transparency and smooth surface.
At present, the main method of industrial production butyl benzyl phthalate is generally reacted by phthalic anhydride and esterified by butyl alcohol to generate phthalic acid mono—n—butylester, neutralize with liquid caustic soda again, generate phthalic acid mono—n—butylester sodium salt, under triethylamine catalysis, then carry out condensation reaction with Benzyl Chloride generate butyl benzyl phthalate.
Generate butyl benzyl phthalate reaction formula:
In the condensation reaction of final step and the Benzyl Chloride produced, Benzyl Chloride has a small amount of hydrolysis and generates benzylalcohol, and the benzylalcohol generated under the condition refluxed in some and system butanols dehydrating condensation generate benzyl butyl ether.In the post-processing stages of reaction, first the benzylalcohol of generation and benzyl butyl ether are distillated out as the low-boiling-point substance in the thick product of butyl benzyl phthalate, and the amount of low-boiling-point substance accounts for 8% of whole butyl benzyl phthalate gross weight.In butyl benzyl phthalate rectifying low-boiling-point substance, benzylalcohol component concentration is about 80% (GC, area %), benzyl butyl ether content is about 20% (GC, area %).Because the boiling point of benzylalcohol and benzyl butyl ether is very close, cannot be separated two components by the method for rectifying, this low mixture that boils can only be used as scrap handling, serious waste of resources at present, financial loss is huge.
Jasmal is a kind of maturation, consumption spices widely, is mainly used in preparing in the essence of jasmine fragrance and soap compound; In addition it or a kind of widely used meticulous Organic chemical products, as the solvent of resin, dyestuff, grease, ink etc.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal, the method is easy and simple to handle, efficiency is high, production cost is low, be suitable for suitability for industrialized production.
For achieving the above object, the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal of the present invention, comprises the following steps:
1) butyl benzyl phthalate rectifying low-boiling-point substance, acetic acid, the first catalyzer and water entrainer are dropped in reactor, be warming up to 90 ~ 130 DEG C of back flow reaction and point water, separate until phase splitter is anhydrous; Described first catalyzer is one or both in thionamic acid or tosic acid; Now, the low benzylalcohol boiled in mixture is converted into jasmal substantially, and the lower benzyl butyl ether of activity can not be deposited in acetic acid reaction and reacts in feed liquid.
2) in reactor, add acetic anhydride and the second catalyzer again, continue to be warming up to 130 ~ 160 DEG C of back flow reaction, gas-chromatography is followed the tracks of, and stops heating when benzyl butyl ether residual in reaction mass is less than 0.2%; Described second catalyzer is one or both in thionamic acid or tosic acid; Now, benzyl butyl ether is converted into jasmal and butylacetate.
3) reaction products therefrom is carried out rectification under vacuum removing impurity, then be washed till neutrality with the sodium carbonate solution that weight percentage is 15 ~ 25%, then obtain finished product ethyl ester benzyl ester through washing, rectifying.The low-boiling-point substances such as the acetic acid that this step obtains, butylacetate can direct reuse.
Preferably, step 1) in, the weight ratio of described butyl benzyl phthalate rectifying low-boiling-point substance and acetic acid is 1 ︰ 0.4 ~ 0.9.
Further, step 1) in, described water entrainer is one or both in butylacetate or toluene.
Also further, step 1) in, add the first catalyzer weight be 0.1 ~ 10% of butyl benzyl phthalate rectifying low-boiling-point substance weight; Step 2) in, add the second catalyzer weight be 0.1 ~ 10% of butyl benzyl phthalate rectifying low-boiling-point substance weight.
Again further, step 1) in, the weight ratio of described butyl benzyl phthalate rectifying low-boiling-point substance and water entrainer is 1 ︰ 0.05 ~ 0.3.
Further, step 2) in, the weight ratio of described butyl benzyl phthalate rectifying low-boiling-point substance and acetic anhydride is 1 ︰ 0.1 ~ 0.5.
The expression formula that this preparation method relates to reaction is:
The benzylalcohol that the present invention is mainly close by boiling point by the means of chemical conversion and not easily pass through in the butyl benzyl phthalate rectifying low-boiling-point substance of rectifying separation and benzyl butyl ether mixture all change into jasmal, utilize low each component of boiling in mixture to greatest extent, achieve the Atom economy of raw material and good economic benefit simultaneously.
Because the boiling point of benzylalcohol and benzyl butyl ether is very close, almost by the method for rectifying, both cannot be separated.In the low mixture that boils, the reactive behavior of benzylalcohol is better, multiple reaction can occur and be converted into other material; The chemically reactive of benzyl butyl ether is very low, and common acid, alkali can not make it decompose or be converted into other material.If benzylalcohol is converted into other products simply by a certain reaction, be then separated with benzyl butyl ether by this product, then can there is following problem: first, transformation efficiency is low, and benzyl butyl ether can be present in system as inert impurities always; Secondly, the energy consumption of separation and the loss of product can be larger, and the benzyl butyl ether separated overstocks owing to not having too large application prospect, causes the huge wasting of resources.Applicant finds after deliberation under catalyzer and water entrainer exist, and the low benzylalcohol boiled in mixture can obtain jasmal with acetic acid through intensification azeotropic reflux water-dividing, the benzyl butyl ether that in azeotropic mixture, activity is lower can not with acetic acid reaction and retaining in the solution.Now, the main component of solution is jasmal and benzyl butyl ether.After benzylalcohol transforms substantially, in system, add acetic anhydride, make it to be obtained by reacting jasmal and ethyl ester butyl ester with benzyl butyl ether high temperature reflux.Like this, through whole chemical conversion, low two component benzylalcohols in mixture and the benzyl butyl ether of boiling reacts with acetic acid, acetic anhydride respectively, two components are all converted into jasmal, thus fundamentally solve the problem that raw material cannot be separated, achieve the Atom economy of whole conversion, economize on resources.After reaction terminates, first the butylacetate in thick product is separated as low the boiling of rectifying, and it can be used as the azeotropic aqua of lower batch of reaction; Jasmal in thick product then obtains commodity jasmal after rectification and purification.
Its production operation simple process of present invention process, stable, the maximized each component that make use of the low mixture that boils, turns waste into wealth, has saved resource, and be beneficial to environmental protection contribution, material cost is cheap simultaneously, and its economic and social benefit is all obvious.
Embodiment
Below in conjunction with specific embodiment, the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal of the present invention is described in further detail.
Embodiment 1
Utilize butyl benzyl phthalate rectifying low-boiling-point substance to prepare a method for jasmal, comprise the following steps:
1) in 100mL there-necked flask, successively 300g O-phthalic ester butyl benzyl rectifying low-boiling-point substance, 200g acetic acid (purity 98%), 30mL toluene (purity 98%) and 1.5g thionamic acid (purity 95%) is added; After testing, in this O-phthalic ester butyl benzyl rectifying low-boiling-point substance, benzylalcohol content is 80% (GC, area %), benzyl butyl ether content is 20% (GC), is heated to 110 DEG C of azeotropic back flow reaction and point water to flask;
2) when going out without obvious moisture in phase splitter, 73g acetic anhydride (purity 98%) and 1.5g thionamic acid (purity 95%) is added again in reactor, be warming up to 140 ~ 150 DEG C and continue reaction, reaction process is monitored by gas-chromatography in reaction process, when benzyl butyl ether component concentration residual in system is lower than 0.2% (GC, area %) time, heating can be stopped, and cool;
3) reaction products therefrom is under reduced pressure distilled the low-boiling-point substance such as remaining acetic acid, acetic anhydride and butylacetate in removing crude product, gained crude product weight percentage is that 20% sodium carbonate solution is washed till neutrality, and then wash, rectifying, obtain 265g jasmal finished product, purity is 99.3% (GC), and yield is 71.2%.
Embodiment 2
Utilize butyl benzyl phthalate rectifying low-boiling-point substance to prepare a method for jasmal, comprise the following steps:
1) 120kg O-phthalic ester butyl benzyl rectifying low-boiling-point substance (component is with embodiment 1), 72kg Glacial acetic acid, 1.5kg tosic acid (purity 95%) is added in 300L reactor, 30kg butylacetate (purity 98%), is heated to 110 DEG C of azeotropic reflux water-dividings to reactor;
2) when going out without obvious moisture in phase splitter, 35kg acetic anhydride and 1.5kg tosic acid is added again in reactor, be warming up to 150 DEG C and continue reaction, reaction process is monitored by gas-chromatography in reaction process, when benzyl butyl ether component concentration residual in system is lower than 0.2% (GC), heating can be stopped, and cool;
3) reaction products therefrom is under reduced pressure distilled the low-boiling-point substance such as remaining acetic acid, acetic anhydride and butylacetate in removing crude product, gained crude product weight percentage be 25% sodium carbonate solution be washed till neutrality and then wash, rectifying, obtain 118kg jasmal finished product, purity is 99.1% (GC), and yield is 79.3%.
Embodiment 3
Utilize butyl benzyl phthalate rectifying low-boiling-point substance to prepare a method for jasmal, comprise the following steps:
1) add 120kg O-phthalic ester butyl benzyl rectifying low-boiling-point substance (component is with embodiment 1), 70kg Glacial acetic acid, 1.5kg thionamic acid, 30kg butylacetate in 300L reactor, be heated to 110 DEG C of azeotropic reflux water-dividings to reactor;
2) when going out without obvious moisture in phase splitter, 35kg acetic anhydride and 1.5kg tosic acid is added again in reactor, be warming up to 160 DEG C of reactions, reaction process is monitored by gas-chromatography in reaction process, when benzyl butyl ether component concentration residual in system is lower than 0.2% (GC), heating can be stopped, and cool;
3) reaction products therefrom is under reduced pressure distilled the low-boiling-point substance such as remaining acetic acid, acetic anhydride and butylacetate in removing crude product, gained crude product weight percentage be 15% sodium carbonate solution be washed till neutrality and then wash, after rectifying 112kg jasmal finished product, purity is 99.0% (GC), and yield is 75.4%.
Embodiment 4
Utilize butyl benzyl phthalate rectifying low-boiling-point substance to prepare a method for jasmal, comprise the following steps:
1) add 120kg O-phthalic ester butyl benzyl rectifying low-boiling-point substance (component is with embodiment 1), 60kg acetic anhydride, 1.5kg thionamic acid, 30kg butylacetate (purity 98%) in 300L reactor, be heated to 130 DEG C of azeotropic reflux water-dividings to reactor;
2) when going out without obvious moisture in phase splitter, add 35kg acetic anhydride again, with 1.5kg tosic acid, be warming up to 150 DEG C of reactions, reaction process is monitored by gas-chromatography, after 6h, in system, remaining benzyl butyl ether component concentration, lower than 0.2% (GC), can stop heating, and cool;
3) reaction products therefrom is under reduced pressure distilled the low-boiling-point substance such as remaining acetic acid, acetic anhydride and butylacetate in removing crude product, gained crude product weight percentage be 15% sodium carbonate solution be washed till neutrality and then wash, after rectifying 127kg jasmal finished product, purity is 99.4% (GC), and yield is 85.0%.
Embodiment 5
Utilize butyl benzyl phthalate rectifying low-boiling-point substance to prepare a method for jasmal, comprise the following steps:
1) add 150kg O-phthalic ester butyl benzyl rectifying low-boiling-point substance (component is with embodiment 1), 75kg Glacial acetic acid, 1.0kg thionamic acid and 0.5kg tosic acid, 20kg butylacetate and 30ml toluene in 300L reactor, be heated to 120 DEG C of azeotropic reflux water-dividings to reactor;
2) when going out without obvious moisture in phase splitter, 40kg acetic anhydride and 2.5kg tosic acid is added again in reactor, be warming up to 150 DEG C of reactions, reaction process is monitored by gas-chromatography in reaction process, when benzyl butyl ether component concentration residual in system is lower than 0.2% (GC), heating can be stopped, and cool;
3) reaction products therefrom is under reduced pressure distilled the low-boiling-point substance such as remaining acetic acid, acetic anhydride and butylacetate in removing crude product, gained crude product weight percentage be 20% sodium carbonate solution be washed till neutrality and then wash, after rectifying 132kg jasmal finished product, purity is 99.0% (GC), and yield is 82.4%.
Claims (7)
1. utilize butyl benzyl phthalate rectifying low-boiling-point substance to prepare a method for jasmal, it is characterized in that, it comprises the following steps:
1) butyl benzyl phthalate rectifying low-boiling-point substance, acetic acid, the first catalyzer and water entrainer are dropped in reactor, be warming up to 90 ~ 130 DEG C of back flow reaction and point water, separate until phase splitter is anhydrous; Described first catalyzer is one or both in thionamic acid or tosic acid; Described butyl benzyl phthalate rectifying low-boiling-point substance is the mixture of benzylalcohol and benzyl butyl ether;
2) in reactor, add acetic anhydride and the second catalyzer again, be heated to 130 ~ 160 DEG C of back flow reaction, gas-chromatography is followed the tracks of, and stops heating when benzyl butyl ether residual in reaction mass is less than 0.2%; Described second catalyzer is one or both in thionamic acid or tosic acid;
3) reaction products therefrom is carried out rectification under vacuum removing impurity, then be washed till neutrality with the sodium carbonate solution that weight percentage is 15 ~ 25%, then obtain finished product jasmal through washing, rectifying.
2. the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal according to claim 1, is characterized in that: step 1) in, the weight ratio of described butyl benzyl phthalate rectifying low-boiling-point substance and acetic acid is 1 ︰ 0.4 ~ 0.9.
3. the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal according to claim 1 and 2, is characterized in that: step 1) in, described water entrainer is one or both in butylacetate or toluene.
4. the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal according to claim 1 and 2, it is characterized in that: step 1) in, add the first catalyzer weight be 0.1 ~ 10% of butyl benzyl phthalate rectifying low-boiling-point substance weight.
5. the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal according to claim 1 and 2, it is characterized in that: step 2) in, add the second catalyzer weight be 0.1 ~ 10% of butyl benzyl phthalate rectifying low-boiling-point substance weight.
6. the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal according to claim 1 and 2, is characterized in that: step 2) in, the weight ratio of described butyl benzyl phthalate rectifying low-boiling-point substance and acetic anhydride is 1 ︰ 0.1 ~ 0.5.
7. the method utilizing butyl benzyl phthalate rectifying low-boiling-point substance to prepare jasmal according to claim 1 and 2, it is characterized in that: step 1) in, the weight ratio of described butyl benzyl phthalate rectifying low-boiling-point substance and water entrainer is 1 ︰ 0.05 ~ 0.3.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143627A (en) * | 1995-08-22 | 1997-02-26 | 烟台市福山科源化工厂 | Process for producing butyl benzyl phthalate |
| CN101434539A (en) * | 2008-12-17 | 2009-05-20 | 武汉有机实业股份有限公司 | Preparation of benzyl acetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143627A (en) * | 1995-08-22 | 1997-02-26 | 烟台市福山科源化工厂 | Process for producing butyl benzyl phthalate |
| CN101434539A (en) * | 2008-12-17 | 2009-05-20 | 武汉有机实业股份有限公司 | Preparation of benzyl acetate |
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