CN105348104A - Production method of glycerin tribenzoate - Google Patents
Production method of glycerin tribenzoate Download PDFInfo
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- CN105348104A CN105348104A CN201510634054.8A CN201510634054A CN105348104A CN 105348104 A CN105348104 A CN 105348104A CN 201510634054 A CN201510634054 A CN 201510634054A CN 105348104 A CN105348104 A CN 105348104A
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- reaction
- phenylformic acid
- benzoate
- glycerine
- dewatering agent
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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 production method of glycerin tribenzoate. The production method comprises the following steps: carrying out heating reflux for water distribution on glycerol and benzoic acid under the existence of an alkaline substance and a dehydrating agent, carrying out a dehydration esterification reaction, carrying out reaction liquid post-treatment after the reaction is finished, to prepare the glycerin tribenzoate. A ratio of the amount of substance of the glycerol to the benzoic acid is 1: (3.0-3.3); and the alkaline substance is carbonate, bicarbonate, hydroxide or benzoate of alkali metals or alkaline-earth metals. In the invention, a dehydration esterification reaction is carried out under the existence of alkaline, so that side reactions such as glycerol polymerization and glycerol dehydration to generate acraldehyde and the like are greatly inhibited, production of corresponding by-products is reduced, and the yield of the principal product and the content of the product are improved. The operation is simple, the process stability is high, the corrosion and material requirements for equipment are greatly reduced, and meanwhile, the product is low and stable in chromaticity, being suitable for industrial production.
Description
(1) technical field
The invention belongs to chemical field, specifically a kind of production method of tribenzoin.
(2) background technology
Tribenzoin has another name called tribenzoin, Glycerin tribenzoate, is that a kind of important solid plasticizer has the features such as applied widely, consistency good, good stability, and toxicity is low.Fine with the consistency of the polymkeric substance such as PVC, polyvinyl acetate (PVA), polymethacrylate, nitrocellulose, cellulose acetate butyrate, ethyl cellulose, polystyrene.Just can increase the flexibility of goods during room temperature, viscosity can be reduced when heating up as processing aid or softening agent, strengthening clinging power or heat sealing strength.Tribenzoin UV resistant, stablize thermal destruction, toxicity is low, and rat oral LD50 is greater than 11.7g/kg body weight.FDA regulation is classified as can make food product pack tackiness agent.Tribenzoin is also used as hot melt adhesive, coating, ink, tackiness agent, wlding, hot melting equipment clean-out system etc.Tribenzoin is also used to the allotment of food flavour and daily chemical essence in addition.
At present the route of existing patent mainly contains two classes: 1, with phenylformic acid and glycerine for raw material, carry out dehydration esterification in acid catalysis and be obtained by reacting GTB.CN201210468175 with phenylformic acid and glycerine for raw material, under Catalyzed by p-Toluenesulfonic Acid, with hexanaphthene-toluene Mixed Solvent for water entrainer, reflux water-dividing reaction 22 ~ 28 hours, reaction finish be separated with separation system of simulated moving bed chromatography, recycling design obtains product.2, with glycerine and Benzoyl chloride for raw material, there is lower synthetic glycerine tribenzoate in alkali.If WO03068828A1 is solvent with tetrahydrofuran (THF), under pyridine exists, glycerine and Benzoyl chloride elder generation normal-temperature reaction back flow reaction 6 hours after 1 hour.Reaction terminates, and adds water, extracts with toluene.Organic phase separates the washing of rear alkali salt water, dry, filters.Steam solvent and obtain white solid, re-crystallizing in ethyl acetate obtains product.
Route 1 is under acid catalysis, and side reaction is more, can generate Polyglycerine and benzoic ether thereof, and propenal and other by product, product purity is low.In addition under acidic catalyst, if temperature of reaction is low, then speed of response is slow and incomplete; Although speed of response increases after raised temperature, color is also deteriorated, and side reaction increases.Reaction scheme 2 technique is more complicated, relates to reagent type more, and Atom economy is low, and environmental pollution is large.
(3) summary of the invention
The technical problem to be solved in the present invention is: it is many that solution prior art exists side reaction, and reaction system color is dark; Or operation is more, the problem that Atom economy low cost is high.There is provided one not only simple and effectively stably can produce tribenzoin, and yield is high, side reaction is few, and product purity is high, outward appearance good, and products obtained therefrom can meet the operational path of the normal usage such as softening agent.This technique Atom economy is high, and only have a part water to remove in theory, other atoms all enter in product.Meet Green Chemistry, a small amount of unreacted phenylformic acid, glycerine and glycerine dibenzoate, glycerine one benzoic ether intermediate product, solvent etc. all can directly overlap for next batch, substantially achieve zero release.
It is as follows that the present invention solves the problems of the technologies described above the technical scheme taked:
A production method for tribenzoin, described method is:
By glycerine and phenylformic acid under the existence of alkaline matter and dewatering agent, reflux divides water, carries out dehydration esterification reaction, and reaction terminates rear reaction solution aftertreatment and obtains tribenzoin; Described glycerine and benzoic amount of substance ratio are 1:3.0 ~ 3.3;
Described alkaline matter is the carbonate of basic metal or alkaline-earth metal, supercarbonate, oxyhydroxide or benzoate; Preferred alkaline matter is sodium carbonate, sodium bicarbonate, sodium hydroxide, Sodium Benzoate, salt of wormwood, saleratus, potassium hydroxide, potassium benzoate, calcium carbonate, calcium hydroxide or calcium benzoate, more preferably sodium hydroxide, salt of wormwood, Sodium Benzoate, potassium benzoate or calcium hydroxide.
The quality consumption of described alkaline matter is 0.1 ~ 3% of qualities of glycerin, preferably 0.1 ~ 1%.
Described dewatering agent is one or more the mixing in toluene, dimethylbenzene, hexane, heptane, octane, nonane, decane, methylcyclohexane, one or more the mixing in preferred toluene, dimethylbenzene, octane, methylcyclohexane, n-decane.
The quality consumption of described dewatering agent is 3 ~ 15% of glycerine and benzoic total mass, preferably 3 ~ 10%.
The temperature of described reflux water-dividing is 120 ~ 260 DEG C.Be preferably 180 ~ 240 DEG C, more preferably 220 DEG C.
In general, the fusing point of different dewatering agents is different, under the kind and consumption of different dewatering agent, the temperature of backflow can change to some extent, the present invention, at the reflux water-dividing temperature of above-mentioned restriction, selects kind and the consumption of suitable dewatering agent, to reach required reflux temperature.
Described reaction end is generally reaction and steams to anhydrous, represents that reaction terminates.
Described reaction solution post-treating method is: after reaction terminates, reaction solution Distillation recovery dewatering agent and phenylformic acid, and the phenylformic acid that finally logical nitrogen distillation removing is residual, residuum cooling i.e. obtained tribenzoin.
The present invention compared with the conventional method, there is following remarkable advantage: 1, reduce side reaction: glycerine easily condensation reaction occurs in acid condition, and in the basic conditions, condensation side reaction temperature improves, far above esterification reaction temperature, therefore, because the present invention carries out dehydration esterification reaction in the presence of a base, glycerol polymerization, dehydrating glycerin is greatly inhibit to generate the side reactions such as propenal, decrease corresponding by product to generate, the yield not only increasing principal product also improves the content of product, lays good basis for simplifying aftertreatment.2, technical process is short, simple to operate, and technology stability is high, and base catalysis greatly reduces corrodibility to equipment and material requirement, and the colourity of product is low and stable simultaneously, is applicable to suitability for industrialized production.Obtained tribenzoin purity is high, can meet the multiple uses such as softening agent, tackiness agent, food flavour blender.3, solvent unit consumption is low, substantially without discharge except water generation reaction, has higher Atom economy, meets Green Chemistry Theory, can accomplish recycled in production process, and reduction production cost reduces the impact on environment simultaneously.
(4) accompanying drawing explanation
The liquid chromatogram of tribenzoin prepared by Fig. 1 embodiment six.
The infrared spectrogram of tribenzoin prepared by Fig. 2 embodiment six.
(5) embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited thereto.Every embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall within the scope of protection of the present invention.
Embodiment one
In 1000L reactor, add glycerine 184Kg, sodium hydroxide 0.3Kg, phenylformic acid 732Kg, toluene 50Kg stirring is warming up to and dissolves clarification, continue to be warming up to 220 DEG C.The reaction of insulation reflux dewatering steams to substantially anhydrous, continues insulation reaction 1 hour.React and finish, Distillation recovery toluene and phenylformic acid, residual benzene formic acid steams by logical nitrogen distillation, and in still, material obtains 800.5Kg white solid, content 98.3% after putting into square plate cooling.The phenylformic acid steamed, toluene can directly overlap for lower batch after undue water.
Embodiment two
In 1000L reactor, add glycerine 184Kg, salt of wormwood 2Kg, phenylformic acid 750Kg, dimethylbenzene 80Kg stirring is warming up to and dissolves clarification, continue to be warming up to 220 DEG C.The reaction of insulation reflux dewatering steams to substantially anhydrous, continues insulation reaction 1 hour.Reaction is finished, Distillation recovery dimethylbenzene and phenylformic acid.Residual benzene formic acid steams by logical nitrogen distillation, and in still, material obtains 806.1Kg white solid, content 99.1% after putting into square plate cooling.The phenylformic acid steamed, dimethylbenzene can directly overlap for lower batch after undue water.
Embodiment three
In 1000L reactor, add glycerine 184Kg, Sodium Benzoate 0.8Kg, phenylformic acid 750Kg, octane 60Kg stirring is warming up to and dissolves clarification, continue to be warming up to 220 DEG C.The reaction of insulation reflux dewatering steams to substantially anhydrous, continues insulation reaction 1 hour.Reaction is finished, Distillation recovery octane and phenylformic acid.Residual benzene formic acid steams by logical nitrogen distillation, and in still, material obtains 805.3Kg white solid, content 98.5% after putting into square plate cooling.The phenylformic acid steamed, octane can directly overlap for lower batch after undue water.
Embodiment four
In 1000L reactor, add glycerine 184Kg, potassium benzoate 1.2Kg, the stirring of phenylformic acid 770Kg, 30Kg methylcyclohexane is warming up to and dissolves clarification, continue to be warming up to 220 DEG C.The reaction of insulation reflux dewatering steams to substantially anhydrous, continues insulation reaction 1 hour.Reaction is finished, Distillation recovery methylcyclohexane and phenylformic acid.Residual benzene formic acid steams by logical nitrogen distillation, and in still, material obtains 795.1Kg white solid, content 98.8% after putting into square plate cooling.The phenylformic acid steamed and methylcyclohexane can directly overlap for lower batch after undue water.
Embodiment five
In 1000L reactor, add the methylcyclohexane stirring of reclaiming in phenylformic acid 770Kg, 30Kg embodiment four of glycerine 184Kg, potassium benzoate 1.2Kg, recovery and be warming up to dissolving clarification, continue to be warming up to 220 DEG C.The reaction of insulation reflux dewatering steams to substantially anhydrous, continues insulation reaction 1 hour.Reaction is finished, Distillation recovery methylcyclohexane and phenylformic acid.Residual benzene formic acid steams by logical nitrogen distillation, and in still, material obtains 795.1Kg white solid, content 99.1% after putting into square plate cooling.The phenylformic acid steamed and methylcyclohexane can directly overlap for lower batch after undue water.
Embodiment six
In 1000L reactor, add glycerine 184Kg, calcium hydroxide 1.5Kg, phenylformic acid 780Kg, n-decane-dimethylbenzene (V:V=1:1) 100Kg stirring is warming up to and dissolves clarification, continue to be warming up to 220 DEG C.The reaction of insulation reflux dewatering steams to substantially anhydrous, continues insulation reaction 1 hour.Reaction is finished, distillating recovering solvent dewatering agent and phenylformic acid.Residual benzene formic acid steams by logical nitrogen distillation, and in still, material obtains 809.5Kg white solid, content 99.2% after putting into square plate cooling.The liquid chromatogram of product is shown in Fig. 1, and infrared spectrogram is shown in Fig. 2.The phenylformic acid steamed, dewatering agent can directly overlap for lower batch after undue water.
Raw material used in the embodiment of the present invention is technical grade, and all at home market can be purchased and obtain.
Claims (8)
1. a production method for tribenzoin, is characterized in that described method is:
By glycerine and phenylformic acid under the existence of alkaline matter and dewatering agent, reflux divides water, carries out dehydration esterification reaction, and reaction terminates rear reaction solution aftertreatment and obtains tribenzoin; Described glycerine and benzoic amount of substance ratio are 1:3.0 ~ 3.3;
Described alkaline matter is the carbonate of basic metal or alkaline-earth metal, supercarbonate, oxyhydroxide or benzoate;
Described dewatering agent is one or more the mixing in toluene, dimethylbenzene, hexane, heptane, octane, nonane, decane, methylcyclohexane.
2. the method for claim 1, is characterized in that described alkaline matter is sodium carbonate, sodium bicarbonate, sodium hydroxide, Sodium Benzoate, salt of wormwood, saleratus, potassium hydroxide, potassium benzoate, calcium carbonate, calcium hydroxide or calcium benzoate.
3. the method for claim 1, is characterized in that the quality consumption of described alkaline matter is 0.1 ~ 3% of qualities of glycerin.
4. the method for claim 1, is characterized in that described dewatering agent is one or more the mixing in toluene, dimethylbenzene, octane, methylcyclohexane, n-decane.
5. the method for claim 1, is characterized in that the quality consumption of described dewatering agent is 3 ~ 15% of glycerine and benzoic total mass.
6. the method for claim 1, is characterized in that the temperature of described reflux water-dividing is 120 ~ 260 DEG C.
7. the method for claim 1, is characterized in that the temperature of described reflux water-dividing is 180 ~ 240 DEG C.
8. the method for claim 1, it is characterized in that described reaction solution post-treating method is: after reaction terminates, reaction solution Distillation recovery dewatering agent and phenylformic acid, the phenylformic acid that finally logical nitrogen distillation removing is residual, residuum cooling i.e. obtained tribenzoin.
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| CN201510634054.8A CN105348104A (en) | 2015-09-29 | 2015-09-29 | Production method of glycerin tribenzoate |
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| CN201510634054.8A CN105348104A (en) | 2015-09-29 | 2015-09-29 | Production method of glycerin tribenzoate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966895A (en) * | 2017-03-27 | 2017-07-21 | 北京恩泽福莱科技有限公司 | A kind of synthetic method of fragrant low carbon acid methyl esters |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0092613A1 (en) * | 1981-04-10 | 1983-11-02 | Uop Inc. | Process for separating esters of fatty and rosin acids |
| US5405992A (en) * | 1994-04-28 | 1995-04-11 | Uop | Process for concurrent esterification and separation using a simulated moving bed |
| JP2007153814A (en) * | 2005-12-06 | 2007-06-21 | Mitsubishi Chemicals Corp | Method for producing dicarboxylic acid diester |
| CN101575285A (en) * | 2009-04-29 | 2009-11-11 | 李普选 | Technical method for continuously producing fatty glyceride and special equipment thereof |
| CN102924273A (en) * | 2012-11-20 | 2013-02-13 | 江南大学 | Clean production process of polyatomic alcohol synthetic esters through reactor coupled simulated moving bed |
-
2015
- 2015-09-29 CN CN201510634054.8A patent/CN105348104A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0092613A1 (en) * | 1981-04-10 | 1983-11-02 | Uop Inc. | Process for separating esters of fatty and rosin acids |
| US5405992A (en) * | 1994-04-28 | 1995-04-11 | Uop | Process for concurrent esterification and separation using a simulated moving bed |
| JP2007153814A (en) * | 2005-12-06 | 2007-06-21 | Mitsubishi Chemicals Corp | Method for producing dicarboxylic acid diester |
| CN101575285A (en) * | 2009-04-29 | 2009-11-11 | 李普选 | Technical method for continuously producing fatty glyceride and special equipment thereof |
| CN102924273A (en) * | 2012-11-20 | 2013-02-13 | 江南大学 | Clean production process of polyatomic alcohol synthetic esters through reactor coupled simulated moving bed |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966895A (en) * | 2017-03-27 | 2017-07-21 | 北京恩泽福莱科技有限公司 | A kind of synthetic method of fragrant low carbon acid methyl esters |
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