CN103450024A - Preparation method of glycerol monostearate p-hydroxybenzoate - Google Patents
Preparation method of glycerol monostearate p-hydroxybenzoate Download PDFInfo
- Publication number
- CN103450024A CN103450024A CN2013104054379A CN201310405437A CN103450024A CN 103450024 A CN103450024 A CN 103450024A CN 2013104054379 A CN2013104054379 A CN 2013104054379A CN 201310405437 A CN201310405437 A CN 201310405437A CN 103450024 A CN103450024 A CN 103450024A
- Authority
- CN
- China
- Prior art keywords
- hydroxybenzoic acid
- preparation
- product
- acid mono
- glycerides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a preparation method of glycerol monostearate p-hydroxybenzoate, which comprises the following steps: (1) proportionally weighing sodium p-hydroxybenzoate and epoxy chloropropane; adopting tetrabutylammonium bromide as a phase transfer catalyst, adding a proper amount of solvent, and reacting in a sealed constant-temperature stirring reactor; and cooling to obtain an intermediate product glycidyl ester p-hydroxybenzoate; (2) measuring the prepared sulfuric acid solution, pouring into a container with the intermediate product obtained by the step (1), putting the container into a water bath kettle for a constant-temperature heating stirring reaction, and flushing a solid phase by use of deionized water to remove residual impurities; and finally transferring the reaction product in the container into watch glass, and drying and cooling to obtain a glycerol monostearate p-hydroxybenzoate product. By adopting the method disclosed by the invention, the obtained product has high purity and yield over 99.9% and 95% respectively; the operation is simple and convenient, the product is pure, and no meta-position byproduct is generated; the method has a great prospect in industrial application and deserves wide popularization and application.
Description
One, technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of preparation method of the P-hydroxybenzoic acid mono-glycerides as sanitas, emulsifying agent.
Two, background technology
P-Hydroxybenzoate is that nipagin esters is one of three large broad spectrum food preservativess of generally acknowledging in the world, with Sodium Benzoate, with potassium sorbate, compare, it mainly has good antimicrobial effect, and applicable PH scope is wide, the advantages such as toxic side effect is little, and use cost is low and easy to use.
The direactive glyceride analog derivative is a kind of polyol-based non-ionic surfactant, and direactive glyceride is a kind of of output maximum in emulsifying agent, has emulsification, dispersion, solubilising, the premium properties such as wetting, is widely used in the departments such as food, daily use chemicals, medicine, plastics.
The P-hydroxybenzoic acid direactive glyceride has anticorrosion and two kinds of functions of emulsification concurrently, and research at present seldom.The preparation method of mono-glycerides has direct esterification, and the direct transformation efficiency of this method is lower, also needs to carry out molecular distillation and extraction etc. and is separated; The Racemic glycidol method, utilize Racemic glycidol to be reacted with acid, and yield is not very high, and, in industrial production, the Racemic glycidol raw material is difficult to obtain.The chemical group protection method, two hydroxyl condensation dehydrations on glycerol molecule generate isobutyl fork glycerine, then change into isobutyl fork direactive glyceride with acid esters, finally divide and take off isobutyl fork blocking group, and this method raw material is easy to get, and product purity is high, but the aftertreatment complexity.Enzyme directionally hydrolyzing method prepares direactive glyceride at a lower temperature, and product color is better, and main drawback is the lipase selling at exorbitant prices, is difficult to obtain the easier inactivation of enzyme.
Three, summary of the invention
The purpose of this invention is to provide a kind of preparation method that can effectively overcome the P-hydroxybenzoic acid mono-glycerides of the many deficiencies that have the preparation method now.
For achieving the above object, the technical solution used in the present invention is: the method comprises the steps:
1. take in proportion P-hydroxybenzoic acid sodium and epoxy chloropropane, take Tetrabutyl amonium bromide as phase-transfer catalyst, add appropriate solvent, react in the stirred reactor of sealed thermostat, obtain intermediate product after cooling---the P-hydroxybenzoic acid glycidyl ester;
2. measure the sulphuric acid soln prepared, pour into and fill step 1. in the container of gained intermediate product, after container being put into to water-bath thermostatically heating stirring reaction again, use the deionized water rinsing solid phase, remove residual impurity, finally the reaction product in container is transferred in watch-glass, obtains P-hydroxybenzoic acid mono-glycerides product after Drying and cooling.
The mol ratio of above-mentioned material is P-hydroxybenzoic acid sodium: epoxy chloropropane: solvent: sulfuric acid=0.8-1.0:1.0-4.0:2.0-5.0:0.03-0.08.
The 1.5-2.5% that the consumption of above-mentioned Tetrabutyl amonium bromide is P-hydroxybenzoic acid sodium quality.
Above-mentioned solvent is toluene, dimethylbenzene or benzyl chloride.
The concentration of above-mentioned sulphuric acid soln is 0.02-0.04mol/L.
Above-mentioned steps 1. middle temperature of reaction is 110-120 ℃.
1. the middle reaction times is 100-120 minute to above-mentioned steps.
Above-mentioned steps temperature of reaction 2. is 80-100 ℃.
2. the middle reaction times is 50-60 minute to above-mentioned steps.
The present invention is that to take P-hydroxybenzoic acid sodium and epoxy chloropropane in solvent be raw material, adopts phase-transfer catalyst, prepares intermediate product P-hydroxybenzoic acid glycidyl ester, then under acidic conditions, its ring opening hydrolysis is prepared to the P-hydroxybenzoic acid direactive glyceride.Purity and the yield of the product that the inventive method obtains are high, can reach respectively more than 99.9% and 95%, and simple to operation, product is pure, and between not having, the position by product does not generate, and has good prospects for commercial application, are worth applying widely.
Four, accompanying drawing explanation
Fig. 1 is 4000-2000cm
-1the infrared spectrum of P-hydroxybenzoic acid direactive glyceride;
Fig. 2 is 2000-500cm
-1the infrared spectrum of P-hydroxybenzoic acid direactive glyceride.
Five, embodiment
Embodiment 1
1. take 2g P-hydroxybenzoic acid sodium, 0.03g Tetrabutyl amonium bromide, 2ml epoxy chloropropane and 4.2ml dimethylbenzene join in the stainless steel reactor with the sealing of magnetic agitation, at 115 ℃ of temperature the reaction 110 minutes after by reactor cooling, open, liquid phase (comprising unreacted chlorocyclopropane and a large amount of solvent) is poured in fixing waste liquid bottle, given over to the rear distillating recovering solvent of reaction end and use.By solid phase with transfer in 50 ml small beakers after rotor separates standby.
2. measure the dilution heat of sulfuric acid 20ml of 0.02mol/L, pour in the small beaker that intermediate product is housed, stir 50 minutes under 80 ℃ of heating conditions, after reaction finishes, by a large amount of deionized water rinsing solid phases, make oily and be with the cooling hardening of sticking solid phase, wash away residual impurity (acid, sodium-chlor, catalyzer etc.), the material obtained is now brown viscosity oily, transfer them in clean container, under 100 ℃, dry after 12 hours and can obtain target product.
1. take 2g P-hydroxybenzoic acid sodium, 0.04g Tetrabutyl amonium bromide, 3ml epoxy chloropropane and 5.6ml dimethylbenzene join in the stainless steel reactor with the sealing of magnetic agitation, at 115 ℃ of temperature the reaction 110 minutes after by reactor cooling, open, liquid phase (comprising unreacted chlorocyclopropane and a large amount of solvent) is poured in fixing waste liquid bottle, given over to the rear distillating recovering solvent of reaction end and use.By solid phase with transfer in 50 ml small beakers after rotor separates standby.
2. measure the dilution heat of sulfuric acid 20ml of 0.03mol/L, pour in the small beaker that intermediate product is housed, stir 50 minutes under 80 ℃ of heating conditions, after reaction finishes, by a large amount of deionized water rinsing solid phases, make oily and be with the cooling hardening of sticking solid phase, wash away residual impurity (acid, sodium-chlor, catalyzer etc.), the material obtained is now brown viscosity oily, transfer them in clean container, under 100 ℃, dry after 12 hours and can obtain target product.
1. take 2g P-hydroxybenzoic acid sodium, 0.05g Tetrabutyl amonium bromide, 3.5ml epoxy chloropropane and 7.0ml dimethylbenzene join in the stainless steel reactor with the sealing of magnetic agitation, at 115 ℃ of temperature the reaction 110 minutes after by reactor cooling, open, liquid phase (comprising unreacted chlorocyclopropane and a large amount of solvent) is poured in fixing waste liquid bottle, given over to the rear distillating recovering solvent of reaction end and use.By solid phase with transfer in 50 ml small beakers after rotor separates standby.
2. measure the dilution heat of sulfuric acid 20ml of 0.04mol/L, pour in the small beaker that intermediate product is housed, stir 50 minutes under 80 ℃ of heating conditions, after reaction finishes, by a large amount of deionized water rinsing solid phases, make oily and be with the cooling hardening of sticking solid phase, wash away residual impurity (acid, sodium-chlor, catalyzer etc.), the material obtained is now brown viscosity oily, transfer them in clean container, under 100 ℃, dry after 12 hours and can obtain target product.
1. take 2g P-hydroxybenzoic acid sodium, 0.04g Tetrabutyl amonium bromide, 2.5ml epoxy chloropropane and 7.0ml dimethylbenzene join in the stainless steel reactor with the sealing of magnetic agitation, at 115 ℃ of temperature the reaction 110 minutes after by reactor cooling, open, liquid phase (comprising unreacted chlorocyclopropane and a large amount of solvent) is poured in fixing waste liquid bottle, given over to the rear distillating recovering solvent of reaction end and use.By solid phase with transfer in 50 ml small beakers after rotor separates standby.
2. measure the dilution heat of sulfuric acid 20ml of 0.02mol/L, pour in the small beaker that intermediate product is housed, stir 50 minutes under 80 ℃ of heating conditions, after reaction finishes, by a large amount of deionized water rinsing solid phases, make oily and be with the cooling hardening of sticking solid phase, wash away residual impurity (acid, sodium-chlor, catalyzer etc.), the material obtained is now brown viscosity oily, transfer them in clean container, under 100 ℃, dry after 12 hours and can obtain target product.
As shown in Figure 1 and Figure 2, the vibration peak that peak 1 is hydrogen on phenyl ring, peak 6, the vibration that peak 7 is C=C in phenyl ring, peak 16 is characteristic peak when para-orientation occurs on phenyl ring, can illustrate that phenyl ring exists and is para-orientation.The characteristic peak that peak 2 is hydroxyl, the characteristic peak that 10， peak, peak 13 is phenolic hydroxyl group, can determine that functional group is phenolic hydroxyl group.The characteristic peak that peak 2 is hydroxyl, the in plane vibration that peak 9 is alcoholic extract hydroxyl group, the characteristic peak that peak 13 is secondary alcohol, the characteristic peak that peak 14 is primary alconol, illustrate functional group's primary alconol, the existence of secondary alcohol.Peak 3, peak 4, the vibration performance peak that peak 8 is C-C, prove and have C-C.The characteristic peak that peak 5 is C=O in ester bond, 11He peak, peak 12 is characteristic peaks of C-O-C, can determine the existence of ester group.
Claims (9)
1. the preparation method of a P-hydroxybenzoic acid mono-glycerides, the method comprises the steps:
1. take in proportion P-hydroxybenzoic acid sodium and epoxy chloropropane, take Tetrabutyl amonium bromide as phase-transfer catalyst, add appropriate solvent, react in the stirred reactor of sealed thermostat, obtain intermediate product after cooling---the P-hydroxybenzoic acid glycidyl ester;
2. measure the sulphuric acid soln prepared, pour into and fill step 1. in the container of gained intermediate product, after container being put into to water-bath thermostatically heating stirring reaction again, use the deionized water rinsing solid phase, remove residual impurity, finally the reaction product in container is transferred in watch-glass, obtains P-hydroxybenzoic acid mono-glycerides product after Drying and cooling.
2. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1, it is characterized in that: the mol ratio of described material is P-hydroxybenzoic acid sodium: epoxy chloropropane: solvent: sulfuric acid=0.8-1.0:1.0-4.0:2.0-5.0:0.03-0.08.
3. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1 and 2, is characterized in that: the 1.5-2.5% that the consumption of described Tetrabutyl amonium bromide is P-hydroxybenzoic acid sodium quality.
4. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1 and 2, it is characterized in that: described solvent is toluene, dimethylbenzene or benzyl chloride.
5. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1 and 2, it is characterized in that: the concentration of described sulphuric acid soln is 0.02-0.04mol/L.
6. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1 and 2 is characterized in that: described step 1. in temperature of reaction be 110-120 ℃.
7. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1 and 2 is characterized in that: described step 1. in the reaction times be 100-120 minute.
8. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1 and 2, it is characterized in that: described step temperature of reaction 2. is 80-100 ℃.
9. the preparation method of a kind of P-hydroxybenzoic acid mono-glycerides according to claim 1 and 2 is characterized in that: described step 2. in the reaction times be 50-60 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104054379A CN103450024A (en) | 2013-09-09 | 2013-09-09 | Preparation method of glycerol monostearate p-hydroxybenzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104054379A CN103450024A (en) | 2013-09-09 | 2013-09-09 | Preparation method of glycerol monostearate p-hydroxybenzoate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103450024A true CN103450024A (en) | 2013-12-18 |
Family
ID=49732920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013104054379A Pending CN103450024A (en) | 2013-09-09 | 2013-09-09 | Preparation method of glycerol monostearate p-hydroxybenzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103450024A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141270A (en) * | 2017-07-07 | 2017-09-08 | 湖南文理学院 | A kind of preparation method of hydroxybenzoic acid ethylene oxidic ester and its application in preparing rich in epoxy-based polymerization thing |
| CN108148485A (en) * | 2018-01-13 | 2018-06-12 | 常州大学 | A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating |
| CN109851503A (en) * | 2019-01-30 | 2019-06-07 | 天津现代职业技术学院 | A kind of method that water phase prepares citric acid mono fatty acid glyceride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1746150A (en) * | 2005-08-31 | 2006-03-15 | 四川大学 | Preparation of benzoyl oxy-aldehyde |
-
2013
- 2013-09-09 CN CN2013104054379A patent/CN103450024A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1746150A (en) * | 2005-08-31 | 2006-03-15 | 四川大学 | Preparation of benzoyl oxy-aldehyde |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141270A (en) * | 2017-07-07 | 2017-09-08 | 湖南文理学院 | A kind of preparation method of hydroxybenzoic acid ethylene oxidic ester and its application in preparing rich in epoxy-based polymerization thing |
| CN108148485A (en) * | 2018-01-13 | 2018-06-12 | 常州大学 | A kind of heatproof shock resistance graphene epoxy anticorrosion composite coating |
| CN109851503A (en) * | 2019-01-30 | 2019-06-07 | 天津现代职业技术学院 | A kind of method that water phase prepares citric acid mono fatty acid glyceride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Han et al. | Preparation of biodiesel from waste oils catalyzed by a Brønsted acidic ionic liquid | |
| CN102295541B (en) | Preparation method of 3,3-dimethyl butyraldehyde | |
| CN103450024A (en) | Preparation method of glycerol monostearate p-hydroxybenzoate | |
| CN104744237A (en) | Preparation method of 2-(4-bromomethylphenyl) propionic acid | |
| CN102020572A (en) | Method for preparing tetrabutyl ammonium bromide | |
| CN103012074B (en) | Prepare the method for aromatic methyl ether compound | |
| CN106478381B (en) | A method of bis ether fluorenes is prepared by catalyzing epoxyethane | |
| CN105126905B (en) | A kind of ionic liquid and preparation method and application of synthesizing long-chain alkyl glucosides | |
| CN104478681B (en) | The method for hydrolysis of chloro-3, the 3-dimethyl butyrate yl acetates of a kind of 1- | |
| CN102267911A (en) | Synthesis method of methyl salicylate | |
| CN103525874A (en) | Method for preparing dimethyl carbonate | |
| CN102180792B (en) | Method for preparing aspirin | |
| CN103508916B (en) | Preparation technology for paracetamol | |
| CN102030665A (en) | Method for preparing tetrabutylammonium hydroxide | |
| CN103468755B (en) | Method for enzymatic synthesis of phenethyl caffeate in complexation extraction agent/ionic liquid system | |
| CN101531577A (en) | A method for preparing 3, 4-dihydroxy benzaldehyde in ionic liquid with one-pot method | |
| CN101703906B (en) | Cationic gemini surfactant containing tri-ester groups and preparation method thereof | |
| CN103420844B (en) | Process for preparing 4,4'-diaminodiphenylmethane through condensation of acidic ionic liquid catalytic aniline and formaldehyde | |
| CN102924967A (en) | Industrialization method for improving purity of lycopene oil resin | |
| CN103554019B (en) | A kind of synthetic method of tilbroquinol | |
| CN101914016A (en) | Quick preparation method of glycerin monostearate | |
| CN103265586B (en) | A kind of method being prepared Lauryl.beta.-maltoside by maltose | |
| CN105647984A (en) | Method for preparing high-purity pinolenic acid by specific enzyme process | |
| CN102399191B (en) | Method for synthesizing analgin | |
| CN101906035A (en) | Refining method of high-purity butyl stearate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C05 | Deemed withdrawal (patent law before 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131218 |