CN104610210B - A kind of sodium dehydroacetate anhydride preparation method - Google Patents
A kind of sodium dehydroacetate anhydride preparation method Download PDFInfo
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- CN104610210B CN104610210B CN201510061262.3A CN201510061262A CN104610210B CN 104610210 B CN104610210 B CN 104610210B CN 201510061262 A CN201510061262 A CN 201510061262A CN 104610210 B CN104610210 B CN 104610210B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
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- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
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Abstract
The present invention relates to a kind of sodium dehydroacetate anhydride preparation method.At 15~40 DEG C, under stirring action, to dehydroacetic acid sodium-hydrate is added in organic solvent, suspension is formed, stirred 0.5~4 hour；Gained suspension is separated, is dried, obtain sodium dehydroacetate anhydride.In order to improve yield, before suspension is separated, suspension can be cooled down, temperature is reduced to 5~10 DEG C.Sodium dehydroacetate anhydride is compared with monohydrate obtained in the application method, the brilliant habit of product is obviously improved, surface is more smooth, filtration drying easily is carried out, the purity of product is also improved, 300 μm or so of main granularity, product purity more than 99%, process yield 70% or so, strengthens anti-corrosion/fresh-keeping effect, can better meet the purposes that sodium dehydroacetate is applied in food and medicine industry.
Description
Technical field
The invention belongs to Chemical Engineering crystallization technique field, more particularly to a kind of sodium dehydroacetate anhydride preparation method.
Background technology
With the continuous improvement of living standard, people become more concerned with the shelf-life of food and the problem of quality.Food exists
During production storage, it is highly prone to the invasion and attack of the microorganisms such as bacterium, yeast, mould and causes the mouldy corruption of food, therefore must
The measure of some anti-corrosive fresh-keepings must be taken to extend the shelf life and shelf life, nutrition loss is reduced.Can wherein compare has
The method for playing to effect anti-corrosive fresh-keeping effect is to use chemical preservative.Sodium Benzoate, nipagin esters, potassium sorbate, calcium propionate
Etc. being the food mould-proof preservative that uses of tradition, but its bacteriostasis in actual applications, antibacterial range is influenceed larger by pH,
Some also have the weak points such as peculiar smell.
Sodium dehydroacetate be FAO (Food and Agriculture Organization of the United Nation) (FAO) and the World Health Organization (WHO) accreditation it is a kind of safety-type, extensively
Spectral pattern, the extremely strong foods/feeds of bacteriostasis are mould proof, antisepsis antistaling agent, be after Sodium Benzoate, nipagin esters, potassium sorbate it
Afterwards, substituted type food and feed anticorrosive mildewproof antistaling agent of new generation.
Sodium dehydroacetate (Sodium dehydroacetate), scientific name dehydroactic acid sodium, (1- hydroxyls are sub- for chemical name 3-
Methyl) -6- methyl isophthalic acids, 2- pyrans -2,4 (3H)-diketone sodium, molecular formula is C8H7NaO4, molecular weight is 190.13, chemical constitution
Formula is as follows：
In annual meeting in 1998, Food Additives Used in China technical committee for standardization (TCST) discusses and is arranged by by sodium dehydroacetate
It is the new varieties of food additives, for food provides the effect such as mould proof, anti-corrosion, fresh-keeping.
The sodium dehydroacetate of current patent literature is related to anhydride and monohydrate two types, wherein monohydrate
Theoretical water content be 8.66%.
Patent CN100445278 elaborates a kind of method for synthesizing sodium dehydroacetate, using dehydroactic acid and NaOH
Or sodium carbonate is raw material, by raw material mixed grinding, direct reaction obtains dehydroacetic acid sodium-hydrate under solid-state.Patent
CN101475550 elaborates the method for preparing high-purity dehydroacetic acid sodium-hydrate, by the anti-of dehydroactic acid and NaOH
Feed liquid is answered to produce product by the method for crystallisation by cooling, the product water content for obtaining shows that it is a hydration 8.5~10.0%
Thing.Patent CN102558124 elaborates a kind of food-grade dehydroacetic acid sodium-hydrate (C8H7NaO4·H2O preparation method),
The reaction material liquid of dehydroactic acid and NaOH is decolourized, after being concentrated into a small amount of solid appearance, crystallisation by cooling in beaker is gone to,
Absolute ethanol washing can obtain the dehydroacetic acid sodium-hydrate of high-purity after the crystal suction filtration for obtaining.There is work in these methods
Skill is complicated, Granularity Distribution is poor, coalescence is serious, poor fluidity, purity low (98% or so) the problems such as, commercially available sodium dehydroacetate
As shown in Figure 1, its main granularity is small for monohydrate crystal electromicroscopic photograph, only 30 μm or so.
In method made above, reaction system generates sodium dehydroacetate, due to only containing water in raw material, by grinding or
Crystal obtained in solution crystallisation by cooling mode is dehydroacetic acid sodium-hydrate, it is impossible to obtain sodium dehydroacetate anhydride.Mesh
What preceding food service industry was mainly used is the water thing of sodium dehydroacetate one, and the active ingredient of food additives is that sodium dehydroacetate is anhydrous
Thing.
Therefore, it is necessary to a kind of preparation method of sodium dehydroacetate anhydride is developed, to improve the purity of product, improve and produce
The brilliant habit of product, strengthens anti-corrosion/fresh-keeping using effect, meets application of the sodium dehydroacetate in food and medicine industry.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of preparation method of sodium dehydroacetate anhydride, obtain
Sodium dehydroacetate anhydride granularity is big and is evenly distributed, purity is high, good fluidity, easy filtration washing, preparation method operation letter
It is single.
The preparation method of sodium dehydroacetate anhydride of the present invention, it is characterized in that：
At 15~40 DEG C, under stirring action, to dehydroacetic acid sodium-hydrate is added in organic solvent, suspension is formed,
Stirring 0.5~4 hour；Gained suspension is separated, is dried, obtain sodium dehydroacetate anhydride.
In described method, in order to further improve yield, before suspension is separated, suspension can be carried out cold
But, temperature is reduced to 5~10 DEG C.
In described method for crystallising, the temperature that dehydroacetic acid sodium-hydrate is dissolved in organic solvent is preferably 20~30 DEG C.
One or more mixing that described organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, ethyl acetate or acetone are molten
Agent；Organic solvent is 20~4 with the mass ratio of the water thing of sodium dehydroacetate one：1；The mother liquor obtained after suspension is separated is recycled
Utilize.
In described method, drying is carried out at 30~60 DEG C.
The preparation method of sodium dehydroacetate anhydride of the present invention, its advantage is operating condition simple and easy to control, is passed through
The stereoscan photograph of accompanying drawing 2 is it can be confirmed that sodium dehydroacetate anhydride product crystallinity is high, plane of crystal is bright and clean, product is easy
Filtering, crystal size are big, 300 μm or so of main granularity, product purity more than 99%；Process yield 70% or so.
The application gained sodium dehydroacetate anhydride product is tested by TGA and found, as shown in Figure 3, product does not find
Dehydration weightlessness, fusing is started at 295 DEG C and is decomposed, therefore may certify that the product for obtaining is sodium dehydroacetate anhydride.
The mechanism of polymorphic transformation is generally divided into solvent mediation and turns brilliant and brilliant two class of solid phase turn.Wherein solvent mediation turns crystalline substance is
Refer to that the larger metastable crystal formation of solubility dissolves first in certain solvent, is then changed into the less stable crystal form of solubility and ties
The process that partial crystallization goes out.It is different crystal forms difference in chemical potential or concentration difference in the solution that solvent mediation turns brilliant motive force.Solvent
Mediation turns crystalline substance can be divided into three steps：(1) dissolving of metastable crystal formation, solution concentration reaches the solubility of metastable crystal formation and is higher than steady
Determine the solubility of crystal formation, i.e., solution concentration now is saturation relative to stable crystal form；(2) nucleation of stable crystal form, solution
In molecule by more stablize in the way of arrange；(3) growth of stable crystal form, with the dissolving of metastable crystal formation, stable crystal form
Nucleus constantly grows.Dehydroacetic acid sodium-hydrate is brilliant for anhydride is typical solvent mediation in the transfer of above organic solvent
Turn brilliant process, its operating process is simple, but internal mechanism is complicated.Using the anhydride product that this solvent mediation rotating crystal method is obtained
Any surface finish, crystal size are larger, product is purity raising, the peace of anti-corrosive fresh-keeping beneficial to filtration drying, the content attenuating of impurity
Full property and effect are more excellent.
In literature method, sodium dehydroacetate is generated after reaction in the solution, due to containing water in system, through supercooling knot
The prepared dehydroacetic acid sodium-hydrate product of crystalline substance, it is impossible to obtain sodium dehydroacetate anhydride.What current food service industry was mainly used
It is dehydroacetic acid sodium-hydrate, and the active ingredient of food additives is sodium dehydroacetate anhydride, due to current production
The purity of dehydroacetic acid sodium-hydrate is low and crystal in it is big containing 8.66% moisture, the amount using required product, while
Introducing a certain amount of impurity will reduce the validity of anti-corrosive fresh-keeping, be less useful for the safety of food and medicine.The application method system
Compared with monohydrate, the brilliant habit of product is obviously improved the sodium dehydroacetate anhydride for obtaining, and surface is more smooth, easily carries out
It is filtered dry dry, the purity of product is also improved, 300 μm or so of main granularity, product purity more than 99%, process yield 70% is left
The right side, strengthens anti-corrosion/fresh-keeping effect, can better meet the purposes that sodium dehydroacetate is applied in food and medicine industry.
Brief description of the drawings
Fig. 1：Commercially available dehydroacetic acid sodium-hydrate stereoscan photograph (amplifying 1000 times)；
Fig. 2：The stereoscan photograph (amplifying 150 times) of sodium dehydroacetate anhydride；
Fig. 3：The thermogravimetric collection of illustrative plates of sodium dehydroacetate anhydride.
Specific embodiment
The present invention is explained by following examples, but is not limited thereto：
Embodiment 1：
Ethanol 50g is taken, stirring adds dehydroacetic acid sodium-hydrate 5g, forms suspension, in constant temperature stirring 2h at 15 DEG C,
Filtering suspension liquid, products obtained therefrom dries 10h at 40 DEG C, obtains sodium dehydroacetate anhydride 3.39g, raw material give money as a gift after receipts
Rate 74.23%, product crystallinity is high, purity 99.3%, 318 μm of main granularity, and epigranular.ESEM is as shown in Fig. 2 produce
The thermogravimetric collection of illustrative plates of product is as shown in Figure 3.
Embodiment 2：
Methyl alcohol 20g is taken, stirring adds dehydroacetic acid sodium-hydrate 5g, forms suspension, in constant temperature stirring 3h at 25 DEG C,
Then 10 DEG C are cooled to the rate of temperature fall of 8 DEG C/h, constant temperature stirring 0.5h, filters suspension liquid, products obtained therefrom at 10 DEG C
Dry 12h at 30 DEG C, obtain sodium dehydroacetate anhydride 2.29g, raw material give money as a gift after yield 50.14%, product is very white, knot
Brilliant degree is high, purity 99.1%, 296 μm of main granularity and epigranular.
Embodiment 3：
Acetone 100g is taken, stirring adds dehydroacetic acid sodium-hydrate 5g, forms suspension, is stirred in constant temperature at 40 DEG C
4h, filters suspension liquid, and products obtained therefrom dries 12h, sodium dehydroacetate anhydride 3.35g obtained, after raw material is given money as a gift at 30 DEG C
Yield 73.35%, product crystallinity is high, purity purity 99.1%, and granularity is big and uniform.
Embodiment 4：
Ethanol 50g is taken, stirring adds dehydroacetic acid sodium-hydrate 5g, forms suspension, is stirred in constant temperature at 30 DEG C
0.5h, then the rate of temperature fall of 10 DEG C/h be cooled to 7 DEG C, at 7 DEG C constant temperature stirring 0.5h, filter suspension liquid, gained produce
Product dry 8h at 50 DEG C, obtain sodium dehydroacetate anhydride 3.59g, raw material give money as a gift after yield 78.61%, product crystallinity
Height, purity 99.2%, 318 μm of main granularity and epigranular.
Embodiment 5：
Ethyl acetate 75g is taken, stirring adds dehydroacetic acid sodium-hydrate 5g, forms suspension, is stirred in constant temperature at 20 DEG C
2h is mixed, then the rate of temperature fall of 10 DEG C/h is cooled to 5 DEG C, the constant temperature stirring 0.5h at 5 DEG C filters suspension liquid, and gained is produced
Product dry 6h at 60 DEG C, obtain sodium dehydroacetate anhydride 3.52g, raw material give money as a gift after yield 77.07%, product crystallinity
Height, purity 99.3%, 306 μm of main granularity and epigranular.
Embodiment 6：
Methyl alcohol and each 12.5g of ethyl acetate are taken, stirring adds dehydroacetic acid sodium-hydrate 5g, suspension is formed, in 20
Constant temperature stirring 4h, filters suspension liquid at DEG C, and products obtained therefrom dries 12h, obtains sodium dehydroacetate anhydride at 30 DEG C
2.45g, raw material give money as a gift after yield 53.65%, product is very white, and crystallinity is high, purity 99.2%, 310 μm of main granularity, and granularity is equal
It is even.
The sodium dehydroacetate anhydride preparation method that the present invention is disclosed and proposed, those skilled in the art can be by using for reference this
The links such as literary content, appropriate feed change, technological parameter are tested.The method of the present invention is carried out by preferred embodiments with product
Description, person skilled can be not substantially being departed from present invention, spirit and scope to method described herein and product
Product are modified or appropriate change realizes the technology of the present invention with combining.In particular, all similar replacements
It is it will be apparent that they are considered as being included in spirit of the invention, scope and content with changing for this technology personnel
In.
Claims (4)
1. a kind of preparation method of sodium dehydroacetate anhydride, it is characterized in that, at 15~40 DEG C, under stirring action, to organic molten
Dehydroacetic acid sodium-hydrate is added in agent, suspension is formed, stirred 0.5~4 hour；Gained suspension is separated, is dried, obtained
To sodium dehydroacetate anhydride；
Described organic solvent is selected from one or more mixed solvents in methyl alcohol, ethanol, propyl alcohol, ethyl acetate or acetone；Institute
The drying stated is carried out at 30~60 DEG C.
2. preparation method as claimed in claim 1, it is characterized in that, before suspension is separated, suspension is cooled down,
Temperature is reduced to 5~10 DEG C.
3. preparation method as claimed in claim 1, it is characterized in that, to adding dehydroacetic acid sodium-hydrate in organic solvent
Temperature is preferably 20~30 DEG C.
4. preparation method as claimed in claim 1, it is characterized in that, organic solvent is with the mass ratio of the water thing of sodium dehydroacetate one
20~4：1.
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| CN107027759A (en) * | 2017-05-31 | 2017-08-11 | 贵阳时代沃顿科技有限公司 | A kind of mould proof protective agent of the NEW TYPE OF COMPOSITE of reverse osmosis membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558124A (en) * | 2011-12-23 | 2012-07-11 | 蚌埠丰原医药科技发展有限公司 | Method for preparing food-grade sodium dehydroacetate |
| CN103450131A (en) * | 2012-12-21 | 2013-12-18 | 南通醋酸化工股份有限公司 | Preparation method of dehydroacetic acid and sodium salt thereof |
| CN103788041A (en) * | 2014-03-25 | 2014-05-14 | 南通奥凯生物技术开发有限公司 | Method for purifying sodium dehydroacetate |
| CN103864739A (en) * | 2014-03-17 | 2014-06-18 | 天津大学 | Sodium dehydroacetate dihydrate and preparation method thereof |
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| UA83504C2 (en) * | 2003-09-04 | 2008-07-25 | Селджин Корпорейшн | Polymorphic forms of 3-(4-amino-1-oxo-1,3 dihydro-isoindol-2-yl)-piperidine-2,6-dione |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558124A (en) * | 2011-12-23 | 2012-07-11 | 蚌埠丰原医药科技发展有限公司 | Method for preparing food-grade sodium dehydroacetate |
| CN103450131A (en) * | 2012-12-21 | 2013-12-18 | 南通醋酸化工股份有限公司 | Preparation method of dehydroacetic acid and sodium salt thereof |
| CN103864739A (en) * | 2014-03-17 | 2014-06-18 | 天津大学 | Sodium dehydroacetate dihydrate and preparation method thereof |
| CN103788041A (en) * | 2014-03-25 | 2014-05-14 | 南通奥凯生物技术开发有限公司 | Method for purifying sodium dehydroacetate |
Non-Patent Citations (1)
| Title |
|---|
| 固相反应生产脱氢醋酸钠物料配比及球磨介质的优化;仝其根 等.;《北京工商大学学报(自然科学版)》;20110531;第29卷(第3期);38-44 * |
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