CN101475592A - Method for improving content of VC-2-tripolyphosphate in VC-2-polyphosphate - Google Patents
Method for improving content of VC-2-tripolyphosphate in VC-2-polyphosphate Download PDFInfo
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- CN101475592A CN101475592A CNA2009100954998A CN200910095499A CN101475592A CN 101475592 A CN101475592 A CN 101475592A CN A2009100954998 A CNA2009100954998 A CN A2009100954998A CN 200910095499 A CN200910095499 A CN 200910095499A CN 101475592 A CN101475592 A CN 101475592A
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- reaction solution
- tripolyphosphate
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- poly phosphate
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Abstract
The invention discloses a method for increasing the content of VC-2-tripolyphosphate in VC-2-polyphosphonate, which comprises the following steps: 1) adding water, L- ascorbic acid, sodium trimetaphosphate and a catalyst in to a reactor to obtain a reaction solution, reacting the reaction solution at 25 to 30 DEG C and keeping the pH value of the reaction solution during reduction at 8 to 10; and stopping the reaction when the pH value of the reaction solution is unstable; and 2) adjusting the pH value of reactants to be 7.5 to 8.5, filtering the reactants, adding an organic solvent into the obtained filtrate for precipitation, filtering the solution again and obtaining a filter cake; washing the filter cake with an organic solvent, drying and crushing the washed filter cake and obtaining the VC-2-polyphosphonate. The VC-2-polyphosphonate produced by the method has higher content of VC-2-tripolyphosphate.
Description
Technical field
The present invention relates to a kind of fodder additives synthesis technique, be specially adapted to V
CSynthesizing of-2-poly phosphate.
Background technology
The L-xitix (below write a Chinese character in simplified form V
C) be requisite nutritive substance in the growth of animal process, but most of animal self can not synthesize, and can only absorb from food.Hydroxyl on xitix the 2nd carbon atom has the unstable group of a tool enol-type structure.Very easily oxidized in feed processing, storage and use, tiring obviously descends.In order to guarantee V
CNot oxidized in feed processing, storage and use, the scientific research personnel is to V
COxidation-resistance carried out big quantity research, what be used for actual production mainly contains ethyl cellulose coating V
C, lipid acid parcel V
C, make V
C-2-sulfuric ester and V
C2-polyphosphate etc.
V
C-2-polyphosphate is with V
CGo up unsettled hydroxy esterification and generate phosphoric acid ester, reach oxidation resistant purpose.The most representative in polyphosphate is V
C-2-tripolyphosphate, its good stability, bioavailability height.V
C-2-tripolyphosphate (below write a Chinese character in simplified form AsTP) is the incipient a kind of high stability V in world market in recent years
CDerivative.In feed processing and storage process, air, heat, water, acid, alkali and enzyme etc. are all showed satisfactory stability as fodder additives for it; Has excellent compatibility with other fodder additivess; Behind the animal edible, under the phosphoesterase action, polymerized therein phosphoric acid ester can be formed V by progressively hydrolysis release substantially in vivo
C-2-two poly phosphates (below write a Chinese character in simplified form AsDP) and V
C-2-phosplate (below write a Chinese character in simplified form AsMP), to the last a phosphate group comes off V
CDissociated out.Thereby just has V in animal body
CBiological activity.It also contains the bioactive P that is easily absorbed by animal simultaneously, so this product one appearance, just is widely used in fodder industry very soon.AsTP meets U.S. FDA about the regulation of GRAS (It is generally accepted into safety) and the regulation of U.S.'s (21 of federal codes).But the present V that produces
CContain more V in the-2-poly phosphate product
C-2-phosplate, V
CLess (the V of-2-tripolyphosphate relative content
CThe high-content of-2-tripolyphosphate only is 10%), influenced the stability of product.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of raising V
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content is produced the V that produces with this method
CThe V that contains high level in the-2-poly phosphate
C-2-tripolyphosphate.
In order to solve the problems of the technologies described above, the invention provides a kind of raising V
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content may further comprise the steps successively:
1), in reaction vessel, add entry, L-xitix, Trisodium trimetaphosphate and catalyzer, reaction solution, described catalyzer is the divalent metal-salt; Reaction solution is reacted in 25～30 ℃, and the pH value of keeping reaction solution in the reaction process is 8～10; When the pH of reaction solution value stabilization is constant, stopped reaction; The mass ratio of Trisodium trimetaphosphate and L-xitix is 1.0～1.5:1, and the mass ratio of catalyzer and L-xitix is 0.05～0.1:1;
2), regulate above-mentioned steps 1) the pH value of gained reaction product is 7.5～8.5, filters, and adds organic solvent in the filtrate of gained, thereby the precipitation of separating out filter once more, must filter cake; Use the organic solvent washing filter cake, filtration cakes torrefaction, pulverizing after will washing promptly get product V again
C-2-poly phosphate.
As raising V of the present invention
CThe improvement of the method for VC-2-tripolyphosphate ester content in the-2-poly phosphate: the divalent metal-salt in the step 1) is calcium salt, manganese salt or magnesium salts; The mass ratio of water and L-xitix is 3～4:1; The pH value of utilizing interpolation milk of lime to keep reaction solution in the reaction process is 8～10.
As raising V of the present invention
CThe further improvements in methods of VC-2-tripolyphosphate ester content in the-2-poly phosphate: utilize hydrochloric acid or milk of lime to regulate the pH value step 2), used organic solvent is ethanol, methyl alcohol, acetone or Virahol etc.
In the method for the invention, L-xitix, Trisodium trimetaphosphate and catalyzer add in the entry under agitation condition, and being reflected under the agitation condition of step 1) carried out.Regulate and when line stabilization is constant, get final product stopped reaction when the pH of reaction solution value need not foreign object, the used time of this reaction is generally 30～60min.
The V that adopts the inventive method to produce
C-2-poly phosphate can significantly improve V wherein
CThe content of-2-tripolyphosphate, thus make the stability of product obviously improve.And method of the present invention has safe and reliable, simple operation and other advantages.
In order to prove the advantage of the inventive method, the contriver measures V respectively with high performance liquid phase and ultraviolet spectrophotometer
CV in the-2-poly phosphate
CThe content and the VC of-2-tripolyphosphate tire:
1, VC-triguaiacyl phosphate salts contg is measured: the HPLC method
A) instrument
Pump KONTRON420
Sampling system KONTRON400 self-actuated sampler
Post stainless steel 250 * 4.6mmi.d.
Detector UV KONTRON430
System ensemble SPECTRA-PHYSICS SP4270
B) working conditions
Stationary phase: the stainless steel tube of internal diameter 4.6mm, long 150mm charges into phase chromatography-use 18 silanized silica gels of particle diameter 5um.
Near stationary phase temperature: the temperature 25 ℃
Mobile phase: potassium primary phosphate 13.6g and TBAH test solution 4.0ml are dissolved in 950ml water, adjust PH=6.0 with the 2mol/L sodium hydroxide test solution, and water adds to 1000ml, add the 50ml acetonitrile and mix in the 950ml aforesaid liquid.
Flow velocity 1.0ml/min
Post is pressed 140-150bar
Wavelength 250nm
Sensitivity 0.5A
Sensitive time 0.5S
Injection volume 10ul
Chromatograph (separation) spectrum time length 30min
2, V
CTitration: take by weighing 0.2g (being accurate to 0.0001g) standard specimen and product respectively, be dissolved in the 50mL water, be settled to 100mL, measure its light absorption ratio and maximum absorption wavelength respectively, counting yield V with ultraviolet spectrophotometer
CContent, and be converted into contained V in the 100g product
CAmount (be V
CTire, unit is g).
After measured, adopt the content of VC-2-tripolyphosphate in the VC-2-poly phosphate that the inventive method produces can be up to 34.58%, and VC tire can be up to 31.78.
Embodiment
Embodiment 1, a kind of raising V
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content, carry out following steps successively:
1), put into 400mL water in the 2000mI of dried and clean four-hole boiling flask, controlled temperature is 25 ℃, adds 100g V down in agitation condition
C, 7g calcium chloride and 120g Trisodium trimetaphosphate, reaction solution; Above-mentioned reaction solution is reacted under agitation condition in 25 ℃, and to keep the pH value of reaction solution be 9 by adding milk of lime in the reaction process, stopped reaction when the pH value of reaction solution does not change, and the used reaction times is 60min at this moment.
2) being that 10% hydrochloric acid is regulated above-mentioned steps 1, with concentration) the pH value of gained reaction product is 7.5, filters, and separates out precipitation thereby add with the isopyknic ethanol of filtrate in the filtrate of gained, filters once more, gets filter cake; With the washing with alcohol filter cake of 500ml, the filtration cakes torrefaction after will washing again (in 105 ℃ of dryings 120 minutes), pulverize, promptly get product VC-2-poly phosphate.
After testing, above-mentioned V
CIn-2-the poly phosphate, V
CThe content of-2-tripolyphosphate is 34.58%, V
CThe content of-2-phosplate is 52.24%, V
CTire is 31.78.
This VC-phosphate ester salt product has the characteristics of good stability, after in 90 days, 100 ℃ processing of room temperature storage 10min, water, handling 60min respectively, its rate of retaining is respectively 96%, 97% and 95.8%, and the rate of retaining of coating VC is respectively 30.4%, 33.4% and 34.2% under the equal conditions.
Embodiment 2, a kind of raising V
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content, carry out following steps successively:
1, put into 300mL water in the 2000mI of dried and clean four-hole boiling flask, controlled temperature is 28 ℃, adds 100g V down in agitation condition
C, 5g Manganous chloride tetrahydrate and 150g Trisodium trimetaphosphate, reaction solution; Above-mentioned reaction solution is reacted under agitation condition in 28 ℃, and to keep the pH value of reaction solution be 8 by adding milk of lime in the reaction process, stopped reaction when the pH value of reaction solution does not change, and the used reaction times is 35min at this moment.
2), regulate above-mentioned steps 1 with milk of lime) the pH value of gained reaction product is 8.5, filters, and separates out precipitation thereby add with the isopyknic methyl alcohol of filtrate in the filtrate of gained, filters once more, gets filter cake; With the methanol wash filter cake of 500ml, filtration cakes torrefaction, pulverizing after will washing promptly get product VC-2-poly phosphate again.
After testing, above-mentioned V
CIn-2-the poly phosphate, V
CThe content of-2-tripolyphosphate is 34.09%, V
CThe content of-2-phosplate is 53.24%, V
CTire is 32.68.
Embodiment 3, a kind of raising V
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content, carry out following steps successively:
1, put into 350mL water in the 2000mI of dried and clean four-hole boiling flask, controlled temperature is 30 ℃, adds 100g V down in agitation condition
C, 10g magnesium chloride and 100g Trisodium trimetaphosphate, reaction solution; Above-mentioned reaction solution is reacted under agitation condition in 30 ℃, and to keep the pH value of reaction solution be 10 by adding milk of lime in the reaction process, stopped reaction when the pH value of reaction solution does not change, and the used reaction times is 40min at this moment.
2) being that 10% hydrochloric acid is regulated above-mentioned steps 1, with concentration) the pH value of gained reaction product is 8, filters, and separates out precipitation thereby add with the isopyknic acetone of filtrate in the filtrate of gained, filters once more, gets filter cake; With the washing with acetone filter cake of 500ml, filtration cakes torrefaction, pulverizing after will washing promptly get product VC-2-poly phosphate again.
After testing, above-mentioned V
CIn-2-the poly phosphate, V
CThe content of-2-tripolyphosphate is 23.94%, V
CThe content of-2-phosplate is 61.38%, V
CTire is 36.15.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (6)
1, a kind of raising V
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content is characterized in that may further comprise the steps successively:
1), in reaction vessel, add entry, L-xitix, Trisodium trimetaphosphate and catalyzer, reaction solution, described catalyzer is the divalent metal-salt; Reaction solution is reacted in 25～30 ℃, and the pH value of keeping reaction solution in the reaction process is 8～10; When the pH of reaction solution value stabilization is constant, stopped reaction; The mass ratio of described Trisodium trimetaphosphate and L-xitix is 1.0～1.5:1, and the mass ratio of catalyzer and L-xitix is 0.05～0.1:1;
2), regulate above-mentioned steps 1) the pH value of gained reaction product is 7.5～8.5, filters, and adds organic solvent in the filtrate of gained, thereby the precipitation of separating out filter once more, must filter cake; Use the organic solvent washing filter cake, filtration cakes torrefaction, pulverizing after will washing promptly get product V again
C-2-poly phosphate.
2, raising V according to claim 1
CThe method of VC-2-tripolyphosphate ester content in the-2-poly phosphate is characterized in that: the divalent metal-salt in the described step 1) is calcium salt, manganese salt or magnesium salts.
3, raising V according to claim 1 and 2
CThe method of VC-2-tripolyphosphate ester content in the-2-poly phosphate is characterized in that: the mass ratio of water and L-xitix is 3～4:1 in the described step 1).
4, raising V according to claim 3
CThe method of VC-2-tripolyphosphate ester content in the-2-poly phosphate is characterized in that: the organic solvent described step 2) is ethanol, methyl alcohol, acetone or Virahol.
5, raising V according to claim 4
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content is characterized in that: the pH value of utilizing interpolation milk of lime to keep reaction solution in the reaction process of described step 1) is 8～10.
6, raising V according to claim 3
CV in the-2-poly phosphate
CThe method of-2-tripolyphosphate ester content is characterized in that: utilize hydrochloric acid or milk of lime to regulate the pH value described step 2).
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100954998A CN101475592B (en) | 2009-01-19 | 2009-01-19 | Method for improving content of Vc-2-tripolyphosphate in Vc-2-polyphosphate |
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|---|---|---|---|
| CN2009100954998A CN101475592B (en) | 2009-01-19 | 2009-01-19 | Method for improving content of Vc-2-tripolyphosphate in Vc-2-polyphosphate |
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| CN101475592A true CN101475592A (en) | 2009-07-08 |
| CN101475592B CN101475592B (en) | 2012-02-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104304680A (en) * | 2014-10-28 | 2015-01-28 | 安徽天寅生物科技有限公司 | L-ascorbic acid-2-phosphate compound and preparation method and application thereof |
| CN109081851A (en) * | 2018-08-17 | 2018-12-25 | 北京英惠尔生物技术有限公司 | The preparation method of feeding L-AA -2- tripolyphosphate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090287A (en) * | 1993-01-13 | 1994-08-03 | 北京市营养源研究所 | The synthetic method of L-xitix-2-tripolyphosphate salt |
-
2009
- 2009-01-19 CN CN2009100954998A patent/CN101475592B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104304680A (en) * | 2014-10-28 | 2015-01-28 | 安徽天寅生物科技有限公司 | L-ascorbic acid-2-phosphate compound and preparation method and application thereof |
| CN109081851A (en) * | 2018-08-17 | 2018-12-25 | 北京英惠尔生物技术有限公司 | The preparation method of feeding L-AA -2- tripolyphosphate |
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| CN101475592B (en) | 2012-02-01 |
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