CN100528933C - Calcium polyaspartate and preparation method thereof - Google Patents
Calcium polyaspartate and preparation method thereof Download PDFInfo
- Publication number
- CN100528933C CN100528933C CNB2006100911607A CN200610091160A CN100528933C CN 100528933 C CN100528933 C CN 100528933C CN B2006100911607 A CNB2006100911607 A CN B2006100911607A CN 200610091160 A CN200610091160 A CN 200610091160A CN 100528933 C CN100528933 C CN 100528933C
- Authority
- CN
- China
- Prior art keywords
- calcium
- polyaspartate
- account
- aspartic acid
- molecular weight
- 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.)
- Expired - Fee Related
Links
Images
Abstract
Preparation of poly-aspartic calcium is carried out by reacting poly-aspartic ammonia acid chain unit with calcium hydroxide or calcium oxide in proportion of 1:5 mol for 2 hrs at room temperature in aqueous solution, depositing by alcohol, thermal filtering, separating, purifying, analyzing element, distributing infrared spectrum and molecular weight, determing ionization degree and surface featuring. It's non-toxic, has polypeptide structure, has slow absorbing speed, long metabolic time and can be used as calcium nutrient enhancer.
Description
Technical field
The present invention relates to a kind of novel calcium-nutrition intensifying agent and preparation method thereof.
Background technology
Calcium lacks the most in the Chinese dietary nutrients, and calcium intake on average only reaches 50% of feed rate every day, and the calcium deficiency phenomenon is more obvious among the crowds such as pregnant woman, children, old man.Replenishing of human calcium is particularly important.
With inorganic salt is that the master comprises that first-generation calsium supplements such as lime carbonate, Calcium of intensifiens, secondary calcium phosphate in the digestive process of human stomach, consume a large amount of hydrochloric acid in gastric juice, has side effect in various degree.Based on s-generation products such as the calcium lactate of organic acid salt, calglucons, the possibility that produces glucose and lactic acid is in vivo also arranged, life-time service glucose is unfavorable to the diabetic subject, makes compound preparation with other calcium salts and uses.This series products must dissolve or be dissociated into calcium ion through hydrochloric acid in gastric juice, and lactic acid can cause the weak untoward reaction of Denging.The calcium of organic acid of chelating belongs to the new generation product in the calcium-nutrition intensifying agent.It is not to be dissociated into calcium ion immediately that this class calcium agent enters blood, but continues to dissociate calcium ion for the body utilization, thereby avoids the too high hypercalcemia that occurs of calcium ion concn in the serum, and the assurance calcium constituent fully absorbs and utilizes.
Calcium polyaspartate has the chemical structure of polypeptide salt, and calcium ion exists with chelated forms in molecule, can progressively dissociate out in human body, and the speed that is absorbed in the human body is wanted slowly relatively, the metabolism time is long, but the long period is utilized by human body.If can be by tests such as safety evaluation and drug metabolisms, calcium polyaspartate might become a kind of novel calcium-nutrition intensifying agent.
Summary of the invention
The present invention relates to a kind of calcium-nutrition intensifying agent calcium polyaspartate, make by following reaction, poly aspartic acid and calcium hydroxide or calcium oxide are mixed in distilled water, stirred 2 hours under the room temperature, filtered while hot behind the heating in water bath to 80 ℃, transfer to neutrality with 0.1mol/LHCl then, the pressure reducing and steaming portion water adds later on behind the dehydrated alcohol the calcium polyaspartate precipitate and separate, calcium polyaspartate solid natural air drying.
In the preparation process of calcium-nutrition intensifying agent calcium polyaspartate, the mol ratio of the chain link of described poly aspartic acid and calcium hydroxide or calcium oxide is 1: 5.
The molecular weight distribution of product calcium polyaspartate is 2,100～31,000, and molecular weight is 10%, 15,000～20,000 17%, 10,000～15,000 account for and account for 44% below 28%, 10,000 of accounting for of accounting for more than 20,000, and molecular-weight average is 8683.
The invention still further relates to a kind of preparation method of calcium-nutrition intensifying agent calcium polyaspartate, this method may further comprise the steps: at first, poly aspartic acid and calcium hydroxide or calcium oxide are mixed in distilled water, stirred 2 hours under the room temperature, filtered while hot behind the heating in water bath to 80 ℃, transfer to neutrality with 0.1mol/LHCl then, the pressure reducing and steaming portion water adds later on behind the dehydrated alcohol the calcium polyaspartate precipitate and separate, calcium polyaspartate solid natural air drying.
In the preparation process of calcium-nutrition intensifying agent calcium polyaspartate, the mol ratio of the chain link of described poly aspartic acid and calcium hydroxide or calcium oxide is 1: 5.
The molecular weight distribution of products therefrom calcium polyaspartate is 2,100～31,000, and molecular weight is 10%, 15,000～20,000 17%, 10,000～15,000 account for and account for 44% below 28%, 10,000 of accounting for of accounting for more than 20,000, and molecular-weight average is 8683.
The invention is characterized in that the calcium polyaspartate of preparation has water-soluble, nontoxic, characteristics such as molecular weight is moderate, can be used as novel calcium-nutrition intensifying agent.
Poly aspartic acid is nontoxic, biodegradable, can select in different scopes by its molecular-weight average of control of polymerization process.Poly aspartic acid is novel water-soluble polymer, at present can mass production, be applied among the different fields as flocculation agent etc.
Poly aspartic acid organic solvent water insoluble and commonly used dissolves in the alkaline aqueous solution.Poly aspartic acid generation hydrolysis under alkaline condition, the ring-type chain link of hydrolysis post polymerization thing is opened into the chain chain link, and hydrolytic process can be expressed as:
Cause trouble for separation purification afterwards for avoiding in preparation process, introducing external metallic cation, directly adopt poly aspartic acid and calcium hydroxide or calcium oxide in the aqueous solution, to react, obtain calcium polyaspartate by magnetic stirrer.Two chain links of poly aspartic acid and a part calcium hydroxide form calcium salt in theory, because calcium hydroxide solubleness in water is less, and the hypoalkalinity of calcium hydroxide is so that the whole hydrolysis of poly aspartic acid, and produces thick water-insoluble.Strengthen the ratio of calcium hydroxide, when the mol ratio to 1 of poly aspartic acid chain link and calcium hydroxide or calcium oxide: in the time of 5, all hydrolysis and generate calcium polyaspartate of poly aspartic acid.
Because calcium hydroxide or calcium oxide are excessive more, dissolved calcium hydroxide can influence the purity of calcium polyaspartate, diminishes according to the solubleness of temperature rising calcium hydroxide, adopts the heat filtering method can effectively reduce the residual of calcium hydroxide.The small amount of residual of calcium hydroxide can be converted into calcium chloride with hydrochloric acid, by the content of calcium chloride in the simulated system, calcium chloride can be stayed among the solution with ethanol precipitation.
With differential thermal analyzer calcium polyaspartate is differed from formula scanning calorimetry (DSC) and measure (Al2O3 is reference, range 20mW, 20 ℃ of starting temperatures, 700 ℃ of final temperatures, 10 ℃/min of temperature rise rate, air atmosphere), can tentatively determine the generation of novel substance and the disappearance of reactant by the calcium polyaspartate characteristic spectrum of accompanying drawing 1.
The DSC collection of illustrative plates of calcium polyaspartate shows that 500 ℃ occur an exothermic peak later on, and calcium polyaspartate has thermostability preferably before this temperature.
Calcium in the calcium polyaspartate and carbon, hydrogen, nitrogen element content are measured with calconum indicator EDTA volumetry and elemental analyser respectively, the results are shown in Table 1.
Table 1: the results of elemental analyses of calcium polyaspartate
From mainly being absorbed with of the visible calcium polyaspartate of infrared spectra of accompanying drawing 2: 537cm
-1, 1409cm
-1, 1594cm
-1, 3384cm
-13384cm wherein
-1The place in the amino acid salts-the medium tenacity stretching vibration peak of NH, 1409cm
-1Be the strong flexural vibration peak of-NH, 537cm
-1(CO-NH-) stretching vibration peak is at 1594cm for secondary amide
-1Vibration peak for carboxyl (COO-).Structure in conjunction with the poly-aspartic acid calcium of ultimate analysis can be represented by the formula:
Adopt gel chromatography (GPC) to measure the molecular weight distribution situation (experiment condition: the 0.1mol/L NaNO of 30 ℃ of temperature, 0.5ml/min flow velocity of calcium polyaspartate
3The aqueous solution is that moving phase, dextran are standard model), the calcium polyaspartate molecular weight distribution is 2,100～31,000, molecular weight is accounting for 10% more than 20,000,15,000～20,000 account for 17%, 10,000～15,000 account for 28%, 10, account for 44% below 000, molecular-weight average is 8683.
Be reference electrode with the mercurous chloride electrode under 25 ℃ of conditions, calcium ion-selective electrode measures 0.005,0.010 respectively, the electromotive force of 0.020mol/L (chain link amount concentration) the calcium polyaspartate aqueous solution, obtains Ca in the solution according to typical curve
2+Concentration, the degree of ionization of calculating calcium polyaspartate the results are shown in Table 2.
Table 2: the degree of ionization of calcium polyaspartate
Mensuration by degree of ionization as can be known, there is dissociation equilibrium in simulation human body environment calcium polyaspartate in the aqueous solution, can progressively discharge calcium ion.
Calcium polyaspartate is through experimentation on animals rough determination hereditary-less toxicity, its mouse oral LD
50＞5000mg/Kg body weight belongs to non-toxic substance.
If calcium polyaspartate is by comprehensive safety evaluation and drug metabolism experiment, calcium polyaspartate might be as a kind of novel calcium-nutrition intensifying agent.
Description of drawings
Fig. 1 is the DSC collection of illustrative plates of calcium polyaspartate of the present invention;
Fig. 2 is the infrared spectra of calcium polyaspartate of the present invention.
Embodiment
Embodiment 1:
Accurately take by weighing 2.28g poly aspartic acid and 7.4g calcium hydroxide, both mix in 80ml distilled water, stir filtered while hot behind the heating in water bath to 80 ℃ under the room temperature 2 hours.Yellow transparent filtrate transfers to neutrality with 0.1mol/LHCl, and pressure reducing and steaming 30ml water white opacity occurs after adding 50 dehydrated alcohols later on, leaves standstill suction filtration after 2 hours, and the solid natural air drying obtains pale yellow powder-calcium polyaspartate.Again precipitate purification with ethanol behind the dissolved in distilled water crude product.
Embodiment 2:
Accurately take by weighing 2.28g poly aspartic acid and 5.6g calcium oxide, both mix in 80ml distilled water, stir filtered while hot behind the heating in water bath to 80 ℃ under the room temperature 2 hours.Yellow transparent filtrate transfers to neutrality with 0.1mol/LHCl, and pressure reducing and steaming 30ml water white opacity occurs after adding 50 dehydrated alcohols later on, leaves standstill suction filtration after 2 hours, and the solid natural air drying obtains pale yellow powder-calcium polyaspartate.Again precipitate purification with ethanol behind the dissolved in distilled water crude product.
Claims (6)
1. calcium-nutrition intensifying agent calcium polyaspartate, it is characterized in that, make by following reaction, poly aspartic acid and calcium hydroxide or calcium oxide are mixed in distilled water, stirred under the room temperature 2 hours, filtered while hot behind the heating in water bath to 80 ℃ transfers to neutrality with 0.1mol/LHCl then, the pressure reducing and steaming portion water adds later on behind the dehydrated alcohol the calcium polyaspartate precipitate and separate, calcium polyaspartate solid natural air drying.
2. calcium-nutrition intensifying agent calcium polyaspartate according to claim 1 is characterized in that, the mol ratio of the chain link of described poly aspartic acid and calcium hydroxide or calcium oxide is 1: 5.
3. calcium-nutrition intensifying agent calcium polyaspartate according to claim 1 is characterized in that, at the 0.1mol/LNaNO of 30 ℃ of temperature, 0.5ml/min flow velocity
3The aqueous solution is that moving phase, dextran are under the experiment condition of standard model, and adopting the molecular weight distribution of the described calcium polyaspartate of gel chromatography is 2,100～31,000, molecular weight is accounting for 10% more than 20,000,15,000～20,000 account for 17%, 10,000～15,000 account for 28%, 10, account for 44% below 000, molecular-weight average is 8683.
4. the preparation method of a calcium-nutrition intensifying agent calcium polyaspartate, it is characterized in that, this method may further comprise the steps: at first, poly aspartic acid and calcium hydroxide or calcium oxide are mixed in distilled water, stirred under the room temperature 2 hours, filtered while hot behind the heating in water bath to 80 ℃ transfers to neutrality with 0.1mol/LHCl then, the pressure reducing and steaming portion water adds later on behind the dehydrated alcohol the calcium polyaspartate precipitate and separate, calcium polyaspartate solid natural air drying.
5. the preparation method of the described calcium-nutrition intensifying agent calcium polyaspartate of claim 4 is characterized in that, the mol ratio of the chain link of described poly aspartic acid and calcium hydroxide or calcium oxide is 1: 5.
6. the preparation method of the described calcium-nutrition intensifying agent calcium polyaspartate of claim 4 is characterized in that, at the 0.1mol/LNaNO of 30 ℃ of temperature, 0.5ml/min flow velocity
3The aqueous solution is that moving phase, dextran are under the experiment condition of standard model, and adopting the molecular weight distribution of the described calcium polyaspartate of gel chromatography is 2,100～31,000, molecular weight is accounting for 10% more than 20,000,15,000～20,000 account for 17%, 10,000～15,000 account for 28%, 10, account for 44% below 000, molecular-weight average is 8683.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100911607A CN100528933C (en) | 2006-07-04 | 2006-07-04 | Calcium polyaspartate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100911607A CN100528933C (en) | 2006-07-04 | 2006-07-04 | Calcium polyaspartate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101100510A CN101100510A (en) | 2008-01-09 |
| CN100528933C true CN100528933C (en) | 2009-08-19 |
Family
ID=39034982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100911607A Expired - Fee Related CN100528933C (en) | 2006-07-04 | 2006-07-04 | Calcium polyaspartate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100528933C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322559B (en) * | 2008-07-18 | 2012-01-11 | 李卫平 | Multifunctional high-efficient calcium replenishing agent |
| CN102504253B (en) * | 2011-10-25 | 2013-05-15 | 石家庄开发区德赛化工有限公司 | Environmental-protection preparation method for calcium polyaspartate as agricultural calcium supplement |
| CN103275318B (en) * | 2013-05-24 | 2016-01-20 | 石家庄中农兴泰生物科技有限公司 | A kind of production method of rich selenium polyaspartic acid calcium salt |
| CN105565910B (en) * | 2015-12-16 | 2017-03-08 | 山东远联化工有限公司 | The preparation method of biologically active polypeptide calcareous fertilisers |
| CN105601918B (en) * | 2015-12-30 | 2016-10-19 | 河北协同环保科技股份有限公司 | A kind of method of catalyzing hydrolysis polysuccinimide |
| CN106290315B (en) * | 2016-08-09 | 2019-06-14 | 青岛大学 | The detection method of calcium in a kind of agricultural fertilizer |
| CN108675917A (en) * | 2018-05-17 | 2018-10-19 | 青岛大学 | The chelated calcium isolation and purification method of sugar alcohol in a kind of organic fertilizer |
| CN113908290B (en) * | 2021-10-22 | 2023-06-02 | 山东大学 | Multifunctional nano-composite and preparation method and application thereof |
| CN117342896B (en) * | 2023-12-04 | 2024-02-02 | 烟台凡西农业科技有限公司 | Preparation method of marine mineral source silicon-calcium-magnesium fertilizer with soil anti-caking effect |
-
2006
- 2006-07-04 CN CNB2006100911607A patent/CN100528933C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 天冬氨酸钙的合成与分离提纯. 李金.食品工业科技，第3期. 2006 |
| 天冬氨酸钙的合成与分离提纯. 李金.食品工业科技，第3期. 2006 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101100510A (en) | 2008-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100528933C (en) | Calcium polyaspartate and preparation method thereof | |
| CN106187797B (en) | A kind of preparation method of complex of ferrous glycine | |
| CN110407714A (en) | Hindered phenol and the compound difunctional antioxidant of amide groups intramolecular and its synthetic method | |
| CN102099295A (en) | Non-caking salt composition, preparation process and use thereof | |
| CN101463075A (en) | Preparation of N(2)-L-alanyl-L-glutamine | |
| CN109761380A (en) | Research of non-phosphorus scale inhibitor and preparation method thereof containing tracer polymer | |
| CN102504253B (en) | Environmental-protection preparation method for calcium polyaspartate as agricultural calcium supplement | |
| CN108530556B (en) | A kind of preparation method for the Modified kelp polysaccharide that acts synergistically | |
| CN102092831B (en) | Method for preparing novel heavy metal chelating agent | |
| US4626577A (en) | Process for preparing a solution of poly(allylamine) | |
| CN103255006B (en) | A kind of Biodegradable phosphorus-free detergent additive and preparation method thereof | |
| CN101717352B (en) | Method for synthesizing agmatine sulfate | |
| JP3790492B2 (en) | Production of metal complexes of amino acids obtained by hydrolysis of soy protein | |
| CN101786962B (en) | Method for producing amino acid chelate iron | |
| CN1587257A (en) | Process for preparing amino acid chelated calcium and its special device | |
| CN105601918B (en) | A kind of method of catalyzing hydrolysis polysuccinimide | |
| Verraest et al. | Synthesis of cyanoethyl inulin, aminopropyl inulin and carboxyethyl inulin | |
| Rao et al. | Solution stability of iron-saccharide complexes | |
| CN109019548B (en) | Preparation method of high-linearity crystal II type ammonium polyphosphate | |
| CN103265616B (en) | N(2)-L-alanyl-L-glutamine synthesis method | |
| CN1281742C (en) | Polycondensed amino-acid coordinated SOD simulatives | |
| CN102875400B (en) | Diethylenetriamine pentaacetic acid preparation method | |
| CN101305810A (en) | Polypeptide calcium and use | |
| CN1048993C (en) | Prepn. method of water soluble sulfonated phenylethylene copolymer | |
| CN111115781A (en) | Production method of high-salinity high-sulfate polyaluminium chloride sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090819 Termination date: 20110704 |