CN100411626C - Slow-released type iodine complement agent, and prepn. method and use-thereof - Google Patents

Slow-released type iodine complement agent, and prepn. method and use-thereof Download PDF

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Publication number
CN100411626C
CN100411626C CNB2006100531735A CN200610053173A CN100411626C CN 100411626 C CN100411626 C CN 100411626C CN B2006100531735 A CNB2006100531735 A CN B2006100531735A CN 200610053173 A CN200610053173 A CN 200610053173A CN 100411626 C CN100411626 C CN 100411626C
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China
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iodine
exchange resin
iodide
resin
iodate
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CN1911241A (en
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徐勇
胡彩虹
夏枚生
朱兴一
熊莉
姚志通
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

A slow-release I-supplement used as the I-supplementing additive of forage or to prepare I-supplementing food or medicine for treating diseases is an anionic exchange resin containing the iodic acid radicals or I ions. It is prepared through the ionic exchange between iodic acid radicals or I ions and anionic exchange resin.

Description

The preparation method of released iodine supplement
Technical field
The present invention relates to a kind of iodine complement agent and preparation method and purposes of spacetabs type.
Background technology
Iodine is requisite composition in the thyroid.Its biochemical function mainly is to show by thyroxin, and is very extensive to the biological action of body.According to " allow use feed additive kind catalogue " of the up-to-date promulgation of China, can be used for trace compound that poultry enrich the iodine has 3 kinds of potassium iodide, potassium iodate and calcium iodate.Other chemical compound that contains iodine also has sodium iodide, ethylenediamine dihydroiodide, Hydro-Giene (Water Science)., 3,5-diiodosalicylic acid, thymiodol etc.Potassium iodide, sodium iodide poor stability are easily caused its biological activity to descend, even completely lose by other trace element oxidation in airborne oxygen and the feedstuff.In addition, when potassium iodide and other trace element (as copper sulfate) compatibility, vitamin A there is the ashamed usefulness of intensive collaborative destruction.Potassium iodate, calcium iodate are more stable, and its biological value is similar to potassium iodide, but stronger oxidant is bigger to the destruction of vitamin, and be stronger to the gastrointestinal irritation of animal.In addition, for culture fishery, aquatic feeds must drop into water body, fish and shrimp just can be ingested, in case and feedstuff entry, just be subjected to the influence of various factors (pH, temperature, osmotic pressure, wave current impact, chemical reaction etc.), produced various reactions, as dissolving, swelling, fracture, efflorescence, peel off etc.Chen Siqing etc. (1995) have studied that the prawn mixed feed is dipped in the wastage of each nutritional labeling in the water and to Effects of water environment, the molten mistake of finding mineral is very rapidly and completely, only with the percentage composition rate of descent, in the time of 5 minutes, descended 16.4~40.8%, in the time of 90 minutes, descended 69.4~76.7%, reach 84.4~93.9% in the time of 120 minutes, if calculate the weightless loss that causes, then molten mistake is totally in the time of 120 minutes for mineral.After inorganic microelement such as potassium iodide, the potassium iodate entry, be easy to molten mistake and be dissolved in the water, cause the waste of propiodal and the pollution of water environment.
Iodine comprises that organic bonded iodine, inorganic iodine and molecular iodine (are I 2), can be used for treating human diseases.Worry it is the probability of toxic reaction about the maximum of administration iodine medicine.Iodism can cause a series of symptom.Described symptom comprises that oral cavity and throat are scorching hot; Tooth and gingiva pain; Salivation increases; Rhinitis, respiratory tract; Cough; Headache; Body of gland increases; Pharynx, larynx and tonsil inflammation; Skin injury; Gastric irritation; Diarrhoea; Fever; Anorexia and depression; May take place serious, be fatal eruption (iododerma) sometimes.
The control slow-released system has selectivity and controllability to release position, speed and the mode of medicine, pesticide, fertilizer, spice, can realize the targeting transmission and the control slow release of object, improve its utilization rate and action effect, the research and the application of control slow-releasing system will bring new technological revolution to relevant industries.The key of control slow release method is the selection of controlled release carrier.Ion exchange resin (Ionexchange resin, IER) be the cancellated macromolecular compound that a class has functional group, its structure is made up of three parts: insoluble three dimensions mesh skeleton, be connected functional group on the skeleton and functional group with the exchangeable ion of opposite charges.According to the different in kind of cation exchange groups, ion exchange resin is divided into six big classes: storng-acid cation exchange resin, weak-acid cation-exchange resin, strong alkalinity anion literary composition change resin, weak-base anion-exchange resin, sequestration ion exchange resin, amphoteric ion-exchange resin, oxidation-reduction quality ion exchange resin.According to resin with tradable ionic nature, ion exchange resin is divided into cation exchange resin and anion exchange resin substantially, has acid function base (highly acid: sulfonic group (SO 3H); Faintly acid: carboxylic acid group (COOH), phosphate (PO 3H 2) etc.), the polymer that can exchange with cation is cation exchange resin; Have alkaline functional base (strong basicity: quaternary ammonium group-N (CH 3) 3Deng; Alkalescence: the primary, the second month in a season, tertiary amine groups (CH 2NH 2,--CH 2NHR ,-CH 2NR 2) etc.), the polymer that can exchange with anion is anion exchange resin.
According to the difference of resin physical arrangement, can be divided into gel-type and macroporous ion-exchange resin two big classes to ion exchange resin again.Gel type resin is the ion exchange resin of the homogeneous phase high-molecular gel structure of a class appearance transparent, the interior mutually micropore that produces of suction back resin, and counter ion can diffuse into and carry out ion exchange in the micropore that is produced by suction.The basic characteristics of macroreticular ion exchange resin be do in whole resin inside, wet or contraction, swelling all exist the duct more, bigger than general gel-type in water, thereby surface area is big, in ion exchange process, the easy diffusion mobility of ion, exchange velocity is very fast.
Full name of ion exchange resin claims to be rearranged by specific name, skeleton (or group) title, basic designation.The model name of ion exchange resin is different and fixed according to structure, form by three Arabic numerals: the classification of the first bit digital representative products, second-order digit is represented the difference of framing structure, and the 3rd bit digital is a serial number, in order to difference group, cross-linking agent etc.All macroreticular ion exchange resins add before model, and-D represents: gel-type ion-exchange resin connects Arabic numerals with " * " and represents after model.Wherein, classification designator has 0,1,2,3,4,5,6, corresponding representative strong-acid type, weak-type, strong base, weak base type, chelating type, both sexes and oxidation-reduction ion-exchange resin.The skeleton code name has 0,1, and 2,3 etc., represent polystyrene, acrylic acid series, phenolic aldehyde system, epoxy system etc. respectively.
Separation and purification pure water preparation that ion exchange resin is applied to analytical chemistry medicine for a long time reach fields such as being used for the environmental conservation blood purification in the recent period.Since proposing ion exchange resin first in 1956 and being used to delay drug release as pharmaceutical carrier, the report that utilizes ion exchange technique to delay drug release constantly increases, and has entered the practicality stage.Ion exchange resin has multiple good characteristic as pharmaceutical carrier, at present its controlled release, transdermal administration, site-specific delivery of drugs, instant, iontophoresis transdermal, nasal cavity, topical and cover side such as bitter taste of drug and application very deep research is all arranged, some product goes on the market.Ion exchange resin is control drug release in gastrointestinal tract mainly, be ion exchange resin controlled-release administrating system (Ion-Exchange ResinControlled Drag Delivery System, IERCDDS), compare with other drug-supplying systems, the main feature of IERCDDS is the volume that the release of medicine does not rely on pH value, enzymatic activity, temperature and gastrointestinal fluid in the gastrointestinal tract, because ionic species and strength maintenance thereof in the gastrointestinal fluid are constant relatively, so medicine can constant rate of speed discharge in vivo.
Summary of the invention
The iodine complement agent and preparation method and the purposes that the purpose of this invention is to provide a kind of spacetabs type.
The iodine complement agent of spacetabs type is a kind of anion exchange resin that contains commutative iodate or iodide ion, and by weight percentage, the content of iodine in anion exchange resin is 0.5~5%.
The preparation method of the iodine complement agent of spacetabs type may further comprise the steps:
1) anion exchange resin is placed 0.5~2mol/L hydrochloric acid solution of 1~2 times of resin volume soaked 2~5 hours, drain after the acid solution with water rinse to neutral, 0.5~2mol/L sodium hydroxide solution with 1~2 times of resin volume soaked 3~6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) is packed in the exchange column, with amount of iodine is the iodate or the iodide of anion exchange resin weight 0.5~5%, be pre-configured to the aqueous solution of 0.01~1.0mol/L, with the flow velocity of 1~10mL/min by exchange column, finish after washing 2~5 times of exchange;
3) with step 2) anion exchange resin of the load iodine of gained is being lower than 70 ℃ of oven dry down, obtains the iodine complement agent of spacetabs type.
The iodic acid that uses among the present invention (salt) is potassium iodate, potassium hydrogen diiodate, sodium iodate or calcium iodate.The said iodide of the present invention are sodium iodide, potassium iodide, ammonium iodide, calcium iodide or magnesium iodide.
The iodine complement agent of spacetabs type is as cattle, sheep, poultry, the aquatic animal feed additive that enriches the iodine.The iodine complement agent of spacetabs type is used to prepare human oral health product and the medicine that enriches the iodine and treat human diseases by the iodine of drug treatment.
Advantage of the present invention is:
(1) utilize anion exchange resin can play the characteristics of exchange interaction with anion, iodate or iodide ion are loaded in the anion exchange resin, implementation method is easy, suitability for industrialized production, and cost is lower;
(2) because ion exchange resin is a kind of control slow-released carrier of function admirable, the iodine of institute's load is had the control slow releasing function, thereby improved the absorption rate of iodine greatly;
(3) iodine complement agent of spacetabs type of the present invention has low toxicity, characteristics of high efficiency, can be used as the feed additive that enriches the iodine; Also can be used for preparing human oral health product and the medicine that enriches the iodine and treat human diseases by the iodine of drug treatment.
The specific embodiment
Anion exchange resin is strong-base anion-exchange resin or weak-base anion-exchange resin, has the alkaline functional base, comprises strong basicity (quaternary ammonium group-N (CH 3) 3) and alkalescence (primary, secondary, tertiary amine groups ,-CH 2NH 2,--CH 2NHR ,-CH 2NR 2) functional group.According to the difference of anion exchange resin physical arrangement, can be gel-type or macroporous ion-exchange resin.The anion exchange resin skeleton is polystyrene or acrylic acid series.
Embodiment 1
1) (this product is equivalent to U.S. AmberliteIRA-400 with commercially available 201 * 7 (717#) strong basicity I type anion exchange resin, West Germany LewatitM500, Japan DiaionSA-10A), place the 0.5mol/L hydrochloric acid solution of 1 times of resin volume to soak 2 hours, drain after the acid solution with water rinse to neutral, 0.5mol/L sodium hydroxide solution with 1 times of resin volume soaked 3 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the potassium iodate of anion exchange resin weight 0.5% with amount of iodine, is pre-configured to the aqueous solution of 0.01mol/L,,, washes 2 times after reaction finishes by exchange column with the flow velocity of 1mL/min;
3) with step 2) anion exchange resin of the load iodine of gained is being lower than 70 ℃ of oven dry down, obtains the iodine complement agent of spacetabs type.By weight percentage, the content of iodine in anion exchange resin is 0.5%.
Embodiment 2
1) be that (this product is equivalent to the U.S. to weak basic anion exchange resin: AmberliteIRA-68 with commercially available D311 macroporous acrylic; Germany: AP-49 D318), place the 2mol/L hydrochloric acid solution of 2 times of resinites to soak 5 hours, drain after the acid solution with water rinse to neutral, the 2mol/L sodium hydroxide solution with 2 times of resin volumes soaked 6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the sodium iodate of anion exchange resin weight 1.5% with amount of iodine, is pre-configured to the aqueous solution of 0.8mol/L,,, washes 5 times after reaction finishes by exchange column with the flow velocity of 1~10mL/min;
3) with step 2) anion exchange resin of the load iodine of gained is being lower than 70 ℃ of oven dry down, obtains the iodine complement agent of spacetabs type.By weight percentage, the content of iodine in anion exchange resin is 1.5%.
Embodiment 3
1) with commercially available D201 macropore alkalescence I type anion exchange resin (the suitable U.S. of this product: AmberliteIRA-900, West Germany: Lewatit MP-500, Japan: Diaion308), place the 1mol/L hydrochloric acid solution of 1.5 times of resin volumes to soak 4 hours, drain after the acid solution with water rinse to neutral, 1mol/L sodium hydroxide solution with 1.5 times of resin volumes soaked 5 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the potassium hydrogen diiodate of anion exchange resin weight 5% with amount of iodine, is pre-configured to the aqueous solution of 1.0mol/L,,, washes 3 times after reaction finishes by exchange column with the flow velocity of 5mL/min;
3) with step 2) anion exchange resin of the load iodine of gained is being lower than 70 ℃ of oven dry down, obtains the iodine complement agent of spacetabs type.By weight percentage, the content of iodine in anion exchange resin is 5%.
Embodiment 4
1) (this product is equivalent to the U.S.: AmberlysteIRA-94 with commercially available D301 macroreticular weakly base styrene series anion exchange resin; Amberlite IRA-93/94 DOWS MWA-1/66), place the 0.5mol/L hydrochloric acid solution of 1.5 times of resin volumes to soak 4 hours, drain after the acid solution with water rinse to neutral, the 2mol/L sodium hydroxide solution with 2 times of resin volumes soaked 4 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column amount of iodine is the calcium iodide of anion exchange resin weight 1.5%, is pre-configured to the aqueous solution of 0.05mol/L,,, washes 5 times after reaction finishes by exchange column with the flow velocity of 10mL/min;
3) with step 2) anion exchange resin of the load iodine of gained is being lower than 70 ℃ of oven dry down, obtains the iodine complement agent of spacetabs type.By weight percentage, the content of iodine in anion exchange resin is 1.5%.
Embodiment 5
1) be that (this product is equivalent to the U.S. to weak basic anion exchange resin: AmberliteIRA-68 with commercially available D311 macroporous acrylic; Germany: AP-49), place the 0.5mol/L hydrochloric acid solution of 2 times of resin volumes to soak 5 hours, drain after the acid solution with water rinse to neutral, the 2mol/L sodium hydroxide solution with 2 times of resin volumes soaked 6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) being packed in the exchange column, is the sodium iodide of anion exchange resin weight 2.5% with amount of iodine, is pre-configured to the aqueous solution of 1.0mol/L,,, washes 4 times after reaction finishes by exchange column with the flow velocity of 5mL/min;
3) with step 2) anion exchange resin of the load iodine of gained is being lower than 70 ℃ of oven dry down, obtains the iodine complement agent of spacetabs type.。By weight percentage, the content of iodine in anion exchange resin is 2.5%.
The iodine complement agent of spacetabs type is as cattle, sheep, poultry, the aquatic animal feed additive that enriches the iodine.Using method is: admix (in iodine) in cattle, sheep, poultry, the aquatic animal feed by following additive capacity: cattle 0.1~0.5mg/kg, sheep 0.1~0.4mg/kg, pig 0.1~0.5mg/kg, chicken 0.1~1mg/kg, duck 0.1~0.5mg/kg, fish 0.1~0.5mg/kg, Trionyx sinensis Wiegmann 0.2~1.5mg/kg, shrimp 0.2~1.5mg/kg.
The iodine complement agent of spacetabs type is used to prepare that the mankind enrich the iodine and treat the health product or the medicine of human diseases by the iodine of drug treatment.Using method is: dosage every day (in iodine) that is used for the treatment of the iodine complement agent of the required spacetabs type of mammary gland dysplasia: the women for body weight 60kg is 0.5~15mg/ days, and the amount ranges of preferred iodine is 2.0~7.5mg/ days.Be used to prevent dosage every day (in iodine) of the iodine complement agent of the required spacetabs type of mammary gland dysplasia: 0.125~1.5mg/ days, the amount ranges of preferred iodine was 0.225~1.25mg/ days.Dosage every day (in iodine) of iodine complement agent that is used for the spacetabs type of acute administration: 15~125mg/ days, the amount ranges of preferred iodine was 20~55mg/ days.

Claims (3)

1. the preparation method of the iodine complement agent of a spacetabs type is characterized in that the step of method is as follows:
1) anion exchange resin is placed 0.5~2mol/L hydrochloric acid solution of 1~2 times of resin volume soaked 2~5 hours, drain after the acid solution with water rinse to neutral, 0.5~2mol/L sodium hydroxide solution with 1~2 times of resin volume soaked 3~6 hours then, drained behind the alkali liquor with water rinse to neutral;
2) resin of step 1) is packed in the exchange column, with amount of iodine is the iodate or the iodide of anion exchange resin weight 0.5~5%, be pre-configured to the aqueous solution of 0.01~1.0mol/L, with the flow velocity of 1~10mL/min by exchange column, finish after washing 2~5 times of exchange;
3) with step 2) anion exchange resin of the load iodine of gained is being lower than 70 ℃ of oven dry down, obtains the iodine complement agent of spacetabs type.
2. the preparation method of the iodine complement agent of a kind of spacetabs type according to claim 1 is characterized in that said iodate is potassium iodate, potassium hydrogen diiodate, sodium iodate or calcium iodate.
3. the preparation method of the iodine complement agent of a kind of spacetabs type according to claim 1 is characterized in that said iodide are sodium iodide, potassium iodide, ammonium iodide, calcium iodide or magnesium iodide.
CNB2006100531735A 2006-08-28 2006-08-28 Slow-released type iodine complement agent, and prepn. method and use-thereof Expired - Fee Related CN100411626C (en)

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Publication number Priority date Publication date Assignee Title
CN108208354B (en) * 2018-01-18 2021-03-23 仲恺农业工程学院 Microspheres capable of slowly releasing calcium iodate and preparation method thereof
CN110037050B (en) * 2019-05-08 2021-02-02 山西大学 High-efficiency compound iodine solution and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947572A (en) * 1974-07-01 1976-03-30 Abbott Laboratories Iron-resin adsorbate
CN1037651A (en) * 1988-05-11 1989-12-06 格拉克索公司 Drug adsorbates
CN1114526A (en) * 1994-12-28 1996-01-10 王文有 Process for preparation of germicide containing triiodo resin
CN1144195A (en) * 1996-01-12 1997-03-05 山西省卫生防疫站 Drinking water iodine-adding method and its device
CN1531399A (en) * 2001-05-14 2004-09-22 瓦西里・彼得罗维奇・安德烈丘克 Biologically active food additive and biologically active forage additive for preventing iodine deficiency and optimising iodine metabolism, food and forage products containing said additive

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947572A (en) * 1974-07-01 1976-03-30 Abbott Laboratories Iron-resin adsorbate
CN1037651A (en) * 1988-05-11 1989-12-06 格拉克索公司 Drug adsorbates
CN1114526A (en) * 1994-12-28 1996-01-10 王文有 Process for preparation of germicide containing triiodo resin
CN1144195A (en) * 1996-01-12 1997-03-05 山西省卫生防疫站 Drinking water iodine-adding method and its device
CN1531399A (en) * 2001-05-14 2004-09-22 瓦西里・彼得罗维奇・安德烈丘克 Biologically active food additive and biologically active forage additive for preventing iodine deficiency and optimising iodine metabolism, food and forage products containing said additive

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