CN102550602A - High-iodine controlled-release type sanitizer - Google Patents

High-iodine controlled-release type sanitizer Download PDF

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Publication number
CN102550602A
CN102550602A CN2011104069642A CN201110406964A CN102550602A CN 102550602 A CN102550602 A CN 102550602A CN 2011104069642 A CN2011104069642 A CN 2011104069642A CN 201110406964 A CN201110406964 A CN 201110406964A CN 102550602 A CN102550602 A CN 102550602A
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iodine
release type
quaternary ammonium
ammonium salt
percent
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王碧清
何帅
冯玉军
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Chengdu Organic Chemicals Co Ltd of CAS
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Chengdu Organic Chemicals Co Ltd of CAS
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Abstract

The invention relates to a high-iodine controlled-release type sanitizer. A preparation method comprises the following steps of: reacting iodine with a complexing agent to obtain stable complex iodine; and coating the complex iodine by using micelle microcapsules formed by gemini quaternary ammonium salt to form a sterilization system which has double stable and controlled release effects on the iodine. The high-iodine controlled-release type sanitizer mainly comprises the following components: 5 to 20 percent of gemini quaternary ammonium salt, 1.6 to 8.0 percent of iodine, 10 to 30 percent of complexing agent, 2 to 16 percent of pH regulator and 30 to 80 percent of solvent. The prepared sanitizer has the advantages of high efficiency, stability, safety, no pollution, and perfect combination of quick sterilization and lasting sterilization, and can be widely applied to places required to be sterilized such as environments, water, epidemic areas, pet hospitals, poultry farming, animal husbandry, aquaculture farms and the like.

Description

A kind of high iodine-containing control release type disinfectant
Technical field
The present invention relates to a kind of high iodine-containing control release type disinfectant, belong to the disinfectant field.
Background technology
Halliday was used for the medical science sterilization with iodine first in 1821, and the American Pharmacopeia official approval tincture of iodine in 1830 can be used as disinfectant and uses, and iodine in 1839 is used to handle specific wound and is seen in report first.Iodine has advantages such as high-efficiency broad spectrum, action effective length, bacterium, the difficult generation of virus drug resistance as disinfectant, this is that other disinfectants institutes are incomparable, so in fields such as skin degerming, assanation, air cleaning, iodine class disinfectant is extremely paid attention to.But iodine also has the shortcoming that can't ignore.Water-soluble very low (100g water can only dissolve about 0.02g iodine at normal temperatures) of iodine, so people usually add KI or sodium iodide generates the triiodide ion (I of solubility with iodine 3 -), thereby the dissolubility of increase iodine.Iodine is very unstable in water, can be hydrolyzed into other iodide very soon, like I -, IO 3 -, H 2OI +, I 3 -Deng, they all do not have bactericidal activity.So the bactericidal property of the aqueous solution goods of iodine is unstable, the storage life is very short.Iodine also has numerous shortcomings such as tinction property, excitant and corrosivity, and this makes its application aspect sterilization receive considerable restraint.
In order to enlarge the range of application of iodine, people overcome the shortcoming of conventional iodine disinfectant through Iodophor (Iodophor).For the conventional iodine disinfectant, Iodophor has low toxicity, non-corrosiveness, to skin, mucous membrane nonirritant and numerous advantages such as easy dyeing or dyeing back fugitive color not.Be that the Iodophor product of representative has obtained in the sterilization field using the most widely with the complex compound of polyvinylpyrrolidone (PVP) and iodine at present.Yet polyvinylpyrrolidone is a kind of high molecular surfactant, and mean molecule quantity is difficult to biological degradation in 10000-70000, the long-term use, and its residual accumulating can be caused environmental pollution and visceral lesion; And polyvinylpyrrolidone self do not have bactericidal action, and the material that really plays bactericidal action is the free molecular iodine that discharges from polyvinylpyrrolidone.In addition, the maximum iodine load capacity of polyvinylpyrrolidone has only 1%, needs other polyvinylpyrrolidone of a large amount of medical grades to stablize iodine in the production, and this will inevitably make the production cost of Operand and selling price increase substantially.
Discovery alkyl amine oxides such as Woodward in 1986 can be used as the excellent carrier of iodine.Alkyl amine oxide is a kind of small-molecule substance to the safe and non-stimulating noresidue of human body, and iodine can be well and the alkyl amine oxide complexing, and the complex compound of formation is more stable than the complex compound of polyvinylpyrrolidone and iodine, and the ultimate load of iodine also is increased to 2%.Yet alkyl amine oxide is a kind of amphoteric surfactant in the aqueous solution; Be nonionic when neutral and alkaline; Become cationic surfactant when acid; The mode of loading and the stability thereof of iodine also change thereupon, so the bactericidal property of alkyl amine oxide chelated iodine receives the especially severe that influences of environment for use, this has limited its scope of application.
In order to reduce the environmental factor dependence of alkyl amine oxide chelated iodine, in experiment, the micella load iodine that we have used gemini quaternary ammonium salt to form.Gemini quaternary ammonium salt is a kind of novel quaternary surfactant, and with respect to traditional quaternary surfactant, its special double end double-tail structure can improve the adsorption rate to bacterium, so have stronger bactericidal property.According to test, the minimum inhibitory concentration of gemini quaternary ammonium salt (MIC) is than the low several magnitude of other quaternary ammonium salts.In addition, the critical micelle concentration of gemini quaternary ammonium salt (CMC) is very low, but micella intensity is very big, and the micella layer is affected by the external environment little.We find in the experiment; When the peripheral parcel of chelated iodine one deck gemini quaternary ammonium salt micella; The stability of complex compound has obtained significantly improving; Not only external environment can't see through gemini quaternary ammonium salt micella layer and remove to influence complex compound, and the pH value that makes complex compound can resist external environment changes and organic matter disturbs; And the maximum negative iodine amount of chelated iodine has been increased to 8% from 2%.The iodine of high-load complexing agent and gemini quaternary ammonium salt dual stable down, stable existence for a long time not only, and do not produce spread effect.Find also that from experiment gemini quaternary ammonium salt and chelated iodine can play the effect of Synergistic biocidal, make that this sterilization system can be in performance high-efficient and lasting sterilizing ability, consumption but can be considerably less.
Summary of the invention
The objective of the invention is to remedy traditional Iodophor preparation content of iodine low with sterilization persistence difference deficiency and the high iodine-containing control release type disinfectant of a kind of safety non-pollution with lasting sterilization is provided.The present invention earlier generates more stable chelated iodine with iodine and complexing agent reaction, and the micella micro-capsule parcel chelated iodine that forms with gemini quaternary ammonium salt again constitutes and a kind of iodine had dual stablizing and the sterilization system of sustained release.
The present invention has following advantage:
1, through the protection of gemini quaternary ammonium salt micella micro-capsule, the stability of iodine is greatly improved, and also the content of iodine than other Iodophor goods is high for content of iodine in the system.
2, gemini quaternary ammonium salt micella micro-capsule can be controlled the stability of inner complexation iodine, and then the release of control iodine, reaches the purpose of sustained release.
3, anti-organic matter ability is strong, can sterilization in complex environment.
The present invention is through the method for the micella micro-capsule solubilising iodo-complexes of gemini quaternary ammonium salt formation, and having constituted complex compound, the shell that a kind of nuclear is iodine is the nucleocapsid structure of gemini quaternary ammonium salt micella microcapsule layer.This structure plays a part dual stable and sustained release to iodine, and bacterium is had the powerful ability of killing, even the Candida albicans that general iodine disinfectant is difficult to kill also can have Disinfection Effect preferably.This product has the advantage of efficient stable, safety non-pollution, quick sterilization and lasting sterilization, can be widely used in that environment, livestock and poultry, culture fishery etc. need to sterilize, the place of sterilization.
The present technique invention realizes through following measure:
High iodine-containing control release type disinfectant contains following component, and the percentage by weight of each component is following:
Gemini quaternary ammonium salt 5%~20%,
Iodine 1.6%~8.0%,
Complexing agent 10%~30%,
PH regulator agent 5%~16%,
Solvent 30%~80%
More than each component sum be absolutely.
Earlier in the aqueous solution of complexing agent, add iodine, be warming up to 60~80 ℃, slowly stir, treat that iodine is all after the dissolving; Add other component, stop heating, stirred fast 2 hours at once; Naturally cool to room temperature, obtain the bronzing thick liquid of homogeneous phase transparent, packing is bactericide of the present invention.
Gemini quaternary ammonium salt is by forming with two positively charged head base and two long alkyl tail chains, and its critical micelle concentration is low especially, when super low concentration, still can form micella parcel and stable complexation iodine.Gemini quaternary ammonium salt also has the effect of good sterilization algae removal in addition, can with the iodine Synergistic biocidal, both can make the bactericidal property of system be greatly improved together.Gemini quaternary ammonium salt can adopt general formula (I), (II) and compound (III).
Complexing agent can generate chelated iodine with iodine, thereby increases the solvability of iodine in water, and preliminarily stabilised iodine.Complexing agent can adopt at least a or mixture of the compound of general formula (IV), (V), (VI) expression.
The pH regulator agent can make the bactericide system be acid.It is well stable that sour environment can not only make iodine obtain, and also can greatly strengthen iodine to the infiltration killing action of bacterium with virus, makes the bactericidal property of iodine perform to maximum.At least a or the mixture of phosphoric acid, citric acid is selected in the pH regulator agent for use.
Solvent mainly is the various components of dissolving, and the viscosity of improvement system and water-soluble.Proper amount of solvent can make very that the bactericide of thickness is transformed into the current system of modest viscosity, and accelerates its dissolving in water, and snap action is in bacterium and virus.Solvent can adopt at least a mixture of water, ethanol, ethylene glycol, isopropyl alcohol.
Experiment finds that the micella that gemini quaternary ammonium salt forms can wrap up chelated iodine well.In this micelle volume, chelated iodine is owing to being in the inner microenvironment of micella, so be not vulnerable to the influence of extraneous factors such as pH value, organic matter, inorganic matter and dilution factor.And the chelated iodine of other Iodophors all is to expose in solution, poor stability.So the stability of chelated iodine is all better than other Iodophors in this micelle volume, realized the dual stable of iodine, overcome the unsettled shortcoming of iodine.
High iodine-containing control release type disinfectant sterilization mechanism is: at first, in sterilization process, the gemini quaternary ammonium salt that forms micella at first adsorbs on the cell wall that is positioned at bacterium; Subsequently, through the effect of infiltration and diffusion, the alkyl tail chain of gemini quaternary ammonium salt can be overflowed from micella, is inserted in the phospholipid bilayer of bacterial cell membrane, the phospholipid bilayer of cell membrane is damaged and permeability changes; Form a space owing to the effusion that the part gemini quaternary ammonium salt is arranged in micella makes micella, therefore the inner residing microenvironment of chelated iodine also changes, and chelated iodine will decompose, and discharges free-iodine; The free-iodine that discharges just in time can directly enter into thoroughly killing bacteria of cytoplasm through the cell membrane that damages from the micella space.So this bactericide is when disinfection, dosage is few, and penetration is strong, and effective acting time is long.
This series bactericidal agent of the present invention's development is mainly used in the disinfection on environment, livestock and poultry and the culture fishery, and low concentration just can efficiently be killed microorganisms such as various viruses, bacterium, mould, fungi and algae.
Embodiment
Embodiment 1
In a 2000mL agitated reactor, add dodecyl amine oxide (OA-12) 848g; Stir also and heat to 60 ℃, add the 32g iodine, be stirred to the whole dispersing and dissolvings of iodine after; Add 48g AEO-3 phosphate, 64g phosphoric acid, 200g gemini quaternary ammonium salt (12-3OH-12) then successively; Thing to be added stops heating after dissolving entirely, continues to stir 2 hours, obtains transparency liquid russet.
Embodiment 2
In a 2000mL agitated reactor, add dodecyl amine oxide (OA-12) 848g; Stirring also heats to 60 ℃, adds the 32g iodine, is stirred to iodine and all dissolves; Add 48g 1-isobutyl-3,5-dimethylhexylphosphoric acid, 64g phosphoric acid, 200g gemini quaternary ammonium salt (12-4-12) then successively; Thing to be added stops heating after dissolving entirely, continues to stir 2 hours, obtains transparency liquid russet.
Embodiment 3
In a 2000mL agitated reactor, add dodecyl amine oxide (OA-12) 1000g; Add the 36g iodine simultaneously, stir and heat to 70 ℃, after iodine all dissolves by the time; Add 48g phosphoric acid, 100g gemini quaternary ammonium salt (14-2-14) and 50g ethanol successively; Thing to be added stops heating after dissolving entirely, continues to stir 2 hours, obtains transparent thick liquid russet.
Embodiment 4
In a 2000mL agitated reactor, add dodecyl amine oxide (OA-12) 640g; Add the 32g iodine simultaneously, stir and heat to 60 ℃, after iodine all dissolves by the time; Add 48g AEO-3 phosphate, 58.4g phosphoric acid, 200g gemini quaternary ammonium salt (12-2-12) successively; Thing to be added stops heating after dissolving entirely, continues to stir 2 hours, obtains transparent thick liquid russet.
Embodiment 5
In a 2000mL agitated reactor, add dodecyl amine oxide 600g; Stirring also heats to 70 ℃, adds the 26g iodine, is stirred to iodine and all dissolves; Add 100g phosphoric acid, 100g gemini quaternary ammonium salt (12-3OH-12) then successively; Thing to be added stops heating after dissolving entirely, continues to stir 2 hours, obtains transparency liquid russet.
The disinfectant of preceding 4 embodiment preparation of the present invention has carried out the sterilization test of Candida albicans.The experiment bacterial strain uses therefor is Candida albicans (ATCC10231), provide by Chinese common micro-organisms DSMZ, the 5th generation culture.Neutralizer consists of: 1%Na 2S 2O 3The PBS solution of the 0.03mol/L of+1% lecithin+1% tween.
Kill the test operation program according to " disinfection technology standard " quantitative approval test operation sequence of (version in 2002) 2.1.1.5.5 neutralizer suspension and 2.1.1.9.5 fungi.
The neutralizer approval test: test is arrived available iodine content 200mg/L with diluted sample.Action time: 3min.20 ℃ of test temperatures, number of repetition 3 times.
Quantitative disinfecting test: test is arrived available iodine content 200mg/L with diluted sample.20 ℃ of test temperatures, number of repetition 3 times.
The prepared product of embodiment 1,2,3,4 to Candida albicans action time respectively the killing effect of 3min, 5min, 10min see table 1:
Table 1 embodiment 1-embodiment 4 products obtained therefroms are to the oidiomycetic killing effect of white
Figure BSA00000632130700051

Claims (5)

1. a high iodine-containing control release type disinfectant is characterized in that this bactericide contains following component, and the percentage by weight of each component is following:
Gemini quaternary ammonium salt 5%~20%,
Iodine 1.6%~8.0%,
Complexing agent 10%~30%,
PH regulator agent 5%~16%,
Solvent 30%~80%,
More than each component sum be absolutely.
2. high iodine-containing control release type disinfectant according to claim 1 is characterized in that gemini quaternary ammonium salt is general formula (I), (II) and (III) compound of expression,
Figure FSA00000632130600011
Wherein:
R 1And R 1' be respectively the alkyl that contains 8~16 carbon atoms, R 1And R 1' can be identical also can be different,
R 2, R 3Be the alkyl that contains 1~4 carbon atom,
N is 1~5 integer,
X -Be the halide anion opinion.
3. high iodine-containing control release type disinfectant according to claim 1 is characterized in that complexing agent adopts at least a mixture of the compound of general formula (IV), (V), (VI) expression,
R-X-(CH 2CH 2O) nH (IV)
Figure FSA00000632130600021
R-N(CH 3) 2→O (VI)
Wherein:
R is the alkyl that contains 8~20 carbon atoms, and X is oxygen, sulphur or nitrogen-atoms, and n is 3~20, x+y=3.
4. high iodine-containing control release type disinfectant according to claim 1 is characterized in that solvent adopts water, ethanol, ethylene glycol, at least a mixture of isopropyl alcohol.
5. a method for preparing the described high iodine-containing control release type of claim 1 disinfectant is characterized in that in the solution of complexing agent, adding iodine, is warming up to 50~80 ℃; Slowly stir, treat that iodine all disperses after, add other component at once; Stop heating; Stir fast, naturally cool to room temperature, obtain transparent thick liquid russet.
CN2011104069642A 2010-11-30 2011-11-30 High-iodine controlled-release type sanitizer Pending CN102550602A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102885707A (en) * 2012-10-09 2013-01-23 杜海峰 Breast washing solution for milking cow and preparation method thereof
CN103720640A (en) * 2013-12-31 2014-04-16 哈尔滨欧替药业有限公司 Povidone-iodine vaginal swelling suppository, as well as preparation method and detection method thereof
CN103891772A (en) * 2014-04-21 2014-07-02 成都科宏达科技有限公司 Compound sterilizing agent
CN104604934A (en) * 2015-01-21 2015-05-13 成都科宏达科技有限公司 Novel composite iodine disinfectant as well as preparation method and application thereof
CN106135274A (en) * 2015-04-22 2016-11-23 苏州泰利三佳纳米科技有限公司 A kind of medicated clothing skin degerming agent composition containing iodine and preparation method thereof
CN111328806A (en) * 2020-03-07 2020-06-26 郑州大学 Double-linear alkyl quaternary ammonium salt complex iodine bactericide
CN111685114A (en) * 2020-07-02 2020-09-22 江苏敖众药业有限公司 Composite iodine solution with high distribution coefficient and preparation method thereof
CN111937901A (en) * 2020-09-15 2020-11-17 四川长宁天然气开发有限责任公司 Special foamless composite bactericide for shale gas well pipeline and preparation method thereof
CN112704080A (en) * 2020-12-30 2021-04-27 佛山市正典生物技术有限公司 Iodine-containing disinfectant with stable component content and preparation method thereof
CN113801028A (en) * 2021-10-15 2021-12-17 成都科宏达科技有限公司 Special surfactant for hydrogen peroxide and compound thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102885707B (en) * 2012-10-09 2014-11-05 杜海峰 Breast washing solution for milking cow and preparation method thereof
CN102885707A (en) * 2012-10-09 2013-01-23 杜海峰 Breast washing solution for milking cow and preparation method thereof
CN103720640A (en) * 2013-12-31 2014-04-16 哈尔滨欧替药业有限公司 Povidone-iodine vaginal swelling suppository, as well as preparation method and detection method thereof
CN103720640B (en) * 2013-12-31 2016-01-13 哈尔滨欧替药业有限公司 Povidone iodine vaginal expansible plug and preparation method thereof and detection method
CN103891772B (en) * 2014-04-21 2016-07-20 成都科宏达科技有限公司 A kind of compound disinfecting antibacterial
CN103891772A (en) * 2014-04-21 2014-07-02 成都科宏达科技有限公司 Compound sterilizing agent
CN104604934B (en) * 2015-01-21 2017-11-03 成都科宏达科技有限公司 A kind of compound iodine disinfectant and its preparation method and application
CN104604934A (en) * 2015-01-21 2015-05-13 成都科宏达科技有限公司 Novel composite iodine disinfectant as well as preparation method and application thereof
CN106135274A (en) * 2015-04-22 2016-11-23 苏州泰利三佳纳米科技有限公司 A kind of medicated clothing skin degerming agent composition containing iodine and preparation method thereof
CN111328806A (en) * 2020-03-07 2020-06-26 郑州大学 Double-linear alkyl quaternary ammonium salt complex iodine bactericide
CN111685114A (en) * 2020-07-02 2020-09-22 江苏敖众药业有限公司 Composite iodine solution with high distribution coefficient and preparation method thereof
CN111937901A (en) * 2020-09-15 2020-11-17 四川长宁天然气开发有限责任公司 Special foamless composite bactericide for shale gas well pipeline and preparation method thereof
CN111937901B (en) * 2020-09-15 2021-06-01 四川长宁天然气开发有限责任公司 Special foamless composite bactericide for shale gas well pipeline and preparation method thereof
CN112704080A (en) * 2020-12-30 2021-04-27 佛山市正典生物技术有限公司 Iodine-containing disinfectant with stable component content and preparation method thereof
CN113801028A (en) * 2021-10-15 2021-12-17 成都科宏达科技有限公司 Special surfactant for hydrogen peroxide and compound thereof
CN113801028B (en) * 2021-10-15 2023-11-10 成都科宏达科技有限公司 Special surfactant for hydrogen peroxide and compound thereof

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Application publication date: 20120711