CN108477209A - A kind of thimerosal and preparation method thereof - Google Patents

A kind of thimerosal and preparation method thereof Download PDF

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Publication number
CN108477209A
CN108477209A CN201810542085.4A CN201810542085A CN108477209A CN 108477209 A CN108477209 A CN 108477209A CN 201810542085 A CN201810542085 A CN 201810542085A CN 108477209 A CN108477209 A CN 108477209A
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Prior art keywords
weight
thimerosal
parts
hydrogen peroxide
present
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CN201810542085.4A
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CN108477209B (en
Inventor
林松
郝丽梅
吴金辉
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Institute of Medical Support Technology of Academy of System Engineering of Academy of Military Science
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Institute of Medical Support Technology of Academy of System Engineering of Academy of Military Science
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02Amines; Quaternary ammonium compounds
    • A01N33/12Quaternary ammonium compounds

Abstract

The present invention provides a kind of thimerosals, by weight, including following components:3~17 parts by weight of hydrogen peroxide, 0.1~10 parts by weight of dodecyl dimethyl Benzyl halides ammonium, 1~5 parts by weight of cosolvent, 1~5 parts by weight of stabilizer, 60~95 parts by weight of water.The present invention compounds the significant sterilizing power for improving thimerosal by carrying out hydrogen peroxide and dodecyl dimethyl Benzyl halides ammonium, avoids the carcinogenic and perishable risk that formaldehydes and acids high effect disinfectants are added in conventional method.And two kinds of main antimicrobial components and other surfaces activating agent do not conflict mutually, enhance respective effect by being used in combination, belong to the composite disinfectant of a kind of less toxic, quick, high-efficiency broad spectrum, low-corrosiveness.

Description

A kind of thimerosal and preparation method thereof
Technical field
The present invention relates to disinfection technology fields more particularly to a kind of thimerosal and preparation method thereof.
Background technology
Hydrogen peroxide is a kind of peroxide disinfectant, can form the very strong hydroxyl radical free radical of oxidability and work in water Property derivative, so as to destroy microorganism cell membrane and plasm and achieve the purpose that sterilizing.Hydrogen peroxide has very strong oxygen Change ability, wide sterilization spectrum can effectively kill various bacterial propagules, fungi, tubercle bacillus and various viruses, in many necks Domain is used widely, and cleaning wound and local disinfecting, antimicrobial are commonly used to, it may also be used for tableware, clothes, drinking-water, contact lenses and The disinfection of heat labile plastic products.But the relatively unstable property of hydrogen peroxide and the not efficient killing effect for gemma It is limited further to be widely applied.
In the prior art, the Chinese patent of Publication No. CN102696674A reports a kind of addition alkyl amine-oxides, gold Belong to the low concentration hydrogen peroxide compound disinfectant (mass concentration of hydrogen peroxide is 0.1~1%) of ionic complexing agent and inorganic acid, And carried out quantitative bacteric idal experiment, the results showed that the hydrogen peroxide compound disinfectant to staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and Candida albicans have preferable killing effect.Chinese Patent Application No. reports for CN101032254A A kind of H 2 O 2 air disinfectant with high, and it is added to polyhydroxylated polymer and Peracetic acid.Chinese Patent Application No. is CN101053330A reports a kind of technology improving hydrogen peroxide bactericidal activity, by adding various acid, acid anhydrides and Organic Alcohol Class molecule is to improve the useful effect concentration and stability of hydrogen peroxide.Chinese Patent Application No. is that CN1379983A discloses one Kind is with peracetic acid, the composite disinfectant of urea and the main sterilizing activity object of hydrogen peroxide.Although above-mentioned thimerosal is one Determine to improve the sterilization effect and stability of thimerosal in degree, but be all added to acidic materials, the acidic materials are sterilizing The electrochemical corrosion generated in liquid will produce prodigious influence to the service life of sterilization objects and performance.
Invention content
The purpose of the present invention is to provide one kind under the premise of ensureing bactericidal effect, the low disinfection of electrochemical corrosion behavior Liquid and preparation method thereof.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
The present invention provides a kind of thimerosals, by weight, including following components:
Preferably, by weight, the thimerosal includes following components:
Preferably, the mass concentration of the hydrogen peroxide is 30%~60%.
Preferably, the dodecyl dimethyl Benzyl halides ammonium is dodecyl benzyl dimethyl ammonium chloride and/or ten Dialkyl dimethyl Benzylphosphonium Bromide ammonium.
Preferably, the cosolvent is lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, spits One or more of temperature -80, PEG-600, PEG200, PEG300 and PEG400.
Preferably, the stabilizer is in ethylenediamine tetra-acetic acid, diethyl triamine pentaacetic acid and N-hydroxyethyl-ethylenediamine triacetic acid One or more.
The present invention also provides the preparation methods of the thimerosal, include the following steps:
Hydrogen peroxide, dodecyl dimethyl Benzyl halides ammonium, cosolvent, stabilizer and water are mixed, be sterilized liquid.
Preferably, the temperature of the mixing is 15~35 DEG C.
Preferably, described to be blended in stirring or carried out under conditions of vibrating.
The present invention provides a kind of thimerosals, by weight, including following components:3~17 parts by weight of hydrogen peroxide, 12 0.1~10 parts by weight of alkyl-dimethyl benzyl ammonium halide, 1~5 parts by weight of cosolvent, 1~5 parts by weight of stabilizer, water 60~95 Parts by weight.The present invention significantly improves thimerosal by compound hydrogen peroxide and dodecyl dimethyl Benzyl halides ammonium Sterilizing power, avoid in conventional method be added formaldehydes and acids high effect disinfectants carcinogenic and perishable wind Danger.And two kinds of main antimicrobial components and other surfaces activating agent do not conflict mutually, and respective effect is enhanced by being used in combination, Belong to the composite disinfectant of a kind of less toxic, quick, high-efficiency broad spectrum, low-corrosiveness.
Description of the drawings
Fig. 1 is that 316 stainless steel of thimerosal pair, copper sheet and aluminium flake described in embodiment 1 show through the appearance before and after corrosion test It is intended to.
Specific implementation mode
The present invention provides a kind of thimerosals, by weight, including following components:
In the present invention, if without specified otherwise, all raw material components are well known to the skilled person commercially available Product.
It counts in parts by weight, thimerosal of the present invention includes the hydrogen peroxide of 3~17 parts by weight, preferably 5~10 weight Part, more preferably 6~8 parts by weight.In the present invention, the mass concentration of the hydrogen peroxide is preferably 30%~60%, more preferably It is 35%~55%, most preferably 40%~50%.
On the basis of the quality of hydrogen peroxide, thimerosal of the present invention includes the dodecyl two of 0.1~10 parts by weight Methylbenzyl ammonium halide, preferably 3~7 parts by weight, more preferably 4~6 parts by weight.In the present invention, the dodecyl two Methylbenzyl ammonium halide is preferably dodecyl benzyl dimethyl ammonium chloride and/or dodecyl dimethyl benzyl ammonium bromide;When When the dodecyl dimethyl Benzyl halides ammonium is two kinds in above-mentioned specific choice, the present invention does not have the ratio of each substance Any special restriction, can mix in any proportion.
In the present invention, the dodecyl dimethyl ammonium halide is compounded with hydrogen peroxide, is played in terms of sterilizing Preferable synergistic effect, bactericidal effect have obtained " 1+1>2 " effect, and avoid addition acidic materials in conventional method and carry The serious electrochemical corrosion generated while high bactericidal effect.
On the basis of the quality of hydrogen peroxide, thimerosal of the present invention includes the cosolvent of 1~5 parts by weight, preferably 2~ 4 parts by weight, more preferably 2.5~3.5 parts by weight.In the present invention, the cosolvent is lauryl sodium sulfate, dodecyl One or more of sodium sulfonate, neopelex, Tween-80, PEG-600, PEG200, PEG300 and PEG400; In the present invention, when the cosolvent be above-mentioned specific choice in it is two or more when, there do not have to the ratio of each substance to be special It limits, can mix in any proportion;In the present invention, the cosolvent is preferably a kind in above-mentioned specific choice.
In the present invention, the cosolvent functions as surfactant, to dodecyl dimethyl benzyl therein Base ammonium halide component plays the effect for accelerating dissolving and solubilising.
On the basis of the quality of hydrogen peroxide, thimerosal of the present invention includes the stabilizer of 1~5 parts by weight, preferably 2~ 4 parts by weight, more preferably 2.5~3.5 parts by weight.In the present invention, the stabilizer is preferably ethylenediamine tetra-acetic acid, diethylamine One or more of pentaacetic acid and N-hydroxyethyl-ethylenediamine triacetic acid;In the present invention, when the stabilizer is above-mentioned specific When two or more in selection, there is no special restriction to the ratio of each substance, can mix in any proportion;In the present invention, The stabilizer is preferably a kind in above-mentioned specific choice.
In the present invention, the effect of the stabilizer is that have certain oxidation resistance, can be formed with metal ion Stable complex compound, can be strong bonded with general impurity, and has certain heat-resisting ability, avoids the decomposition of hydrogen peroxide.
On the basis of the quality of hydrogen peroxide, thimerosal of the present invention includes the water of 60~95 parts by weight, preferably 70~ 90 parts by weight, more preferably 75~85 parts by weight.The present invention does not have any special restriction to the type of the water, using ability The type of water known to field technique personnel.
The present invention also provides the preparation methods of the thimerosal, include the following steps:
Hydrogen peroxide, dodecyl dimethyl Benzyl halides ammonium, cosolvent, stabilizer and water are mixed, be sterilized liquid.
In the present invention, the temperature of the mixing is preferably 15~35 DEG C, more preferably 20~30 DEG C, most preferably 22~ 28℃
In the present invention, the mixing preferably carries out under conditions of stirring or oscillation.The present invention is to the stirring or shakes The velocity and time swung can be such that each component in mixed liquor is sufficiently mixed without any special restriction.
The addition sequence of each substance does not have any special restriction when the present invention is to the mixing, using people in the art Order by merging known to member is mixed.
In a specific embodiment of the present invention, the mixing preferably includes following steps:
1) stabilizer, cosolvent are mixed with water;
2) dodecyl dimethyl Benzyl halides ammonium and hydrogen peroxide are sequentially added in mixed liquor obtained by the step 1).
Thimerosal provided by the invention is described in detail with reference to embodiment, but they cannot be interpreted as pair The restriction of the scope of the present invention.
Embodiment 1
83 weight are added in the lauryl sodium sulfate of the ethylenediamine tetra-acetic acid (EDTA), 4 parts by weight that weigh 4 parts by weight respectively In the water of part, made it completely dissolved by vibrating stirring;
At ambient temperature, dodecyl benzyl dimethyl ammonium chloride and the stirring of 4 parts by weight are added in above-mentioned solution It is completely dissolved to it, the hydrogen peroxide mixing for being 60% with the mass concentration of 5 parts by weight after the completion of dissolving, be sterilized liquid.
Embodiment 2
83 weight are added in the lauryl sodium sulfate of the ethylenediamine tetra-acetic acid (EDTA), 4 parts by weight that weigh 4 parts by weight respectively In the water of part, made it completely dissolved by vibrating stirring;
At ambient temperature, dodecyl dimethyl benzyl ammonium bromide and the stirring of 4 parts by weight are added in above-mentioned solution It is completely dissolved to it, the hydrogen peroxide mixing for being 60% with the mass concentration of 5 parts by weight after the completion of dissolving, be sterilized liquid.
Embodiment 3
The lauryl sodium sulfate of the ethylenediamine tetra-acetic acid (EDTA), 4 parts by weight that weigh 4 parts by weight respectively is added 71.33 In the water of parts by weight, made it completely dissolved by vibrating stirring;
At ambient temperature, the dodecyl dimethyl benzyl ammonium bromide and 2 weight of 2 parts by weight are added in above-mentioned solution Part dodecyl benzyl dimethyl ammonium chloride and stirring to it be completely dissolved, after the completion of dissolving with the quality of 16.67 parts by weight A concentration of 30% hydrogen peroxide mixing, be sterilized liquid.
Comparative example 1
87 weight are added in the lauryl sodium sulfate of the ethylenediamine tetra-acetic acid (EDTA), 4 parts by weight that weigh 4 parts by weight respectively In the water of part, made it completely dissolved by vibrating stirring;
At ambient temperature, the hydrogen peroxide mixing for being 60% by the mass concentration of above-mentioned solution and 5 parts by weight, is sterilized Liquid.
Comparative example 2
The lauryl sodium sulfate of the ethylenediamine tetra-acetic acid (EDTA), 4 parts by weight that weigh 4 parts by weight respectively is added 75.33 In the water of parts by weight, made it completely dissolved by vibrating stirring;
At ambient temperature, the hydrogen peroxide mixing for being 30% by the mass concentration of above-mentioned solution and 16.67 parts by weight, obtains Thimerosal.
Comparative example 3
88 weight are added in the lauryl sodium sulfate of the ethylenediamine tetra-acetic acid (EDTA), 4 parts by weight that weigh 4 parts by weight respectively In the water of part, made it completely dissolved by vibrating stirring;
At ambient temperature, by the dodecyl benzyl dimethyl ammonium chloride mixing of above-mentioned solution and 4 parts by weight, disappeared Venom.
Comparative example 4
88 weight are added in the lauryl sodium sulfate of the ethylenediamine tetra-acetic acid (EDTA), 4 parts by weight that weigh 4 parts by weight respectively In the water of part, made it completely dissolved by vibrating stirring;
At ambient temperature, by the dodecyl dimethyl benzyl ammonium bromide mixing of above-mentioned solution and 4 parts by weight, disappeared Venom.
Embodiment 4
Corrosive nature test is carried out to thimerosal prepared by embodiment 1, it is specific as follows:
316 stainless steels, copper sheet and aluminium flake are immersed respectively in the thimerosal, and impregnate 72 hours, copper sheet, aluminium flake and 316 stainless steels, which impregnate front and back quality, does not have apparent significant difference, serious corrosion does not occur.
Corrosion results are as shown in Figure 1:There are the corrosivity blackening of small area on copper coin and aluminium sheet, only have to copper coin and aluminium sheet Slight corrosion, 316 stainless steels do not occur corrosivity blackening, and preferable tolerance is all had to 316 stainless steels, copper sheet and aluminium flake Can, wherein the tolerance performance to 316 stainless steels is best.
The thimerosal prepared to Examples 1 to 3 and comparative example 1~4 carries out the killing to bacillus subtilis black variety gemma Effect performance test, it is specific as follows:
Specific test result such as table 1:
Thimerosal prepared by 1 Examples 1 to 3 of table and comparative example 1~4 is to bacillus subtilis var bud
The killing effect of spore
Note:The expression for drawing whippletree is preferable due to killing curve calculating and practical fitting, and has been in obviously gentle slack-off Trend, therefore do not carry out sampling site sampling and testing in the point.
As seen from the above table, thimerosal of the present invention kills the logarithm of gemma in 45min can reach 6 or more, Comply fully with FDA and《Disinfection technology standard》Defined disinfection standard.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.

Claims (9)

1. a kind of thimerosal, by weight, including following components:
2. thimerosal as described in claim 1, which is characterized in that by weight, the thimerosal includes following components:
3. thimerosal as claimed in claim 1 or 2, which is characterized in that the mass concentration of the hydrogen peroxide is 30%~60%.
4. thimerosal as claimed in claim 1 or 2, which is characterized in that the dodecyl dimethyl Benzyl halides ammonium is ten Dialkyl dimethyl benzyl ammonium chloride and/or dodecyl dimethyl benzyl ammonium bromide.
5. thimerosal as claimed in claim 1 or 2, which is characterized in that the cosolvent is lauryl sodium sulfate, dodecane One kind or several in base sodium sulfonate, neopelex, Tween-80, PEG-600, PEG200, PEG300 and PEG400 Kind.
6. thimerosal as claimed in claim 1 or 2, which is characterized in that the stabilizer is ethylenediamine tetra-acetic acid, diethylamine five One or more of acetic acid and N-hydroxyethyl-ethylenediamine triacetic acid.
7. the preparation method of claim 1~6 any one of them thimerosal, includes the following steps:
Hydrogen peroxide, dodecyl dimethyl Benzyl halides ammonium, cosolvent, stabilizer and water are mixed, be sterilized liquid.
8. preparation method as claimed in claim 7, which is characterized in that the temperature of the mixing is 15~35 DEG C.
9. preparation method as claimed in claim 7 or 8, which is characterized in that it is described be blended in stirring or oscillation under conditions of into Row.
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Cited By (4)

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CN109907070A (en) * 2019-04-04 2019-06-21 上海恤世化学技术有限公司 A kind of thimerosal and preparation method
WO2020215349A1 (en) * 2019-04-22 2020-10-29 肇庆大华农生物药品有限公司 Compound hydrogen peroxide disinfection diluent, use thereof and method for disinfecting surface of egg
CN114747568A (en) * 2022-04-27 2022-07-15 山东利尔康医疗科技股份有限公司 Medium-level disinfection wet tissue and preparation method thereof
CN115245174A (en) * 2022-08-15 2022-10-28 山东大学 Water-soluble compound potassium hydrogen persulfate disinfectant and preparation method thereof

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
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CN114747568A (en) * 2022-04-27 2022-07-15 山东利尔康医疗科技股份有限公司 Medium-level disinfection wet tissue and preparation method thereof
CN115245174A (en) * 2022-08-15 2022-10-28 山东大学 Water-soluble compound potassium hydrogen persulfate disinfectant and preparation method thereof

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