CN108077252A - Double-chain quaternary ammonium salt thimerosal - Google Patents
Double-chain quaternary ammonium salt thimerosal Download PDFInfo
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- CN108077252A CN108077252A CN201711401257.8A CN201711401257A CN108077252A CN 108077252 A CN108077252 A CN 108077252A CN 201711401257 A CN201711401257 A CN 201711401257A CN 108077252 A CN108077252 A CN 108077252A
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- quaternary ammonium
- ammonium salt
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/02—Acyclic compounds
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- Pest Control & Pesticides (AREA)
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Abstract
The invention discloses a kind of double-chain quaternary ammonium salt thimerosal, which includes the following ingredient according to mass parts meter:10 50 parts of double decyl dimethyl ammonium bromides, 0.1 20 parts of organic stabilizer, 0.01 10 parts of inorganic stabilizers and 0.1 15 parts of nonionic surfactant.Double-chain quaternary ammonium salt thimerosal disclosed by the invention has the advantages that stable storage and germicidal efficiency are good.
Description
Technical field
The invention belongs to thimerosal fields, and in particular to a kind of double-chain quaternary ammonium salt thimerosal.
Background technology
Double-chain quaternary ammonium salt class compound is as thimerosal has performance stabilization, toxicity irritation is small, corrosivity is low, smell is small
The advantages that.Meanwhile the biological degradability of double-chain quaternary ammonium salt thimerosal is good, it is pollution-free to environment (waters), therefore can extensive utilization
In the disinfection of industrial or agricultural, hospital, family and public environment health.
It is mostly that chemical disinfection liquid is compound makes with other for double-chain quaternary ammonium salt in the formula of existing double-chain quaternary ammonium salt thimerosal
With after a period of time is prepared, under the conditions of existing for natural light, oxygen or moisture etc., interaction is easy between each ingredient of solution
Change colour, thimerosal becomes yellow or even dark-brown from colourless, can be in disinfection object remained on surface when carrying out disinfection to object
Color stain, influences using effect and appearance.
The content of the invention
In order at least solve one of technical problem existing in the prior art mentioned above, the invention discloses a kind of double-strand seasons
Ammonium salt thimerosal has the advantages that sterilization is fast, the stability of product is good, non-discolouring and do not generate contamination precipitation.
Double-chain quaternary ammonium salt thimerosal disclosed by the invention, including the following ingredient according to mass parts meter:10-50 parts of pair
Decyl dimethyl ammonium bromide, 0.1-20 parts of organic stabilizer, 0.01-10 parts of inorganic stabilizers and 0.1-15 parts of nonionic
Surfactant.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the inorganic stabilizers are sulfites
Compound.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the inorganic stabilizers are sodium sulfite, Asia
One or more combinations in niter cake, potassium sulfite and potassium bisulfite.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the inorganic stabilizers are gone back to be water-soluble
Former agent.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the inorganic stabilizers sodium borohydride and boron
The combination of one or both of hydrofining.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the organic stabilizer is polyethylene glycol
200th, one or more combinations in polyethylene glycol 400, propylene glycol, polyvinyl alcohol.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the nonionic surfactant is 12
Alkyl dimethyl amine oxide, octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, water-soluble high-carbon fatty alcohol polyoxyethylene
One or more combinations in ether and polyether nonionic surfactant.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, which further includes 1-20 parts of synergy
Agent.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the synergist is 1,3-BDO.
In some embodiments, in the double-chain quaternary ammonium salt thimerosal, the pH value of the thimerosal is 7-9.
Specific embodiment
Dedicated word " embodiment " herein, any embodiment illustrated by as " exemplary " should not necessarily be construed as being better than or
It is better than other embodiments.Testing performance index in this law embodiment, unless stated otherwise, using this field conventional methods.
It is to be understood that heretofore described term is only to describe special embodiment, being not intended to limit disclosed by the invention
Content.
Unless otherwise stated, technical and scientific terms used herein has the common of the technical field of the invention
The normally understood identical meanings of technical staff;Represent that the unit of material content is based on quality in terms of part.As in the present invention
Other not especially dated raw material, reagents refer both to usually used raw material and reagent in the art.
In the present invention, the quaternary ammonium salt is also known as quarternary ammonium salt, be four hydrogen atoms in ammonium ion be all optionally substituted by a hydroxyl group and
The compound of generation, general formula R4NX, quaternary ammonium salt is similar to inorganic salts property, soluble easily in water, aqueous conductive.Quaternary ammonium salt has
Sterilizing function and by as thimerosal, sterilizing mechanisms are:Quaternary ammonium salt dissociates quaternary ammonium cation in water, bacterium surface it is thin
Cell wall carries negative electrical charge, and the positive charge in quaternary ammonium molecules of salt has stronger suction-operated to bacterium, passes through what is permeated and spread
Effect, enters cell membrane through the surface of bacterium, cell damage and cell interior metabolite coenzyme is caused to reveal, so as to hinder
The semi-permeable effect of cell membrane, and cell interior is further penetrated through, make cell enzymatic inactivation, it is impossible to protease is generated, so that
Protein denaturation is obtained, achievees the purpose that kill bacterial cell.
In the present invention, added in 10-50 parts of double decyl dimethyl ammonium bromides organic stabilizer, inorganic stabilizers and it is non-from
Sub- surfactant.Organic stabilizer can strengthen sterilizing the intermiscibility of each component in liquor, improve the stabilization of thimerosal
Property.Inorganic stabilizers are added in double decyl dimethyl ammonium bromides, the surface tension of thimerosal is reduced using inorganic stabilizers, are prevented
Only light, thermal decomposition or oxygenolysis increase disinfection liquor and are deposited in natural light irradiation, ultraviolet light, heat, oxygen and/or moisture
Environment in stability.Meanwhile nonionic surfactant is added in thimerosal, improve the penetrating of bacteria cell wall
Property, accelerate the outflow of inclusion in bacterium, so as to accelerate cell death, promote sterilization rate.Add in nonionic surfactant
Thimerosal afterwards is not easy to be influenced by acid, alkali, and can be used in mixed way with other types surfactant, and compatibility is good, various
There is good dissolubility in solvent, strong adsorption does not occur on a solid surface, improve the cleaning journey after thimerosal use
Degree.
In the present invention, the inorganic stabilizers are sulfites compound, and sulfites compound has anti-oxidant
Effect, can inhibit the activity of oxidizing ferment, prevent discoloration problem caused by oxidizing ferment.Also, sulphite has strong reducing property
Sulfur dioxide, sulphite can be combined with coloring matter, and the thimerosal after discoloration is bleached, is disappeared so as to solve quaternary ammonium salt
The discoloration problem of venom.Preferably, the inorganic stabilizers are sodium sulfite, sodium hydrogensulfite, potassium sulfite and bisulfite
One or more in potassium, more preferably, the inorganic stabilizers are sodium sulfite.
In the present invention, the inorganic stabilizers are water-soluble reducing agent, and the coloring matter of variation will be aoxidized using reducing agent
Colourless substance is reduced into, keeps the stability of color.
Double-chain quaternary ammonium salt thimerosal disclosed by the invention, has that sterilization is fast, the stability of product is good, non-discolouring and do not generate
The advantages of contamination precipitation.
Embodiment
Embodiment 1
A kind of double-chain quaternary ammonium salt thimerosal, includes according to mass parts meter, 10 parts of double decyl dimethyl ammonium bromides, 0.1
The dodecyldimethylamine oxide, 0.1 part of polyethylene glycol 400,0.01 part of sodium sulfite and 1 part of 1,3- fourths two of part
Alcohol, remaining is water.
Preparation method:Water is added in into charging tank, is stirred, adds in double decyl dimethyl ammonium bromides, 12 thereto successively
Alkyl dimethyl amine oxide, polyethylene glycol 400, sodium sulfite and 1,3-BDO, after stirring and dissolving is uniform, when precipitation 24 is small,
Filtering.
Embodiment 2
A kind of double-chain quaternary ammonium salt thimerosal, includes according to mass parts meter, 20 parts of double decyl dimethyl ammonium bromides, 10 parts
Dodecyldimethylamine oxide, 5 parts of polyethylene glycol 400,2 parts of sodium sulfite and 10 parts of 1,3-BDO, remaining
For water.
Preparation method:Water is added in into charging tank, is stirred, adds in double decyl dimethyl ammonium bromides, 12 thereto successively
Alkyl dimethyl amine oxide, polyethylene glycol 400, sodium sulfite and 1,3-BDO, after stirring and dissolving is uniform, when precipitation 24 is small,
Filtering.
Embodiment 3
A kind of double-chain quaternary ammonium salt thimerosal, includes according to mass parts meter, 12 parts of double decyl dimethyl ammonium bromides, 1 part
Octyl phenol polyoxyethylene ether, 0.5 part of propylene glycol, 0.08 part of sodium hydrogensulfite and 2 parts of 1,3-BDO, remaining is
Water.
Preparation method:Water is added in into charging tank, is stirred, adds in double decyl dimethyl ammonium bromides, octyl group thereto successively
Phenol polyethenoxy ether, propylene glycol, sodium hydrogensulfite and 1,3-BDO, after stirring and dissolving is uniform, when precipitation 24 is small, filtering.
Embodiment 4
A kind of double-chain quaternary ammonium salt thimerosal, includes according to mass parts meter, 15 parts of double decyl dimethyl ammonium bromides, 2 parts
Nonylphenol polyoxyethylene ether, 3 parts of polyvinyl alcohol, 1 part of potassium sulfite and 5 parts of 1,3-BDO, remaining is water.
Preparation method:Water is added in into charging tank, is stirred, adds in double decyl dimethyl ammonium bromides, nonyl thereto successively
Phenol polyethenoxy ether, polyvinyl alcohol, potassium sulfite and 1,3-BDO, after stirring and dissolving is uniform, when precipitation 24 is small, filtering.
Embodiment 5
A kind of double-chain quaternary ammonium salt thimerosal, includes according to mass parts meter, 17 parts of double decyl dimethyl ammonium bromides, 2.5
The dodecyldimethylamine oxide, 4 parts of polyethylene glycol 200,1.5 parts of potassium bisulfite and 8 parts of 1,3-BDO of part,
Remaining is water.
Preparation method:Water is added in into charging tank, is stirred, adds in double decyl dimethyl ammonium bromides, 12 thereto successively
Alkyl dimethyl amine oxide, polyethylene glycol 200, potassium bisulfite and 1,3-BDO, after stirring and dissolving is uniform, precipitation 24 is small
When, filtering.
The performance detection of embodiment 1 to 5
1. physicochemical property
The average value of double-chain quaternary ammonium salt thimerosal pH described in embodiment 1 to embodiment 5 is 8.71.The double-strand season of the present invention
Ammonium salt thimerosal 1:30 dilutions to the corrosion rate category moderate corrosion grade of carbon steel, belong to slight to the corrosion rate of aluminium and copper
Corrosion class belongs to no corrosion to the corrosion rate of stainless steel.
2. neutralizer qualification test
Neutralization test is carried out using the double-chain quaternary ammonium salt thimerosal neutralized described in dilution method embodiment 1 to embodiment 5,
In, by the thimerosal described in embodiment 1 to 5 and standard hard water proportionally 1:50 are mixed into the first mixed solution, using by
It is molten that the neutralizer of the PBS compositions of 10g/L histidines, 3.0% Tween-80 and 3g/L lecithin can neutralize above-mentioned first mixing
Liquid, and neutralization agent solution and the corresponding solution of above-mentioned neutralization reaction product do not influence the growth of staphylococcus aureus;It will be real
Apply thimerosal described in example 1 to 5 and standard hard water proportionally 1:30 are mixed into the second mixed solution, using by 10g/L group ammonia
The neutralizer of the PBS compositions of acid, 3.0% Tween-80 and 3g/L lecithin can neutralize above-mentioned second mixed solution, and neutralizer
Solution and the corresponding solution of above-mentioned neutralization reaction product do not influence the growth of bacillus subtilis black variety gemma.
3. kill microbiological test
By the thimerosal described in embodiment 1 to 5 and standard hard water proportionally 1:50 are mixed into the first mixed solution, 20
Under the conditions of DEG C ± 1 DEG C, 5min is acted on staphylococcus aureus, Escherichia coli and pseudomonas aeruginosa, and microorganism is killed in detection
Numerical value, wherein, staphylococcus aureus is averagely killed to numerical value > 5.00, and Escherichia coli are averagely killed to numerical value > 5.00,
Pseudomonas aeruginosa is averagely killed to numerical value > 5.00;By the thimerosal described in embodiment 1 to 5 and standard hard water proportionally 1:
3 are mixed into the second mixed solution, under the conditions of 20 DEG C ± 1 DEG C, act on 20min to bacillus subtilis black variety gemma, detection is killed
The numerical value of microorganism killing, the killing of bacillus subtilis black variety gemma is 0.25 to numerical value.
4. surface disinfection field test
Thimerosal described corresponding to embodiment 1 to 5 is prepared 6, totally 30 test specimens, by each test sample
It is 1 according to mixed proportion:50 mix test specimen with standard hard water, uniformly smearing and body surface, detection object after 5min
The killing bacterial strain quantity on surface, body surface natural bacteria are averagely killed to numerical value > 1.00.
5. medical apparatus sterilizing Simulation field test
Thimerosal described corresponding to embodiment 1 to 5 is prepared 6, totally 30 test specimens, by each test sample
It is 1 according to mixed proportion:50 mix test specimen with standard hard water, under 20 DEG C of ± 1 DEG C of water bath conditions, by the examination after dilution
It tests sample to be uniformly applied to respectively on 30 medical instrument carrier samples, acts on 20min, detect each medical instrument carrier sample
The killing number of upper bacillus subtilis black variety gemma, the average killing of bacillus subtilis black variety gemma is 0.15 to numerical value.
6. stability test
(1) appearance stability is tested.Thimerosal described corresponding to embodiment 1 to 5 is attached separately in closed container, is put
In observing its state after 14 days in 54 DEG C of insulating boxs.The color of the thimerosal is unchanged corresponding to embodiment 1 to 5, in equal
First, clear state, no precipitation or suspended matter generate, and appearance stability is good.
(2) chemical assay measures stability test.Thimerosal described corresponding to embodiment 1 to 5 is attached separately to close
It closes in container, puts 14d in 54 DEG C of insulating boxs.In the forward and backward measure thimerosal bactericidal active ingredient content respectively of placement.Through titration
It measures, active ingredient rate of descent≤10% meets the requirements.Storage life is 1 year.
The toxicity test detection of embodiment 1 to 5
1. acute oral toxicity test
By points 5 groups at random of weighed in 50 mouse (when fasting 16 is small), then to each group mouse with oral gavage
Method is once contaminated.Gavage volume is 20mL/kg.When continuation fasting 3-4 is small after contamination.Observe and record contamination process and observation period
The poisoning of interior mouse and death condition, observing time 14d.Stoste chmice acute Oral toxicity LD50=926mg/kg weight,
95% credible is limited to 636-1350mg/kg weight, toxicity grading category low toxicity level.
Configuration concentration is the double-chain quaternary ammonium salt thimerosal of 5 times of highest application concentration, and carries out acute oral toxicity examination to it
It tests, is computed tested material concentration as 50g/L, then operates as stated above.Mouse LD50 > 5000mg/kg weight, true border
It is nontoxic.
2. mice bone marrow micronucleus
Respectively using the thimerosal corresponding to embodiment 1 to 3 as 3 dosage groups, each dosage group 10 mouse, male and female
It is fifty-fifty.It is another to set negative (solvent) and positive controls.Method is contaminated to mouse contamination using oral gavage 30.At cervical dislocation
Dead animal, takes femur.0.1mL calf serums are drawn with syringe, rinse ossis.It, will after drying with flushing liquor routine smear
The smear fixes 5min-10min in methyl alcohol.10min-15min is dyed with Ji's nurse Sa application liquid, is then rushed with pH6.8PBS liquid
It washes, dries.Positive group selects cyclophosphamide (40mg/kg weight).Negative (solvent) control group tested material solvent.Under oil mirror
Count polychromatic erythrocyte (PCE) number containing micronucleus.Every animal counts 1000 PCE.Observe PCE/NCE ratios simultaneously.It is real
Test the result shows that, the thimerosal to mouse bone marrow polychromatic erythrocytes without cause micronucleus effect.
A 3. intact skin irritant test
Before the test for 24 hours, the hair of guinea pig back backbone both sides is removed with depilatory agent, unhairing scope, left and right Ge Yue 3cm ×
3cm.Next day directly drips the thimerosal 0.5mL corresponding to embodiment 4 complete in the one side unhairing that area is 2.5cm × 2.5cm
On skin.Opposite side skin of unhairing is as blank control.The application time is 4h.The 1h, for 24 hours and 48h after tested material is removed
Local skin reaction is observed, and is pressed《Disinfection technology standard》Respective list carries out stimulate the reaction scoring.Integral mean is 1.67,
Skin irritation index < 2.0, stimulus intensity category slight stimulation.
Double-chain quaternary ammonium salt thimerosal disclosed by the embodiments of the present invention, have sterilization is fast, the stability of product is good, it is non-discolouring and
Not the advantages of not generating contamination precipitation.
In the case of without departing substantially from the scope or spirit of the invention, the specific embodiment of description of the invention can be done more
Kind is improved and variation, this will be apparent to those skilled in the art.Other realities obtained by the specification of the present invention
It is apparent obtain for technical personnel to apply mode.Present specification and embodiment are only exemplary.
Claims (10)
1. a kind of double-chain quaternary ammonium salt thimerosal, which is characterized in that the thimerosal includes, according to mass parts meter, 10-50 parts of double last of the ten Heavenly stems
Base ditallowdimethyl ammonium bromide, 0.1-20 parts of organic stabilizer, 0.01-10 parts of inorganic stabilizers and 0.1-15 parts of nonionic table
Face activating agent.
2. double-chain quaternary ammonium salt thimerosal according to claim 1, which is characterized in that the inorganic stabilizers are sulphite
Class compound.
3. double-chain quaternary ammonium salt thimerosal according to claim 2, which is characterized in that the inorganic stabilizers are sulfurous acid
One or more combinations in sodium, sodium hydrogensulfite, potassium sulfite and potassium bisulfite.
4. double-chain quaternary ammonium salt thimerosal according to claim 1, which is characterized in that the inorganic stabilizers are water-soluble
Reducing agent.
5. double-chain quaternary ammonium salt thimerosal according to claim 4, which is characterized in that the inorganic stabilizers are sodium borohydride
With the combination of one or both of potassium borohydride.
6. double-chain quaternary ammonium salt thimerosal according to claim 1, which is characterized in that the organic stabilizer is polyethylene glycol
200th, one or more combinations in polyethylene glycol 400, propylene glycol, polyvinyl alcohol.
7. double-chain quaternary ammonium salt thimerosal according to claim 1, which is characterized in that the nonionic surfactant is ten
Dialkyl dimethyl amine oxide, octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, water-soluble high-carbon fatty alcohol polyoxy second
One or more combinations in alkene ether and polyether nonionic surfactant.
8. double-chain quaternary ammonium salt thimerosal according to claim 1, which is characterized in that the thimerosal further includes 1-20 parts of increasing
Imitate agent.
9. double-chain quaternary ammonium salt thimerosal according to claim 8, which is characterized in that the synergist is 1,3-BDO.
10. double-chain quaternary ammonium salt thimerosal according to claim 1, which is characterized in that the pH value of the thimerosal is 7-9.
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CN112106788A (en) * | 2020-09-29 | 2020-12-22 | 湖北一末环保实业有限公司 | Low-odor low-corrosivity neutral disinfectant and preparation method thereof |
CN112369415A (en) * | 2020-11-09 | 2021-02-19 | 杨振强 | Non-toxic seedling culture aqueous agent for tobacco seedling culture link |
CN112655704A (en) * | 2020-12-23 | 2021-04-16 | 合肥天一生物技术研究所有限责任公司 | Quaternary ammonium salt composite disinfectant |
CN114805671A (en) * | 2022-04-25 | 2022-07-29 | 水木聚力接枝新技术(深圳)有限责任公司 | Double-long-chain alkane quaternary ammonium salt polymer disinfectant, preparation method thereof and disinfectant |
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CN112106788A (en) * | 2020-09-29 | 2020-12-22 | 湖北一末环保实业有限公司 | Low-odor low-corrosivity neutral disinfectant and preparation method thereof |
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CN114946841B (en) * | 2022-06-16 | 2023-07-21 | 江西健宝医药科技有限公司 | Double-chain quaternary ammonium salt disinfectant and preparation method thereof |
CN114920863A (en) * | 2022-06-21 | 2022-08-19 | 水木聚力接枝新技术(深圳)有限责任公司 | Amphiphilic long paraffin quaternary ammonium salt polymer disinfectant, preparation method thereof and disinfectant |
CN114920863B (en) * | 2022-06-21 | 2023-11-24 | 水木聚力接枝新技术(深圳)有限责任公司 | Amphiphilic long-chain alkane quaternary ammonium salt high-molecular disinfectant, preparation method thereof and disinfectant |
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