CN104496893A - Gemini quaternary ammonium salt for preservative and preservative - Google Patents
Gemini quaternary ammonium salt for preservative and preservative Download PDFInfo
- Publication number
- CN104496893A CN104496893A CN201410856930.7A CN201410856930A CN104496893A CN 104496893 A CN104496893 A CN 104496893A CN 201410856930 A CN201410856930 A CN 201410856930A CN 104496893 A CN104496893 A CN 104496893A
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- quaternary ammonium
- ammonium salt
- sanitas
- gemini
- preservative
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/025—Preservatives, e.g. antimicrobial agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Materials Engineering (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a new Gemini quaternary ammonium salt and a preservative containing the quaternary ammonium salt and a bactericide. The structure of the Gemini quaternary ammonium salt is shown in a formula 4 in the specification. The preservative comprises the Gemini quaternary ammonium salt disclosed by the invention and at least one bactericide selected from 1-bromo-3-chloro-5,5-dimethyl hydantoin and 2,-bromo-2-nitro-1,3-propylene glycol. The preservative disclosed by the invention has effects of rapid sterilization and long-term sterilization. In the formula 4, y is an integer from 0 to 4, n is an integer from 3 to 15, and X is halogen selected from Br, Cl and I.
Description
Technical field
The present invention relates to a kind of Gemini geminus quaternary ammonium salt for sanitas and sanitas, relate more specifically to the storage sanitas in Lacquered Tin Plate Can.
Background technology
Water-borne coatings is dispersion medium with water and is rich in various can, by the additive of microorganism as nutritional utilization, therefore be the desirable hotbed of microbial growth.When amount reproduction after the microbial contamination such as bacterium, yeast and mold coating can cause the change of coating products surface discolouration, mobility variations, pH value, use properties change, cohesion, breakdown of emulsion, the generation peculiar smell even series of problems such as surperficial mildew.Therefore control microbial contamination and breeding, for ensure coating products whole life cycle comprise store in tank time in quality be very important.Since Heidelberger is after reporting quaternary ammonium salt for 1915 and having the sterilizing function of wide spectrum, low toxicity, although water-soluble strand quaternary ammonium salt is widely applied in the fields such as medicine, food, health as sterilant, but studies have found that some bacterium, particularly Gram-negative bacteria has resistance (Sopery PR to QAS, Maxey RB.Toerance of bacteria for quternary ammonium compounds.J.FoodSci, 1968; 24; 141-50; Davies J.Bacteria on the rampage.Nature, 1996; 383:219-20.).
Along with development and the enhancing of global environmental consciousness of chemical industry, people's Surfactant proposes many new requirements, and the tensio-active agent science that appears as of Gemini surface active of new generation has opened up open prospect.Gemini geminus quaternary ammonium salt is because having efficient bactericidal properties and being used in commercial sterilization field to the mildness of environment.
People study and have found the surfactivity of bi-quaternary ammonium salt 2 ~ 3 orders of magnitude high compared with the tensio-active agent of strand quaternary ammonium salt, and adopt bi-quaternary ammonium salt to solve insensitive to quaternary ammonium salt of Gram-negative bacteria, the problem easily developed immunity to drugs obtains good effect.
But because double quaternary ammonium salt type antibacterial moleucles is comparatively large, be easy to cell surface absorption and cause germicidal action to compare the sterilant of other types slowly, i.e. quick sterilization scarce capacity.
Summary of the invention
For overcoming above-mentioned defect, the invention provides a kind of storage sanitas, described sanitas comprises a kind of new Gemini geminus quaternary ammonium salt and a kind of sterilant B, effectively can improve the sterilization timeliness of quaternary ammonium salt, improves sterilization speed.
Sanitas Gemini geminus quaternary ammonium salt of the present invention, its structure as shown in Equation 4:
Wherein y is the integer of 0 ~ 4, and n is the integer of 3 ~ 15, and X is the halogen being selected from Br, Cl and I.
The Gemini geminus quaternary ammonium salt preferential according to the present invention, wherein y be 0,1 or 2, n be 7,9,11 or 13, and X is Br or Cl.
Another aspect of the present invention is a kind of for the storage sanitas in Lacquered Tin Plate Can, comprise Gemini geminus quaternary ammonium salt of the present invention and sterilant, described sterilant is selected from least one of chloro-5, the 5-dimethyl hydantion of the bromo-3-of 1-and 2-bromo-2-nitro-1,3-propylene glycol.
Preferably, the weight ratio of quaternary ammonium salt and described sterilant described in described sanitas is 90:10 ~ 95:5.
Preferably, described sanitas is the aqueous solution comprising described Gemini geminus quaternary ammonium salt and described sterilant.
Preferably, the total concn of Gemini geminus quaternary ammonium salt and described sterilant described in described aqueous preservative solution is 1% ~ 8% (weight).
According to embodiments of the invention, as the aqueous solution sanitas described in the total concn of Gemini geminus quaternary ammonium salt and described sterilant be 4 ~ 6%.
The present invention also provides a kind of aqueous latex paint, comprises claim sanitas of the present invention.
Preferably, the described Gemini geminus quaternary ammonium salt of weight ratio 0.1 ~ 0.2% is comprised in aqueous latex paint of the present invention and the total concn of described sterilant is the aqueous solution of 4 ~ 6%.
Present invention also offers a kind of synthetic method of quaternary ammonium salt, comprise synthetic route:
Wherein y is the integer of 0 ~ 4, and n is the integer of 3 ~ 15, and X is the halogen being selected from Br, Cl and I.
The method of the invention comprises the steps:
The step of compound 3 is obtained after reacting some hours with triphenyl phosphite when being dissolved in appropriate solvent by compound 1 and compound 2.Solvent is dry pyridine.
To be dissolved under suitable solvent case with halogenated alkane as bromododecane reacts the step of several as a child obtained compounds 4 by compound 3.Solvent is CH3CN.
The higher final product of purity 4 is obtained by the method for column chromatography for separation by crude product 4.
Accompanying drawing explanation
Accompanying drawing 1 compound 4a
1h nmr spectrum.
Embodiment
the preparation example of Gemini geminus quaternary ammonium salt (with the compound 4 of y=1, n=9, X=Br for example)
(1) preparation of compound 3
Compound 1 and compound 2 (y=1) are dissolved in respectively in dry pyridine, temperature remains on room temperature Keep agitation 10min, temperature rising reflux, dropwise triphenyl phosphite is added when refluxing, be added dropwise to complete rear back flow reaction 4 ~ 12h, TLC follows the tracks of reaction, until reactant is not at minimizing stopped reaction.After reaction, decompression steams solvent, adds dry chloroform, uses water, unsaturated carbonate potassium solution, water washing respectively for several times.Add appropriate anhydrous sodium sulphate to leave standstill.Steam solvent after suction filtration, cooling adds diethyl ether, and washs for several times, obtains solution after drying by column chromatography, with Rotary Evaporators except after desolventizing, obtain the compound 3 of faint yellow solid after suction filtration with the mixing solutions of ether and chloroform.
(2) preparation of compound 4
Be dissolved in by compound 3 in dry acetonitrile solution, drip the bromododecane of 2.1 equivalents, back flow reaction 12 ~ 36h, TLC follow the tracks of reaction, until raw material reaction complete after, stopped reaction; Steaming desolventizes, and obtains solution by column chromatography, and with Rotary Evaporators, except obtaining brown solid after desolventizing, (compound 4 is specifically designated as gemini quaternary ammonium salt 4a below.), productive rate is 57%.Compound 4a's
1h nuclear magnetic spectrogram is shown in accompanying drawing 1.
Other compounds 4 of y, n and X different choice all can obtain with method similar above.
sterilization and anticorrosion test example
(1) formula that sanitas is composite
The quaternary ammonium salt (gemini quaternary ammonium salt 4a) of preparation is made into the aqueous solution of 5%, sterilant B2-bromo-2-nitro-1,3-propylene glycol and DBNPA are made into the aqueous solution of 1.64% respectively.The sterilant of 5% aqueous solution and 20g1.64% of getting 80g quaternary ammonium salt is mixed and made into the combination solution (being designated as sanitas S1 and S2 respectively) of 100g.In gained mixing solutions, the content ratio of quaternary ammonium salt is 92.4%, and the content ratio of sterilant B is 7.6%.
(2) for the sample of Bacterial challenges experiment
Two kinds of obtained sanitas S-1 and S2 sanitas (two kinds of namely obtained in (1) combination solutions) adding proportion with 0.1% and 0.2% are added in emulsion paint (ippon emulsion paint QB469), as the Bacterial challenges test sample of inspection sanitas preservative effect.
(3) process of the test:
A) Sterility testing: Initial microorganisms content detection is carried out to feeding sample.
Bacterial count: sample and the diluent substratum-TSA being applicable to bacterial growth thereof are carried out plate count, puts into constant incubator 30 DEG C and cultivate five days, observe the growing state of bacterium and count.
B) in-can preservation challenge experiment
The 7 kinds of microbionations of the listed conventional industrial class of table 1 are carried out to sample and pollutes (inoculum size 107cfu/ml), adopt repeatedly challenge experiment to investigate the quick sterilization ability of sample protective system and tolerate the ability repeatedly challenged
The bacterial species of table 1 industrial test
(4) appraisal procedure
Content of microorganisms different in sample pot is represented with 1-10 mark section.Numerical value 3 and be the requirement meeting water-borne coatings in-can preservation below, namely sterilizing rate is 99.99%.Numerical value is greater than the requirement that 3 all do not meet water-borne coatings in-can preservation.Refer to table 2.
Table 2 content of microorganisms standards of grading
State in table 3 adding proportion and tank
In paint sample tank, state and paint film appearance reflection is the intermiscibility of sanitas and emulsion paint, and in good condition and paint film is smooth just can carry out next step antibacterial test without particle, as shown in table 3.
S-1, S-2 are the anticorrosion and bactericidal agent combination solution of preparation in aforementioned (1), and contained sterilant is respectively B2-bromo-2-nitro-1,3-propylene glycol, DBNPA;
S-3 component is single quaternary ammonium salt, namely gemini quaternary ammonium salt 4a 5% the aqueous solution;
Sanitas AA091ULF is contrast scale pine.
(5) preservation challenge test effect
Table 4 sample Initial microorganisms pollution situation
The content of the Initial microorganisms that table 1 represents all is less than 102cfu/ml.Showing can next step test.
Test-results challenged by table 5
Challenge experiment is divided into four circulations, and each loop cycle is 7 days, and each front and back of choosing two days are test point.Again plant the bacterial strain into 107cfu/ml after being circulated throughout at every turn.
Sample C is single quaternary ammonium salt component, and the result of Bacterial challenges is greater than 3 at the first time numerical value of each circulation challenge, and second time numerical value is all less than 3, shows that this quaternary ammonium salt has long-acting antibacterial effect, does not but have sterilization effect fast;
Sample A1, A2, B1 show the sanitas of present method numerical value are within 3 when adding proportion is 0.1% and 0.2%, and product has both the effect of quick sterilization and long-acting bactericidal;
Sample E is existing conventional Kathon CG component, and all detected results are all less than 3;
Sample F is blank sample.
Claims (9)
1. a sanitas Gemini geminus quaternary ammonium salt, its structure as shown in Equation 4:
Wherein y is the integer of 0 ~ 4, and n is the integer of 3 ~ 15, and X is the halogen being selected from Br, Cl and I.
2. according to the Gemini geminus quaternary ammonium salt shown in claim 1, wherein y be 0,1 or 2, n be 7,9,11 or 13, and X is Br or Cl.
3. a sanitas, comprises the Gemini geminus quaternary ammonium salt described in claim 1 or 2 and sterilant, and described sterilant is selected from least one of chloro-5, the 5-dimethyl hydantion of the bromo-3-of 1-and 2-bromo-2-nitro-1,3-propylene glycol.
4. sanitas according to claim 3, the weight ratio of wherein said quaternary ammonium salt and described sterilant is 90:10 ~ 95:5.
5. the sanitas according to claim 3 or 4, it is the aqueous solution comprising described Gemini geminus quaternary ammonium salt and described sterilant.
6. sanitas according to claim 5, the total concn of Gemini geminus quaternary ammonium salt and described sterilant described in the wherein said aqueous solution is 1% ~ 8% (weight).
7. sanitas according to claim 6, wherein said total concn is 4 ~ 6%.
8. an aqueous latex paint, comprises the sanitas according to any one of claim 3 to 7.
9. aqueous latex paint as claimed in claim 7, it comprises the sanitas according to claim 7 of weight ratio 0.1 ~ 0.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410856930.7A CN104496893B (en) | 2014-12-29 | 2014-12-29 | Preservative Gemini Geminis quaternary ammonium salt and preservative |
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| CN201410856930.7A CN104496893B (en) | 2014-12-29 | 2014-12-29 | Preservative Gemini Geminis quaternary ammonium salt and preservative |
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| CN104496893A true CN104496893A (en) | 2015-04-08 |
| CN104496893B CN104496893B (en) | 2017-06-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968043A (en) * | 2016-05-13 | 2016-09-28 | 华东理工大学 | Gemini quaternary ammonium salt and use thereof |
| CN109096183A (en) * | 2018-08-02 | 2018-12-28 | 山西大学 | A kind of pyridines Bis-quaternary Ammonium Salt Surfactant and its preparation method and application |
| CN109810596A (en) * | 2017-11-20 | 2019-05-28 | 立邦涂料（中国）有限公司 | A kind of exploitation and application of New-type latex paint protective system |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968043A (en) * | 2016-05-13 | 2016-09-28 | 华东理工大学 | Gemini quaternary ammonium salt and use thereof |
| CN105968043B (en) * | 2016-05-13 | 2020-07-31 | 华东理工大学 | Gemini quaternary ammonium salt and use thereof |
| CN109810596A (en) * | 2017-11-20 | 2019-05-28 | 立邦涂料（中国）有限公司 | A kind of exploitation and application of New-type latex paint protective system |
| CN109810596B (en) * | 2017-11-20 | 2021-05-25 | 立邦涂料（中国）有限公司 | Development and application of novel latex paint anticorrosion system |
| CN109096183A (en) * | 2018-08-02 | 2018-12-28 | 山西大学 | A kind of pyridines Bis-quaternary Ammonium Salt Surfactant and its preparation method and application |
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| CN104496893B (en) | 2017-06-16 |
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