CN104496893B - Preservative Gemini Geminis quaternary ammonium salt and preservative - Google Patents
Preservative Gemini Geminis quaternary ammonium salt and preservative Download PDFInfo
- Publication number
- CN104496893B CN104496893B CN201410856930.7A CN201410856930A CN104496893B CN 104496893 B CN104496893 B CN 104496893B CN 201410856930 A CN201410856930 A CN 201410856930A CN 104496893 B CN104496893 B CN 104496893B
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- Prior art keywords
- preservative
- quaternary ammonium
- ammonium salt
- gemini
- geminis
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Classifications
-
- 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
Abstract
A kind of new Gemini Geminis quaternary ammonium salt and the preservative comprising the quaternary ammonium salt and bactericide.Its structure of Gemini Geminis quaternary ammonium salt is as shown in Equation 4.The preservative includes Gemini Geminis quaternary ammonium salt of the present invention and selected from the DMH of 1 bromine, 3 chlorine 5,5 and at least one bactericide of the propane diols of 2 bromine, 2 nitro 1,3.Preservative product of the invention has both the effect of quick sterilization and long-acting bactericidal.(y is 0~4 integer, and n is 3~15 integer, and X is the halogen selected from Br, Cl and I).
Description
Technical field
The present invention relates to a kind of Gemini Geminis quaternary ammonium salt and preservative for preservative, relate more specifically to coating
Storage preservative in tank.
Background technology
Water paint therefore can be by microorganism as the additive of nutritional utilization as decentralized medium and rich in various using water
The preferable hotbed of microbial growth.Amount reproduction can cause after the microorganism pollution coating such as bacterium, yeast and mold
Coating products surface discolouration, mobility variations, pH value change, performance change, cohesion, demulsification, generation peculiar smell even surface
A series of problems, such as mildew.Therefore control microorganism pollution and breeding, for ensureing that coating products include in whole usage cycles
Quality in when being stored in tank is very important.Since Heidelberger reported in 1915 quaternary ammonium salt have wide spectrum,
After the sterilizing function of low toxicity, although water-soluble single-stranded quaternary ammonium salt is obtained as bactericide in the fields such as medicine, food, health
Extensive use, but studied and be found that some bacteriums, particularly Gram-negative bacteria have the resistance to the action of a drug (Sopery to QAS
PR,Maxey RB.Toerance of bacteria for quternary ammonium compounds.J.Food Sci,
1968;24;141-50;Davies J.Bacteria on the rampage.Nature,1996;383:219-20.).
Development and global environmental consciousness with chemical industry strengthen, and people's Surfactant proposes many new wanting
Ask, the surfactant science that appears as of Gemini surface active of new generation has opened up open prospect.Gemini Gemini seasons
Ammonium salt has been used in commercial sterilization field because of the mildness with efficient bactericidal properties and to environment.
People's research is found that surfactant 2~3 quantity high of the more single-stranded quaternary ammonium salt of surface-active of bi-quaternary ammonium salt
Level, Gram-negative bacteria is solved to the insensitive of quaternary ammonium salt using bi-quaternary ammonium salt, and the problem for easily developing immunity to drugs obtains good
Effect.
But because double quaternary ammonium salt type antibacterial moleucles are larger, it is easy to which cell surface absorption causes bactericidal action to compare other classes
The bactericide of type is slow, i.e. quick sterilization scarce capacity.
The content of the invention
To overcome drawbacks described above, the present invention provides a kind of storage preservative, and described preservative includes a kind of new
Gemini Geminis quaternary ammonium salt and a kind of bactericide B, can effectively improve the sterilized timeliness of quaternary ammonium salt, improve sterilized speed.
Preservative of the invention Gemini Gemini quaternary ammonium salts, its structure is as shown in Equation 4:
Wherein y is 0~4 integer, and n is 3~15 integer, and X is the halogen selected from Br, Cl and I.
According to the preferential Gemini Gemini quaternary ammonium salts of the present invention, wherein y is 0,1 or 2, n are 7,9,11 or 13, and X is
Br or Cl.
Another aspect of the present invention is a kind of storage preservative in paint can, including Gemini of the present invention
Gemini quaternary ammonium salt and bactericide, the bactericide are selected from chloro- 5, the 5- DMHs of the bromo- 3- of 1- and bromo- 2- nitro -1 of 2-, 3-
At least one of propane diols.
Preferably, quaternary ammonium salt described in the preservative and the weight ratio of the bactericide are 90:10~95:5.
Preferably, the preservative is the aqueous solution comprising the Gemini Geminis quaternary ammonium salt and the bactericide.
Preferably, the total concentration of Gemini Geminis quaternary ammonium salt and the bactericide is described in the aqueous preservative solution
1%~8% (weight).
Embodiments in accordance with the present invention, the quaternary ammonium salts of Gemini Geminis described in the preservative as the aqueous solution and described kill
The total concentration of microbial inoculum is 4~6%.
The present invention also provides a kind of aqueous latex paint, comprising claim preservative of the invention.
Preferably, the Gemini Gemini quaternary ammonium of the weight than 0.1~0.2% is included in aqueous latex paint of the invention
The total concentration of salt and the bactericide is 4~6% aqueous solution.
Present invention also offers a kind of synthetic method of quaternary ammonium salt, including synthetic route:
Wherein y is 0~4 integer, and n is 3~15 integer, and X is the halogen selected from Br, Cl and I.
The method of the invention comprises the following steps:
By compound 1 and compound 2 after some hours are reacted with triphenyl phosphite in the case of being dissolved in appropriate solvent
The step of compound 3 are obtained.Solvent is dry pyridine.
It is dissolved in by compound 3 and reacts several with halogenated alkane such as bromododecane under appropriate solvent case and as a child made
The step of obtaining compound 4.Solvent is CH3CN.
Purity final product 4 higher is obtained by the method for column chromatography for separation by crude product 4.
Brief description of the drawings
The compound 4a of accompanying drawing 11H nmr spectrums.
Specific embodiment
Gemini Gemini quaternary ammonium salts preparation example (With y=1, as a example by the compound 4 of n=9, X=Br)
(1) preparation of compound 3
Compound 1 and compound 2 (y=1) are dissolved in dry pyridine respectively, temperature is maintained at room temperature and persistently stirs
10min, temperature rising reflux is added dropwise over triphenyl phosphite in backflow, is added dropwise to complete rear 4~12h of back flow reaction, TLC tracking
Reaction, until reactant stops reaction not untill reduction.Decompression steams solvent after reaction, adds dry chloroform, uses respectively
Water, unsaturated carbonate potassium solution, water washing are for several times.Appropriate anhydrous sodium sulfate is added to stand.Solvent, cooling plus second are steamed after suction filtration
Ether, is washed for several times after suction filtration with the mixed solution of ether and chloroform, and solution is obtained by column chromatography after drying, and uses rotary evaporation
After instrument removes solvent, the compound 3 of faint yellow solid is obtained.
(2) preparation of compound 4
Compound 3 is dissolved in dry acetonitrile solution, the bromododecane of 2.1 equivalents of dropwise addition, back flow reaction 12~
36h, TLC tracking reaction, until after raw material reaction is complete, stopping reaction;Solvent is evaporated off, solution is obtained by column chromatography, with rotation
Turn evaporimeter remove solvent after brown solid (compound 4 is designated as gemini quaternary ammonium salt 4a in detail below.), yield is 57%.Change
Compound 4a's1H nuclear magnetic spectrograms are shown in accompanying drawing 1.
Other compounds 4 of y, n and X different choice can be obtained with similar method with more than.
Sterilization and anticorrosion test example
(1) formula of preservative compounding
The quaternary ammonium salt (gemini quaternary ammonium salt 4a) for preparing is made into 5% aqueous solution, bromo- 2- nitro -1 of bactericide B2-, 3- third
Glycol and the bromo- 3- nitrilo-s propionamides of 2,2- bis- are made into 1.64% aqueous solution respectively.Take 5% aqueous solution of 80g quaternary ammonium salts with
The bactericide of 20g1.64% is mixed and made into the combination solution (being designated as preservative S1 and S2 respectively) of 100g.In gained mixed solution
The content ratio of quaternary ammonium salt is 92.4%, and the content ratio of bactericide B is 7.6%.
(2) for the sample of Bacterial challenges experiment
By obtained two kinds of preservative S-1 and S2 preservatives (obtained two kinds of combination solutions i.e. in (1)) with 0.1% He
0.2% adding proportion is added in emulsion paint (ippon emulsion paint QB469), is chosen as the bacterium of inspection preservative antiseptic effect
War test specimen.
(3) process of the test:
A) Sterility testing:Initial microorganisms content detection is carried out to feeding sample.
Count of bacteria:Sample and its dilution are carried out into plate count with the culture medium-TSA for being adapted to bacterial growth, is put into
Cultivated five days for 30 DEG C in constant incubator, observe the growing state of bacterium and count.
B) in-can preservation challenge experiment
Sample is carried out to commonly use 7 kinds of microbionations pollution (inoculum concentration 107cfu/ml) of industry class listed by table 1, using multiple
The ability of the multiple challenge of quick sterilization ability and tolerance that challenge tests to investigate sample protective system
The bacterial species of the industrial test of table 1
(4) appraisal procedure
Content of microorganisms different in sample jar is represented with 1-10 fraction section.Numerical value 3 and its aqueous the following is meeting
Corrosion-resistant requirement in paint can, i.e., sterilizing rate is 99.99%.Numerical value does not meet the requirement of water paint in-can preservation more than 3.
Refer to table 2.
The content of microorganisms standards of grading of table 2
State in the adding proportion of table 3 and tank
What state and paint film appearance reflected is the intermiscibility of preservative and emulsion paint, in good condition and paint in paint sample tank
Film is smooth can just to 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 foregoing (1), and contained bactericide is respectively the bromo- 2- nitre of B2-
The bromo- 3- nitrilo-s propionamide of base -1,3- propane diols, 2,2- bis-;
S-3 components are single quaternary ammonium salt, i.e. the aqueous solution of the 5% of gemini quaternary ammonium salt 4a;
Preservative AA091ULF is control sample Kathon CG.
(5) preservation challenge test effect
The sample Initial microorganisms pollution situation of table 4
The content of the Initial microorganisms that table 1 is represented is respectively less than 102cfu/ml.Show to be tested with next step.
Table 5 challenges result of the test
Challenge experiment is divided into four circulations, and each cycle period is 7 days, and it front and rear two days is test point that each is chosen.Every time
Again the bacterial strain into 107cfu/ml is planted after being circulated throughout.
Sample C is single quaternary ammonium salt component, and the result of Bacterial challenges is more than 3 in the first time numerical value of circulation challenge every time,
And second numerical value is respectively less than 3, show that the quaternary ammonium salt has long-acting antibacterial effect, but without quick bactericidal effect;
Sample A1, A2, B1 show the preservative of this method when adding proportion is 0.1% and 0.2% numerical value within 3,
Product has both the effect of quick sterilization and long-acting bactericidal;
Sample E is existing conventional Kathon CG component, and all testing results are respectively less than 3;
Sample F is blank sample.
Claims (3)
1. a kind of preservative, it is characterised in that Gemini Geminis quaternary ammonium salt and sterilization shown in the preservative contained 4
The aqueous solution of agent:
Wherein, y is that 1, n is that 9, X is Br, and the bactericide elects 2- bromo-2-nitro-1,3-propylene glycols as or 2,2- bis- is bromo- 3- times
Nitrogen base propionamide, in the preservative, the weight ratio of the Gemini Geminis quaternary ammonium salt and the bactericide for 90: 10~
95∶5。
2. a kind of aqueous latex paint, it is characterised in that the aqueous latex paint includes the preservative described in claim 1.
3. aqueous latex paint as claimed in claim 2, it is characterised in that weight of the preservative in the aqueous latex paint
Amount content is 0.1%~0.2%.
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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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CN104496893B true CN104496893B (en) | 2017-06-16 |
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CN105968043B (en) * | 2016-05-13 | 2020-07-31 | 华东理工大学 | Gemini quaternary ammonium salt and use thereof |
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 |
Family Cites Families (7)
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GB1339764A (en) * | 1971-03-29 | 1973-12-05 | Ici Ltd | Pyridine derivatives |
US3939169A (en) * | 1971-03-29 | 1976-02-17 | Imperial Chemical Industries Limited | Alkylene bis(pyridiniumareylene quaternary salts) |
JP2001089482A (en) * | 1999-09-24 | 2001-04-03 | Fuji Photo Film Co Ltd | Azamethine compound |
CN1243604C (en) * | 2004-01-13 | 2006-03-01 | 西华师范大学 | Gemini quaternary surfactant containing pyridine rings and preparing method thereof |
CN100376316C (en) * | 2005-11-22 | 2008-03-26 | 华东理工大学 | Gemini surface active agent |
CN101385957B (en) * | 2008-08-30 | 2010-10-06 | 西南石油大学 | Cation gemini surfactants and synthesis method thereof |
CN101781253A (en) * | 2009-01-16 | 2010-07-21 | 南京理工大学 | Method for preparing gemini ionic liquid with fluorous biphasic property |
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Granted publication date: 20170616 Termination date: 20211229 |