CN1128578C - Polymer-type amphoteric disinfectant and its preparing process - Google Patents
Polymer-type amphoteric disinfectant and its preparing process Download PDFInfo
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- CN1128578C CN1128578C CN 99100353 CN99100353A CN1128578C CN 1128578 C CN1128578 C CN 1128578C CN 99100353 CN99100353 CN 99100353 CN 99100353 A CN99100353 A CN 99100353A CN 1128578 C CN1128578 C CN 1128578C
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Abstract
The present invention relates to polymer-type amphoteric bactericide with a formula of *-CH2-[A]y, which has a structure that (P) is resin which can be carried out by chloromethylation; A is an amino acid type surface active agent; Q is trialkylamine of a fatty group; Y<-a> is an inorganic anion. The bactericide is obtained by fixedly carrying amino acid and quaternary ammonium salt on the resin. The bactericide has the advantage of excellent bactericidal activities, can be repeatedly used by regeneration because the bactericide is insoluble in water, and can be widely used for the sterilization and the disinfection of various fluid media, such as industrial water, domestic used water, etc.
Description
The invention belongs to disinfectant and preparation thereof, a kind of more precisely is the polymer-type amphoteric disinfectant and the preparation thereof of carrier with the resin.
At present, the water-soluble nitrogenous bactericide such as amphoteric surfactant of quaternary ammonium salt cationic surfactant, Tego type occupy very big proportion in the bactericide of selling on the market.Water-soluble nitrogenous bactericide all has very strong inhibition and kills ability various bacterium, algae and microorganism etc., but also exists unsurmountable shortcoming, mainly is to have toxicity and excitant, in addition with also producing residual poison after the sewage discharge, causes environmental pollution.At this problem, insoluble polymer type bactericide has appearred again in recent years.
US4,349,646 resins (as crosslinked or not crosslinked polystyrene resin or contain the cross-linked poly-methyl methacrylate ester resin of chloromethyl) by having chloromethyl react with tertiary amine, two uncles base diamines, make the insoluble polyquaternium type bactericide of different structure.This bactericide regeneration back is reusable.
US4,826,924 usefulness contain polystyrene or the SDEB styrene diethylenebenzene resin and bipyridyl list father-in-law who has chain alkyl or bi-quaternary ammonium salt reaction of chloromethyl, make another kind of cationic polymer type bactericide, and it is all effective to Gram-positive, negative bacterium.
The above water-insoluble cationic polymer type bactericide has stronger sterilizing ability, but because of its immobilized active group is a cationic surface active agent, also exist the various shortcomings of water-soluble cationic surfactant in the use inevitably, mainly be when materials such as protein, phosphine fat and heavy metal ion are arranged exist, bactericidal activity reduces greatly, when some anion surfactant or some macromolecular anionic compound existed, sterilizing ability was also very influenced.US4,349,646 have compared the influence of different anions to polyquaternium type bactericide bactericidal activity, show that the existence of big molecular anion compound can reduce bactericidal activity.For these reasons, the range of application of cationic water insoluble germicide is subjected to certain limitation.
The objective of the invention is on the basis of above-mentioned prior art, to overcome its defective, provide a kind of and not only have stronger bactericidal activity, and safe in utilization, be widely used reusable insoluble polymer type amphoteric disinfectant.
Another object of the present invention is to provide the preparation method of above-mentioned polymer-type amphoteric disinfectant.
Bactericide provided by the invention is to be made of resin carrier, amino acid and quaternary ammonium salt three parts, and its structural formula is as follows:
Wherein [P] be can chloromethylation resin, A is an amino acid type surfactant, y is the supported quantity of amino acid on every gram bactericide, Q is an aliphatic tertiary amine, f is the supported quantity of quaternary ammonium group in every gram bactericide, Y
-aBe inorganic anion, a is the chemical valence of Y.
Specifically, bactericide provided by the invention is to be made of resin carrier, amino acid and quaternary ammonium salt three parts, wherein:
Described resin carrier partial structural formula is
Resin [P] be can chloromethylation resin, be preferably gel-type or macroporous ion-exchange resin that polystyrene resin or styrene and divinylbenzene copolymerization obtain.The degree of cross linking of gel type resin can be 1～10%, preferred 1～4%; The degree of cross linking of macroporous ion-exchange resin can be 1～20%, preferred 1～10%.
Described amino acid can be alkyl polyamine polycarboxylate-type, alkyl polyamine monocarboxylic acid type, alkyl monoamine polycarboxylate-type, and alkyl monoamine monocarboxylic acid type, for example, can be the compound that is selected from one of following structure: R
1(NHCH
2CH
2)
nNHCH
2COOH, (R
2NHCH
2CH
2)
2NCH
2COOH, R
2(NHCH
2CH
2)
2N (CH
2COOH)
2R wherein
1Be C
4～C
24Alkyl, C preferably
6～C
18The alkyl of straight or branched, R
2Be C
4～C
16Alkyl, C preferably
6～C
12The alkyl of straight or branched, n are 0～3 integer, preferred 0～2 integer.Any nitrogen-atoms in the amino acid all can link to each other with the methylene on the resin, and the supported quantity of amino acid on resin can be 0.02～1mmol/g bactericide, is generally 0.02～0.6mmol/g bactericide and gets final product.Certainly supported quantity is high more, and bactericidal property is good more.Amino acid whose structure difference, the bactericidal activity of the bactericide that obtains after immobilized be difference to some extent also.
The structural formula of described quaternary ammonium moiety is:
Wherein Q is an aliphatic tertiary amine, can be the tertiary amine that contains a N atom, also can be the tertiary amine that contains a plurality of N atoms.For example, the tertiary amine that contains a N atom can be C
1～C
18The trialkyl tertiary amine, preferred C
1～C
12The trialkyl tertiary amine, more preferably at least one alkyl is C
1～C
6The trialkyl tertiary amine of alkyl.The tertiary amine that contains a plurality of N atoms can be: R
aR
bN (CH
2)
pNR
cR
d, R wherein
a, R
b, R
cAnd R
dCan be C
1～C
18Alkyl, preferred C
1～C
12Alkyl, more preferably at least one alkyl is C
1～C
6Alkyl, p are 1～10 integer, preferred 1～8 integer, more preferably 2～5 integer.Consider steric effect, R
a, R
b, R
cAnd R
dChain length to be complementary with the chain length of methylene, when the chain length of methylene is longer, R
a, R
b, R
cAnd R
dChain length can not be oversize, the alkyl that links to each other with one of them N atom should be shorter at least; Otherwise, methene chain more in short-term, alkyl chain length can correspondingly increase.F is the supported quantity of quaternary ammonium group in every gram bactericide, can be 0.1～4mmol/g bactericide, and general 0.5～3.0mmol/g bactericide gets final product.Y
-aBe inorganic anion, can be selected from Cl
-, Br
-, I
-, NO
3 -, SO
4 2-, CO
3 2-Or OH
-, a is the chemical valence of Y.
The preparation of polymer-type amphoteric disinfectant provided by the invention comprises the steps:
(1) with chloromethylation resin, organic solvent or organic solvent mix with the mixed solvent and the amino acid type surfactant of water, under reflux temperature, reacted 12～84 hours, separated product obtains polyaminoacid.
(2) tertiary amine, organic solvent and above-mentioned polyaminoacid are mixed, reacted under reflux temperature 12～84 hours, separated product obtains containing the polyaminoacid of quaternary ammonium group, is polymer-type amphoteric disinfectant provided by the invention.
Specifically, bactericide provided by the invention prepares as follows:
(1) immobilized amino acid type surfactant on the resin of chloromethylation, make polyaminoacid, that is: with the resin of chloromethylation, consumption is 0.05～4 times of molal quantity chloride in every gram resin, preferred 0.1～2 times amino acid type surfactant, and consumption is the reaction dissolvent mixing of every gram resin 40～100ml, be heated to backflow, reacted 12～84 hours, preferably 36～72 hours, filter then, consumption by every gram resin 10～50ml solvent, product in the mixed solvent of organic solvent or organic solvent and water, is heated to backflow, extracting 1～2 hour, to remove unreacted amino acid, refilter,, get final product in oven dry below 100 ℃ at last with the mixed solvent of 30～75 ℃ organic solvents or organic solvent and water washing 2～3 times.
In addition, also can in reactant, add the Anhydrous potassium carbonate powder with molal quantity such as amino acid, make amino acid change into corresponding sylvite, be beneficial to the dissolving of amino acid type surfactant in reaction dissolvent.
Described chloromethylation resin be preferably gel-type or the macroporous ion-exchange resin that the polystyrene resin of chloromethylation or styrene and divinylbenzene copolymerization get.The degree of cross linking of gel type resin can be 1～10%, preferred 1～4%; The degree of cross linking of macroporous ion-exchange resin can be 1～20%, preferred 1～10%.Chloromethyl on the resin also can replace with the group of other allylic structure, as bromomethyl, iodomethyl etc.Chlorinity on the resin can be 5～30%, preferably 10～25%.The particle diameter of resin is generally 0.2～1.5mm.For macroporous ion-exchange resin, small particle diameter is easier to reaction, therefore, can carry out suitable fragmentation in case of necessity.In addition, in order to improve supported quantity, can be earlier with resin swelling 1～2 hour in solvent, react again.
Described amino acid type surfactant can be alkyl polyamine polycarboxylate-type, alkyl polyamine monocarboxylic acid type, alkyl monoamine polycarboxylate-type, and alkyl monoamine monocarboxylic acid type, for example, can be the compound that is selected from one of following structure: R
1(NHCH
2CH
2)
nNHCH
2COOH, (R
2NHCH
2CH
2)
2NCH
2COOH, R
2(NHCH
2CH
2)
2N (CH
2COOH)
2R wherein
1Be C
4～C
24Alkyl, C preferably
6～C
18The alkyl of straight or branched, R
2C for straight or branched
4～C
16Alkyl, C preferably
6～C
12Alkyl, n is 0～3 integer, preferred 0～2 integer.
Described reaction dissolvent can dissolve amino acid whose solvent again for both resin being had swelling action.For example, can be C
1～C
3Alcohol also can be by being selected from C
1～C
3Any one organic solvent among alcohol, dioxane, the oxolane and water are according to 4～25: 1 volume ratio is formed, can also be by the mixed solvent of two or more arbitrary proportion in the above-mentioned organic solvent and water according to 4～25: 1 volume ratio is formed.
Described extraction solvent and cleaning solvent can be that wet concentration is from C
1～C
3Any one organic solvent among alcohol, dioxane, the oxolane, or the mixed solvent of two or more arbitrary proportion wherein, the also mixed solvent that can form according to arbitrary proportion by a kind of, two or more mixed solvent in the above-mentioned organic solvent and water.Extraction solvent can be identical with cleaning solvent, also can be different.
The reaction equation of this step is:
Wherein, P be can chloromethylation resin, A is an amino acid type surfactant.Weightening finish by as the resin of the chloromethylation of raw material can calculate amino acid whose supported quantity.
The polyaminoacid that above-mentioned reaction makes also has certain bactericidal property, still, if the chlorine on the remaining chloromethyl in the polyaminoacid resin is replaced with quaternary ammonium group, then can further improve its bactericidal activity.
(2) chlorine on the remaining chloromethyl in the above-mentioned polyaminoacid resin is replaced with quaternary ammonium group, preparation end-product-the contain polyaminoacid of quaternary ammonium group, that is: with above-mentioned polyaminoacid, consumption is 1～10 times of contained chloromethyl molal quantity in every gram polyaminoacid resin, preferred 2～8 times tertiary amine, and consumption is every gram polyaminoacid 5～50ml, the organic solvent of preferred 10～40ml mixes, under reflux temperature, reacted 12～84 hours, preferably 24～72 hours, filter then, is backflow extracting 1～2 hour in the solvent of every gram polyaminoacid 5～50ml with product at consumption, to remove unreacted tertiary amine, refilter, with 30～75 ℃ solvent washs 1～3 time, the consumption of each solvent is 1/2～1/4 of a reaction dissolvent.At last in oven dry below 100 ℃.
After the oven dry, product can also be carried out acidification, make the amino acid in the product change into stable hydrochloride, concrete grammar is as follows: will dry thing and stir 0.5～3 hour in the acidified solvent by 1: 6～6: 1 volume ratio compositions at organic solvent and inorganic acid, and get final product according to above-mentioned steps filtration, washing, oven dry.
Described tertiary amine can be the tertiary amine that contains a N atom, also can be the tertiary amine that contains a plurality of N atoms.For example: the tertiary amine that contains a N atom can be C
1～C
18The trialkyl tertiary amine, preferred C
1～C
12The trialkyl tertiary amine, more preferably at least one alkyl is C
1～C
6Alkyl; The tertiary amine that contains a plurality of N atoms can be: R
aR
bN (CH
2)
pNR
cR
d, R wherein
a, R
b, R
cAnd R
dCan be C
1～C
18Alkyl, preferred C
1～C
12Alkyl, more preferably at least one alkyl is C
1～C
6Alkyl.P is 1～10 integer, preferred 1～8 integer, more preferably 2～5 integer.
Described reaction dissolvent can dissolve the organic solvent of tertiary amine again for both resin being had swelling action, for example, can be C
1～C
4Alcohol, dioxane, oxolane etc. also can be the mixtures of two or more solvent among them.
Described extraction solvent can be C
1～C
4Alcohol, dioxane, oxolane etc. also can be the mixtures of two or more solvent among them.Extraction solvent can be identical with reaction dissolvent, also can be different.
Described cleaning solvent can be water or be selected from C
1～C
3Any one organic solvent among alcohol, dioxane, the oxolane, or the mixed solvent of two or more arbitrary proportion wherein, the also mixed solvent that can form according to arbitrary proportion by a kind of, two or more mixed solvent in the above-mentioned organic solvent and water.
Described acidified solvent is for being selected from C
1～C
3Any one organic solvent among alcohol, dioxane, the oxolane and the mixture of inorganic acid, or the wherein mixed solvent of two or more arbitrary proportion and the mixture of inorganic acid, preferred above-mentioned organic solvent and concentration are the mixture of the hydrochloric acid of 1～6N, the volume ratio of organic solvent and inorganic acid is 1: 6～6: 1, preferred 2: 5～5: 2.
The reaction equation of this step is:
Wherein, Q is an aliphatic tertiary amine.By weightening finish, can calculate the supported quantity of quaternary ammonium group as the polyaminoacid of raw material.
After above-mentioned reaction is finished, Cl
-Can also with other inorganic anion exchange of existing in the solution, in addition, amino acid and quaternary ammonium group all have certain supported quantity on resin, therefore, but the structure complete representation of bactericide provided by the invention is:
Wherein, y is an amino acid whose supported quantity in every gram bactericide, and f is the supported quantity of quaternary ammonium group in every gram bactericide, Y
-aFor being selected from Cl
-, Br
-, I
-, NO
3 -, SO
4 2-, CO
3 2-Or OH
-Inorganic anion, a is the chemical valence of Y.
Polymer-type amphoteric disinfectant provided by the invention uses the back renewable.Renovation process is as follows: used bactericide is isolated from the solution at its place, in being the mixed solvent of the hydrochloric acid of 4～12N of 1: 0.5～3 and absolute ethyl alcohol, volume ratio soaks 1～3h, filter, use absolute ethanol washing 1～2 time, oven dry below 100 ℃ gets final product.
Bactericide provided by the invention has excellent bactericidal activity, and 15 minutes sterilizing rate can be up to 99.99%.This bactericide is water insoluble, and can reuse after the regeneration, can be widely used in the sterilizing of fluid media (medium)s such as various industry and domestic use of water.
Further specify the present invention below by embodiment, but not thereby limiting the invention.
The styrene of employed chloromethylation and divinylbenzene copolymer resins (calling the chlorine ball in the following text) are to be made through chloromethylation by the Archon of buying from the market in the following example.Cholromethylation method is as follows: add the desirable Archon 10g of the degree of cross linking in reaction bulb, 20～40ml chloromethyl ether and 20～40ml anhydrous methylene chloride, stirring swelling 20～30 minutes under the room temperature, be cooled to below 0 ℃, is 0.2～0.6gAlCl with 10～50ml concentration
3The solution of/ml nitrobenzene adds reaction bulb in batches, and adding speed is so that reaction temperature is no more than 0 ℃, and reaction is finished, and under agitation drips volume ratio and be 1: 1 6N HCl and dioxane mixed solution, drips off that filter the back, washing, and drying gets final product.Concrete grammar is referring to " ion exchange resin " (R. Ke Ning work, Zhu Xiuchang etc. translate, Science Press, 1966).
Employed other raw material and reagent are the commercial industrial product in the example.In table 1, the table 2, each solvent and compound code name are represented respectively:
MA-methyl alcohol
EA-ethanol
The THF-oxolane
The DOX-dioxane
The structural formula of TMEDA is (CH
3)
2N (CH
2)
2N (CH
3)
2Example 1～4 is the preparation of alkyl polyamine.
Example 1
This example is N-dodecyl ethylenediamine (C
12H
25-NHCH
2CH
2NH
2) preparation (referring to F.Linsker et al, J.Am.Chem.Soc., 1945,67:1581).
In the 1000ml reaction bulb, add ethylenediamine 50g (0.8mol, purity 95%) and absolute ethyl alcohol 400ml, in 2 hours, drip bromododecane 50g (0.2mol), drip off the back and continued back flow reaction 3 hours.Reaction is finished, boil off ethanol, obtain the white solid thing, be transferred to and be heated to 40～50 ℃ of stirrings 0.5 hour in the 200ml water, cooling is left standstill, after waiting to separate out white wax, filter, solids with 20ml ether washing secondary, promptly gets N-dodecyl ethylenediamine 38g successively, yield 85%, 36～38 ℃ of product fusing points.
Example 2
This example is N-octyl group diethylenetriamine (C
8H
17(NHCH
2CH
2)
2NH
2) preparation, referring to " amphoteric surfactant " (volume such as Wang Zumo, light industry publishing house, nineteen ninety).
In the 500ml there-necked flask, add diethylenetriamine 206g (2mol), be heated to 180 ℃, under constantly stirring, in 4h, slowly drip chloro-octane 74.0g (0.5mol), drip and finish, in 180 ℃ of following stirring reaction 1h, leave standstill again, be chilled to about 40 ℃, separate and remove the diethylenetriamine hydrochloride, the filtrate decompression distillation, the fraction of 150～200 ℃/2.0KPa of collection, product is a light yellow viscous liquid, heavy 67.0g, yield 62%.
Example 3
This example is N, N '-dioctyl diethylenetriamine
Preparation.
The diethylenetriamine that adds 180g (1.75mol) in the 500ml there-necked flask is heated to 180 ℃, stirs the chloro normal octane that drips 150g (about 1mol) down in 4h, drip to finish, at 180 ℃ of stirring reactions 1 hour again, reaction is finished, leave standstill, be chilled to 40～50 ℃, remove by filter the diethylenetriamine hydrochloride, the filtrate decompression distillation, collect the fraction of 200～250 ℃/2.67KPa, obtain light yellow viscous liquid, heavy 109g, yield 67%.
Example 4
This example is N-dodecyl diethylenetriamine (C
12H
25-NHC
2H
4NHC
2H
4NH
2Preparation.
In the 250ml there-necked flask, add diethylenetriamine 103g (about 1mol), be heated to 140 ℃, stir the bromododecane that in 4h, drips 75g (about 0.3mol) down, drip and finish, stirring reaction is 1 hour again, leave standstill, be chilled to 40～50 ℃, separate and remove the diethylenetriamine hydrobromate, the filtrate decompression distillation, collect the fraction of 163～173 ℃/0.133KPa, obtain light yellow viscous liquid 40g, yield 50%.Example 5～8 is amino acid whose preparation
Example 5
This example is N, the preparation of N '-dioctyl diethylenetriamine glycine.
The N that in the 100ml there-necked flask, adds example 3 preparations, N '-dioctyl diethylenetriamine 33 gram (about 0.1mol) and 10ml water is heated to backflow, dripping 46.8 gram concentration under stirring condition in 2 hours is the sodium chloroacetate aqueous solution of 25 heavy %, after dripping off, continues reaction 2 hours again, steam water then, add dioxane, separate out white solid, filter, oven dry, get crude product, use ethyl alcohol recrystallization again, get pure product.
Example 6
This example is the preparation of N-dodecyl diethylenetriamine glycine
Add N-dodecyl diethylenetriamine 27 gram (0.1mol) and the 10ml water of example 4 preparations in the 100ml there-necked flask, all the other steps are with example 5, and obtaining product at last is white solid.
Example 7
This example is the preparation of N-octyl group diethylenetriamine glycine
Add N-octyl group diethylenetriamine 21.5 gram (0.1mol) and the 10ml water of example 2 preparations in the 100ml there-necked flask, all the other steps are with example 5, and obtaining product at last is the white plates crystallization.
Example 8
This example is the preparation of N-dodecyl ethylenediamine glycine
Add N-dodecyl ethylenediamine 22.8 gram (0.1mol) and the 10ml water of example 1 preparation in the 100ml there-necked flask, all the other steps are with example 5, and obtaining product at last is white solid.
Example 9～15
This group example is the preparation of polyaminoacid
Press consumption shown in the table 1, with the styrene of chloromethylation and divinylbenzene copolymer resins (being called for short the chlorine ball in the table) swelling 1 hour under the room temperature in reaction dissolvent, add the amino acid that is selected from one of example 5～8 again, the back flow reaction certain hour, filtered while hot, successively with the extracting 1 hour that respectively refluxes of 50% ethanol water and ethanol, filtered while hot then, use the hot ethanol about 70 ℃ more respectively, volume ratio is that 1: 1 dioxane and the mixed solvent of water and about 70 ℃ hot water and about 70 ℃ hot ethanol respectively wash 1 time, and each washing agent consumption is 1/4 of a reaction dissolvent consumption.At last with product in oven dry below 100 ℃, weigh, calculate chlorine ball weightening finish.
Example 16～22
This group example is the preparation that end-product contains the polyaminoacid of quaternary ammonium group.
Press consumption shown in the table 2, the polyaminoacid, the tertiary amine that are selected from 9～15 are mixed with reaction dissolvent, after certain hour is stirred in backflow, filtered while hot, with the solvent refluxing extracting identical with consumption 1 hour with the reaction dissolvent title, filter, the gained solids replaces washed twice with 60 ℃ of hot ethanols and hot water, and each washing agent consumption is 1/3 of a reaction dissolvent consumption.Product is dried below 100 ℃.Can calculate the supported quantity of quaternary ammonium group in every gram product by the weightening finish of polyaminoacid.Increase weight according to the chlorine ball simultaneously and calculate the supported quantity of every gram bactericide upper amino acid.Product after oven dry weighed is by the consumption of acidified solvent shown in the table 2, under room temperature, stirred acidification 1 hour, 1/3 50 ℃ hot water and the hot ethanol that filter respectively with the acidified solvent consumption replace washed twice again, product promptly gets polymer-type amphoteric disinfectant provided by the invention in oven dry below 100 ℃.
Table 1
| Example | 9 | 10 | 11 | 12 | 13 | 14 | 15 | |
| The chlorine ball | Form | Gel | Macropore | Macropore | Gel | Gel | Macropore | Macropore |
| The degree of cross linking, % | 1 | 4 | 4 | 1 | 2 | 7 | 7 | |
| Chlorinity, % | 22 | 20 | 20 | 22 | 16 | 21 | 21 | |
| Particle diameter, mm | ≤0.2 | ≤0.4 | ≤0.4 | ≤0.2 | ≤0.2 | 0.8～1.2 | ≤0.4 | |
| Consumption, g | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Amino acid | Be selected from example | 7 | 6 | 5 | 5 | 8 | 7 | 7 |
| Consumption, g | 2.5 | 4.2 | 3.2 | 4.0 | 3.2 | 2.0 | 2.0 | |
| Solvent | Title | DOX: EA: water 5: 12: 3 | THF: EA: water 8: 12: 5 | EA | EA | EA: water 9: 1 | EA: water 15: 1 | EA: water 15: 1 |
| Consumption, ml | 400 | 250 | 240 | 300 | 200 | 160 | 160 | |
| Potassium carbonate powder, g | 1.26 | 1.76 | 1.15 | 1.44 | 1.54 | 1.01 | 1.01 | |
| Reaction time, h | 60 | 72 | 72 | 72 | 72 | 60 | 60 | |
| Product weight, g | 5.50 | 5.41 | 5.64 | 5.72 | 5.36 | 5.06 | 5.20 | |
Table 2
| Example | 16 | 17 | 18 | 19 | 20 | 21 | 22 | |
| Polyaminoacid | Be selected from example | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| Consumption, g | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Reaction dissolvent | Title | THF | DOX | EA | THF∶EA 2∶1 | DOX∶EA 2∶1 | DOX | DOX |
| Consumption, ml | 60 | 75 | 100 | 150 | 120 | 120 | 120 | |
| Tertiary amine | Title | Trimethylamine | Triethylamine | TMEDA | Trimethylamine | Trimethylamine | Trimethylamine | Trimethylamine |
| Consumption, g | 5.2 | 5.0 | 8.0 | 6.0 | 4.6 | 7.0 | 7.0 | |
| Reaction time, h | 30 | 36 | 48 | 36 | 36 | 48 | 48 | |
| Product weight, g | 5.55 | 5.66 | 5.80 | 5.58 | 5.36 | 5.80 | 5.96 | |
| Acidified solvent | Title | THF∶6NHCl 5∶3 | DOX∶EA∶4NHCl 2∶3∶3 | EA∶4NHCl 1∶2 | DOX∶3NHCl 5∶4 | THF∶EA∶4NHCl 3∶2∶3 | EA∶6NHCL 3∶1 | EA∶3NHCl 4∶3 |
| Consumption, ml | 80 | 80 | 90 | 90 | 80 | 80 | 140 | |
| The amino acid supported quantity, the mmol/g bactericide | 0.299 | 0.203 | 0.253 | 0.292 | 0.220 | 0.037 | 0.117 | |
| The quaternary ammonium group supported quantity, the mmol/g bactericide | 1.68 | 1.147 | 1.19 | 1.762 | 1.138 | 2.338 | 2.73 | |
Example 23
This example is the bactericidal activity evaluation.
Because the bacterial classification that exists in the industrial circulating cooling water mainly is various heterotrophs, as motionless bacterium, pseudomonad, enterobacteria etc., so the present invention also selects the bacteria suspension that contains different heterotroph bacterial strains preparations when sample is evaluated for use.
The bactericidal activity assessment method is as follows:
1. strain culturing
Get and wait to try bacterial strain and on slant medium, cultivated 72 hours, the medium preparation: agar 15 grams, add suitable distilled water heating for dissolving, add peptone 10 grams more successively, beef extract 3 grams, sodium chloride 5 gram, and stirring and evenly mixing, adding distil water to 1 liter, regulate about pH value to 7.5 with 1N HCl and 1N NaOH solution, packing while hot, in 121 ℃ of high pressure steam sterilizations 30 minutes, sterilization back pH value was 7.2～7.4.
2. system bacteria suspension
72 hours bacterial strain of inoculated and cultured is transferred in the conical flask with stroke-physiological saline solution, and fully vibration is well-dispersed in the physiological saline lawn, is diluted to about 10 with sterile water
8～10
11The bacteria suspension concentration of individual/ml.
3. assessment method
According to the form below takes by weighing each series bactericidal agent provided by the invention of phase application quantity respectively in the 150ml conical flask, the bacteria suspension oscillation action 15 minutes that adds 50ml again, leave standstill, after getting bacteria suspension after the 1ml effect and making gradient dilution, get 1ml in culture dish, add the medium that is chilled to after melting about 40 ℃, shake up, in 30 ℃ of cultivation 72h, calculate and deposit viable count and sterilizing rate.
Concrete grammar is referring to Feng Junzhu " water for industrial use processing microbiological analysis " (Guangdong science and technology publishing house, 1985).
Table 3 is the bactericidal activity evaluation result of polymer-type amphoteric disinfectant provided by the present invention.The selected bacterial strain of test is in the table: acinetobacter calcoaceticus, staphylococcus aureus, Alcaligenes faecalis, pseudomonas mendocina, have a liking for aqueous vapor pseudomonad, clostridium perfringen, Fu Shi citric acid bacterium, Pseudomonas stutzeri, pseudomonas aeruginosa.
From table 1～3 as can be known, the carrier of (1) the same form and the degree of cross linking, particle diameter is thin more, and is high more to the supported quantity of bactericidal activity functional group, and with bacterial strain bigger contact gear ratio surface arranged in sterilization process, so bactericidal effect is good more; (2) under suitable dosage, polymer-type amphoteric disinfectant provided by the invention all has rapidly and efficiently the activity of killing to various heterotrophs, therefore can be widely used in the sterilizing of fluid media (medium)s such as various industry and domestic use of water.
Table 3
| Bactericide is selected from instance number | 16 | 17 | 18 | 19 | 20 | 21 | 22 |
| The bactericide consumption, mg | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 80 | 8.0 |
| Action time, min | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Initial bacterium number, * 10 9Individual/ml | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
| Deposit viable count, * 10 5Individual/ml | 0.7 | 9.1 | 1.5 | 1.2 | 14 | 160 | 24 |
| Sterilizing rate, % | 99.996 | 99.95 | 99.992 | 99.993 | 99.92 | 99.11 | 99.87 |
Example 24
This example is the bactericidal property evaluation after the bactericide regeneration once.
Example 18 described bactericide are used the back isolated by filtration, in the mixed solvent of 1: 3 6N hydrochloric acid of volume ratio and absolute ethyl alcohol, soaked 3 hours, filter, use the washing with alcohol secondary, oven dry below 100 ℃, according to the method evaluation bactericidal activity of example 23, test strain is with table 3 test bacterial strain uses therefor again, be 15 minutes action time, initial bacterium several 2.4 * 10
7Individual/ml, deposit viable count 2.2 * 10
3Individual/ml, sterilizing rate 99.991%.
The explanation of this example still has good bactericidal activity after the bactericide regeneration provided by the invention, and is therefore reusable.
Claims (12)
1. polymer-type amphoteric disinfectant is characterized in that having following structure:
[P] gel-type or macroporous ion-exchange resin of obtaining for polystyrene resin or styrene and divinylbenzene copolymerization wherein, A is an amino acid type surfactant, y is the supported quantity of amino acid on every gram bactericide, the y value is 0.02～1mmol/g bactericide, Q is an aliphatic tertiary amine, f is the supported quantity of quaternary ammonium group in every gram bactericide, and the f value is 0.1～4mmol/g bactericide, Y
-aBe inorganic anion, a is the chemical valence of Y.
2. according to the described bactericide of claim 1, it is characterized in that: A is the amino acid that is selected from one of following structure: R
1(NHCH
2CH
2)
nNHCH
2COOH, (R
2NHCH
2CH
2)
2NCH
2COOH, R
2(NHCH
2CH
2)
2N (CH
2COOH)
2, R wherein
1Be C
4～C
24Alkyl, R
2Be C
4～C
16Alkyl, n is 0～3 integer.
3. according to claim 1 or 2 described bactericide, it is characterized in that: R
1Be C
6～C
18Alkyl, R
2Be C
6～C
12Alkyl, n is 0～2 integer, the y value is 0.02～0.6mmol/g bactericide.
4. according to the described bactericide of claim 1, it is characterized in that: Q is C
1～C
18Trialkyl tertiary amine or structure are R
aR
bN (CH
2)
pNR
cR
dTertiary amine, R wherein
a, R
b, R
cAnd R
dBe C
1～C
18Alkyl, p are 1～10 integer.
5. according to claim 1 or 4 described bactericide, it is characterized in that: Q is C
1～C
12Trialkyl tertiary amine or structure are R
aR
bN (CH
2)
pNR
cR
dTertiary amine, R wherein
a, R
b, R
cAnd R
dBe C
1～C
12Alkyl, p are 1～8 integer, and the f value is 0.5～3.0mmol/g bactericide.
6. according to the described bactericide of claim 5, it is characterized in that: Q is C
1～C
6Trialkyl tertiary amine or structure are R
aR
bN (CH
2)
pNR
cR
dTertiary amine, R wherein
a, R
b, R
cAnd R
dBe C
1～C
6Alkyl, p are 2～5 integer, Y
-aBe selected from Cl
-, Br
-, I
-, NO
3 -, SO
4 2-, CO
3 2-Or OH
-
7. the preparation method of the described bactericide of claim 1 is characterized in that comprising the steps:
(1) with chloromethylation resin, reaction dissolvent and amino acid type surfactant mix, under reflux temperature, reacted 12～84 hours, separated product obtains polyaminoacid, and wherein the consumption of amino acid type surfactant is 0.05～4 times of molal quantity chloride in every gram resin;
(2) tertiary amine, organic solvent and above-mentioned polyaminoacid are mixed, reacted under reflux temperature 12～84 hours, separated product gets final product, and wherein the consumption of tertiary amine is 1～10 times of contained chloromethyl molal quantity in every gram polyaminoacid resin;
Reaction dissolvent in the step (1) is selected from C
1～C
3Alcohol, or by being selected from C
1～C
3A kind of, two or more organic solvent among alcohol, dioxane or the oxolane and water are according to 4～25: the mixed solvent of 1 volume ratio composition, the organic solvent in the step (2) is selected from C
1～C
4One of alcohol, dioxane, oxolane or the mixture of two or more solvent wherein.
8. according to the described preparation method of claim 7, it is characterized in that chloromethylation resin be gel-type or the macroporous ion-exchange resin that the polystyrene resin of chloromethylation or styrene and divinylbenzene copolymerization get, the degree of cross linking of gel type resin is 1～10%, and the degree of cross linking of macroporous ion-exchange resin is 1～20%.
9. according to the described preparation method of claim 7, it is characterized in that amino acid type surfactant is selected from the compound of one of following structure: R
1(NHCH
2CH
2)
nNHCH
2COOH, (R
2NHCH
2CH
2)
2NCH
2COOH, R
2(NHCH
2CH
2)
2N (CH
2COOH)
2, R wherein
1Be C
4～C
24Alkyl, R
2Be C
4～C
16Alkyl, n is 0～3 integer.
10. according to the described preparation method of claim 7, it is characterized in that tertiary amine is C
1～C
18Trialkyl tertiary amine or structure are R
aR
bN (CH
2)
pNR
cR
dTertiary amine, R wherein
a, R
b, R
cAnd R
dBe C
1～C
18Alkyl, p are 1～10 integer.
11. according to the described preparation method of claim 7, the consumption that it is characterized in that step (1) reaction dissolvent is every gram resin 40～100ml, the reaction time is 36～72 hours.
12. according to the described preparation method of claim 7, the consumption that it is characterized in that step (2) organic solvent is every gram polyaminoacid 5～50ml, the reaction time is 24～72 hours.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99100353 CN1128578C (en) | 1999-01-25 | 1999-01-25 | Polymer-type amphoteric disinfectant and its preparing process |
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|---|---|
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| CN1128578C true CN1128578C (en) | 2003-11-26 |
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ID=5269959
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|---|---|---|---|---|
| CN102304225B (en) * | 2011-05-27 | 2012-11-28 | 天津大学 | Polymer liposomes based on polyamino acid and quaternary ammonium salt and preparation method for polymer liposomes |
| CN115073804A (en) * | 2022-07-21 | 2022-09-20 | 河北利江生物科技有限公司 | Preparation method and application of amino acid loaded high-molecular resin |
-
1999
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