• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    Water soluble liquid quaternary ammonium polyhalides and quaternary ammonium polyhalides in water soluble admixture with surfactants, and their use in the control of biofouling in aqueous systems.
    公开号:SU1743353A3
    申请号:SU884355742
    申请日:1988-05-23
    公开日:1992-06-23
    发明作者:Е.Гэннон Джеймс；Торнберг Скотт
    申请人:Грейт Лейкс Кемикал Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of water treatment and can be used in the subglotting of bio-accumulations in various water systems.
    The aim of the invention is to increase the efficiency of the process.
    To implement the process, tetraalkylammonium polyhalo genus of the general formula is introduced into the treated water system.

    RI-N-R}. h
    H2Vg
    where Ri-R4 is alkyl. alkyl ether, cyclic alkyl, hydroxyethyl, polyether, halogen-substituted alkyl, and at least one of the substituents Ri-R4 contains at least 8 carbon atoms in
    its chain, no more than one of the substituents Ri-R4 is hydrogen; X - chlorine, bromine and iodine.
    The substituents are chosen so that the resulting polyhalide is water soluble and liquid at ambient temperature or insoluble in water and solid at ambient temperature, which dissolves in water when pre-mixed with surfactant , selected from a polyoxyethylene-polyoxypropylene row copolymer, echoxylated alkylphenol, ethoxylated phosphoric acid ester, glycol salt of alkylplyoxyethylene moVI

    with so sl
    CJ
    s
    not, or their mixture in the following ratio, wt.%: Polyhalide tetraalkylammonium 5-95
    Surfactant5-95 Thus, by varying the substituents R and X, it is possible to maximize the solubility of polyhalide in water or surfactant and to ensure optimal efficiency when using biocides.
    Examples of liquid water-soluble quaternary ammonium polyhalides that can be used as biocides are M-methyl-M, M, H-tris (3.b-dioxaheptyl) ammonium dibromide did, 1M-propyl-M, M, M- tris (3,6-dioxaheptyl) ammonium tribromide, W.1. 1-tris (3,6-dioxaheptyl) am and n hydrotribor id. M-ethoxyethyl-1 1, M, M-trimethylammonium tri bromide, M- (2-hydroxyethyl) -M, M.1 1-trimethylammonium tribromide, M. M-dimethyl-M-ethyl-N-propylammonium dichlorobromide, M, M -diethyl-M, M-dimethylammonitribromi d, M, M, M-triethylaminehydrotribromide, G, S, M-trimethylaminehydrotribromide and their mixtures.
    Examples of liquid Quaternary ammonium polyhalides, which can be used as a mixture with surfactants. are M, M-dimethyl-M-ethyl-M-propylammonium ibromide, M, M-dimethyl-1M, M-dioctylammonium dibromochloride, M-methyl-M, M, M-tris (3,6-dioxaheptyl) ammonium dibromodiodide , 1 1-propyl-M, M, M-tris (3,6-dioxaheptyl) ammonium tribromide; M, g.M-tris (3.6-dioxaheptyl) amine hydrotribromide, NN-dmmethyl-M-octylamine hydrotribromide, M, M-dimethyl-N-ethyl-N-propylammonium ntabromide, M, M-didecyl-M.Y. -dimethylammonium dibromochloride, M-methyl-M, M-bis (polyoxyethylene) -M-cocoammonium dibromochloride, M-methyl-M, 1H-bis (polyoxyethylene) -M- (9,10-dibromoctadecyl) -ammonium dibromochloride, M, 1M-diethyl-M, M-dimethylammonium tribromide, NN-tributyl, min hydrotribble, M, M, M-triethylamine hydrotribromide and Y, M, M-trimethylamine hydrotribromide.
    Examples of solid Quaternary ammonium polyhalides, which can be used in a mixture with pdv in the form of a water-soluble composition. are M-ethyl-M, M, M-trimethylammonium tribromide, N-ethyl-M-methylmorpholine tribromide, N-benzyl-M, M-dimethyl-M-myristylammonium dibromochloride. M, M, S, M-tetrabutylammonium tribromide and N.N.N.N-tetrabutylammonium dibromochloride.
    Quaternary ammonium polyhalides are preferably used, which have a high biocidal effect as polyhalides, and in the reduction of
    are converted to quaternary ammonium halides with non-oxidizing biocidal activity.
    Examples of Quaternary ammonium polyhalides, which are soluble in water, either in pure form or in a mixture with surfactants, which restores the bioactive quaternary ammonium halides, are M-methyl-M, M, M-trioctylammonium dibromide loride (liquid), S, M -didecyl-S, M-dimethi5 lammonium dibrochloride (liquid), M, M-dioxyl l-M, M-dimeti l ammonium dibromochloride (liquid), M-benzyl-M M-dimethyl-M-myristilammonium dibromochloride ( solid), N-methyl-Y, M-bis (polyoxyethylene) -M-cocoam
    0 moniyydibromochloride (liquid) and M-methylM. (Polyoxyethylene) -M- (9,10-dibromo
    Catadecyl) ammonium dibromide (liquid).
    In each of the above options
     the quaternary ammonium 5 cation substituent may be replaced to provide a liquid product, a solid product, and / or to improve the solubility of polyhalide in water. Should only be excluded substituents containing easy
    0 oxidizable functional groups.
    Groups that increase solubility and are sufficiently stable, thus avoiding the rapid oxidation of the polyhalide ion, include simple
    5 esters, alcohols, carboxylic acids and sulfates. The solubility in water of polyhalides can be increased by replacing one of the bromine atoms in the polyhalide with chlorine. So for the same cation
    0 Quaternary ammonium Q +, the solubility of the polyhalide complex in water increases in the order of Q + Bgz Q + CIBr2 Q + CIBr. Liquid polyhalide compounds can also be obtained by bromination.
    5 selected vz mixtures of two or more quaternary ammonium salts. While many polyhalides are solids individually, a mixture of two or more of these compounds can
    0 reduce the melting point of the mixture sufficiently so that the mixture becomes liquid at ambient temperature.
    Quaternary ammonium liquid polyhalides are prepared by adding molecular bromine or bromine chloride to a concentrated aqueous solution of the corresponding quaternary ammonium halide salt. The amount of water should be sufficient to dissolve all quaternary ammonium halide salt, but
    minimal to prevent loss on exit due to the solubility of the product in water. Bromine should be added at a sufficiently low rate to prevent excess bromine from precipitating to the bottom of the reaction vessel at the initial stages of the reaction. The quaternary ammonium polyhalide is yut from the solution in the form of a dark red liquid layer. The reaction temperature should be sufficient for the polyhalide to remain liquid, but below the temperature at which bromine is released from the complex. The optimum temperature range is 10-90 ° C.
    Solid quaternary polyhalides can be obtained in a similar way by using vigorous stirring during the reaction so that the solid particles of the product are well dispersed. The product is obtained from the cooled mixture by filtration and drying.
    Example 1. Obtaining M, M-dimethyl-M-ethyl-M-propylammonium tribromide.
    In a three-liter flask equipped with a condenser, a funnel in 250 ml, a thermometer and a mechanical stirrer, place N.N-dimethyl-M-ethylamine (256.0 g, 3.50 mol) and 1000 ml of water. To the stirred solution is added 1-bromopropane (430.5 g, 3.50 mol). The biphasic mixture is heated to 50 ° C with vigorous shaking. After 8.5 hours, the nuclear magnetic resonance spectrum of 1 H-NMR of the upper layer showed that N.N-dimethyl-M-ethylamine was completely consumed. The amber solution is cooled to room temperature and bromine (560 g, 3.50 mol) is added dropwise over 1.5 hours with vigorous stirring. The tribromide is separated as a dark red bottom layer. The remaining water (approximately 25 is removed from the tribromide layer by distillation at 50 ° C under reduced pressure. The yield of the dark red 1 M, M-dimethyl-N-ethyl-N-propylammonium tribromide was 1083.0 g (87% of
    N, M-dimethyl-M-ethylamine). Analysis,%: Вг0бщ68,73 (experts), 67.35 (theoretically); Vg0kis. 47.58 (expert), 44.90 (theoretical)
    Example 2. Preparation of M- (2-hydroxy-ethyl) -Y, M, M-trimethylammonium tribromide.
    The reaction is carried out in an oven-dried equipment under a nitrogen atmosphere. In a dry flask with a capacity of 500 ml equipped with a magnetic stirrer, thermometer, bubbler with mineral oil, a septum and a condenser with dry ice, 67.18 g of a 24.4% aqueous solution of trimethylamine in methanol (277 mol) are placed. The amine is cooled in a ice-cold bath and ethylene oxide is added. The introduction of ethylene oxide was stopped after 36.35 g (825 mol) was added. Stirring is continued for 5.5 hours. The reaction is stopped by carefully adding an aqueous solution of HBg, until the acid reaction to the litmus. The reaction mixture was concentrated in vacuo. The crude quaternary ammonium salt is obtained in the form of a thick yellow oil. The oil is dissolved in 60 ml of boiling isopropyl alcohol and the product is crystallized by cooling at 0 ° C overnight. The crystals are filtered off with suction, pressed and vacuum dried.
    5 Get 29,21 g of dry product (so pl. 280-1 ° C. Decomposition). An analysis of the bromine content and 1H-NMR spectrum confirms the presence of the mono-ethoxylated product N- (2-hydroxyethyl) -M, M, M-trimethylammonium
    0 romide, so pl. 298 ° C (decomposition). Analysis,%: Vg total 43.34 (experts), 43.41 (theoretically.).
    The recrystallized M- (2-hydroxyethyl) -Y, M, M-trimethylammonium bromide (55.86 g, 0.30 mol) is placed in a 100 ml flask equipped with a magnetic stirrer and an additional funnel to equalize the pressure. Water (29 ml) is added to obtain a 50% solution, and the solution is vigorously stirred, while at the same time adding 48.5 g (0.30 mol) of bromine from the addition funnel, dropwise. Tribromide drops out of solution in the form of a dark red oil. The product is separated from the aqueous layer by decanting and the remaining water is removed, heating to 50 ° C under aspiratory pressure for 15 minutes. Yield of M- (2-hydroxyethyl) -M, 1M, M-trimethylammonium tribromide 103.16 g. Analysis,%: Vg total. 67.63 (exger.). 69.71 (theoretical);
    0 Vgozhid 44.10 (experts). 46.41 (theoretical).
    Example 3. Getting M, K | -dimethyl-M-octylamine hydrotrioromide.
    In a three-neck flask with a capacity of 50 ml, equipped with a magnetic stirrer, 13.49 g of 48% HBr (0.08 mol) and 60 ml of water are placed. The solution is cooled in a water bath and 12.58 g (0.08 mol) of dimethyloctylamine is added dropwise over 30 minutes. The acidification of the solution is checked by litmus paper, the water is removed under vacuum. The residue is recrystallized from ethyl acetate and dried under vacuum. N, N-dimethyl-M-octylamine hydrobromide is obtained in the form of hygroscopic white particles, m.p. 1565 158.5 ° С (yield 14 01 g. 74%).
    The recrystallized dimethyloctylamine hydrobromide (11.14 g, 46.8 mmol) is placed in a 250 ml round-bottomed flask and E is dissolved in a minimum amount of water (21 ml). Add dropwise
    bromine (2.40 ml, 7.47 g, 46.8 mmol) with vigorous stirring from a burette with a volume of 10.0 ml. The product is isolated as a dark red oil at the bottom of the flask. The upper aqueous layer is decanted, the remaining traces of water are removed; the flask is heated to 50 ° C under aspiration pressure, the product is obtained in the form of pure red oil (yield 16.47 g, 89%), Analysis,%: Br0.47.47 (theoretically. 60.23); Hg0 36.68 (theorem. 40.15).
    Example 4. Preparation of M-propenyl- M, M, M-tris (3,6-dioxaheptyl) ammonium bromide.
    In a flask with a capacity of 500 ml, equipped with a reflux condenser and a preheating shell, put tris (3,6-dioxaheptyl) amine (14.55 g, 45 mmol) and 150 ml of acetone. Allyl bromide (6.53 g, 54 mmol, 20% excess) was added, and the solution was refluxed. After 28 hours, the 1H-NMR spectrum showed that the starting amine was reacted. After removal of the solvent, the crude product N- (2-propenyl) -M, M, M-tris (3., 6-dioxaheptyl) ammonium bromide is obtained as an amber oil (yield 19.66 g, 98%).
    The crude product (12.00 g, 27 mmol) is dissolved in 25 ml of ethanol and added to a hydrogenation apparatus under atmospheric pressure, which contains 530 ml of ethanol, 25 ml of glacial acetic acid and 1.0 g of palladium on barium sulfate. The reaction is complete after stirring for 2 hours under a hydrogen atmosphere. After removal of the solvent and acetic acid in vacuo, the product M-propyl-M, S, M-tris (3,6-dioxaheptyl:) ammonium bromide is obtained in the form of an amber liquid (yield 1097 g, 91%), the purity of which is confirmed by proton NMR -spectrum
    The crude quaternary ammonium salt (5.36 g, 12 mmol) is placed in a round bottom flask and bromine (0.61 ml, 1.92 g, 12 mmol) is added dropwise from the burette with vigorous stirring. The product M-propyl-N.N.N- tris (3,6-dioxaheptyl) ammonium tribromide is a dark red oil (yield: 27% g. 100%). Analysis. %: Vg0bsch 39.18 (experts). 39.54 (theoretically): Br0kis 20.38 (experts). .36 (theoretical).
    Example 5. Preparation of N.N-dimethyl-M-ethyl-M-propylammonium dichlorobromide.
    In a 125 ml flask equipped with a magnetic stirrer and a tube to disperse the gases, place N.N-dimeshl-M-ethyl-M-propylaminium bromide (19.61 g, 0.10 mol) and 20 ml of water. Chlorine gas is bubbled into the stirred solution until the introduced amount of chlorine is 7.12 g (0.10 mol). The transformation of the liquid phase is red, which
    collected at the bottom, in yellow-orange indicates the end of the reaction. The aqueous upper phase is separated, a yellow-orange oil is obtained (yield 23.83 g,
    89%), Analysis,%: Br0bsch 32.44 (theorem. 29.92); С10бщ 27.01 (theorem 26.55); oxidizing halogen 6.82 mg-eq (theoretical. 7.49 mg-eq).
    Example 6. Getting M, M-dimethyl-M, M-dioctylammonium dibromide.
    0 In a 1000 ml flask equipped with a magnetic stirrer, place N.N-dimethyl-M, M-dioctylammonium chloride (7.65 g, 25 mmol). Bromine is added dropwise (1.28 ml, 4.00 g, 25 mmol) with vigorous
    5 stirring. The product M, M-dimethyl-M, M-dioctylammonium chloride - orange-red oil (yield 11.20 g, 96%). Analysis,%: Vg total 33.31 (theorem. 34.31); 6.43 (theoretical 7.61); oxidizing halogen 3.25 mg-eq.
    0 Table 1 shows the physicochemical characteristics of the Quaternary ammonium polyhalides obtained by the interaction of the 0 + X halide with the molecular halogen Xa.
    5 The reagents obtained are introduced into the system.
    in quantities sufficient to effectively suppress bio-contamination. Depending on the nature of the system and the halide used, the necessary amounts of the reagent agent range from 0.120 to 65.9 mg / l. This range of input reagent allows you to maintain the concentration of active halogen in the system 0.05--30 mg / l, preferably from 1 mg / l.
    5 The effectiveness of the Quaternary ammonium polyhalides used can be improved by combining them with one or more surfactants, such as polyoxyethylene0 polyoxypropylene block copolymers (PeuronicL-62 and Macol 1 trademarks), ethoxylated alcohols, such as polyoxyethylene trideridyl alcohol (Macol TD-8), branched chain fatty alcohol polyethylene glycol ether (Agpoch 1007), tridecyloxypoly (ethyleneoxy) ethanol (Emulphogene BC 720) and alcohol ethoxylate (Neodo 23-6.5), ethoxylated alkyl phenols, such as nonylphenoxy poly (ethylenoxy) ethanol (Igepal C0730), nonylphenoxypolyethoxyethanol (Agpoh 912) and a simple alkylide | enoxypolyethyleneglycol ether (Agpoh 910 and Agpoh 908), polyoxyethyleneglycerol monoisostearate
    5 (Tagat 1) and ethoxylated caprylic-capric acid mono-diglycipids (Soffigen 767), ethoxylated alkylphenols (Pluradine OP-10), polyethylene glycolmonolaurate (Chemax E400 ML and Chemax E600 ML), modified with ethyl ethoxide and duct synthesis, modified polyethylene glycol monolaurate (Chemax E400 ML and Chemax E600 ML), modified with polyethylene glycol laurate (Chemax E400 ML and Chemax E600 ML), modified with ethylene glycol laurate, artificial lye-colmonolaurate (Chemax E400 ML and Chemax E600 ML), modified with polyethylene glycol laurate (Armax x400 ML and Chemax E600 ML), modified with ethylene glycololaurate, arthritic glycol laurate (Chemax E400 ML and Chemax E600 ML), modified with polyethylene glycol laurata (Armax et 400 ML and Chemax E600 ML), modified with ethylene glycol laurate, Arnol et 4 alkoxylirons & biodegradable hygrophobes (Polytergent SL42), alkyl polyoxyalkylene ethers (Surfonic LF 17). phosphate esters (Chemfac P8109) and aliphatic phosphate esters (ethylene oxide adducts) (Jordaphos IA60 and IS41), polyesters (Pluradyne D82564), quaternary surfactants, such as polyoxyethylene ammonium chloride (Tomahs Q-18-15 and K-18-15 and K15-15 and K15-15-15). Tel) and coco (polyoxyethylene) methyl ammonium chloride (Tomahs Q-15-C).
    Preferred surfactants are: polyoxyethylene-polyoxypropylene block copolymer, ethoxylated alkylphenols, phosphate esters, glycol esters and quaternary ammonium bases, which are used in amounts of 5-95% by weight, preferably 40-95% by weight . If a foaming problem arises with the introduction of a surfactant, antifoaming agents can be added to the mixture. The compositions are prepared by thoroughly mixing the components at room temperature and administered in amounts sufficient to effectively suppress bio-contamination, approximately 0.238-179.7 mg / l, preferably 2.40-5.9.9 mg / l. Enter the amount of the mixture provides a concentration of active halogen in the system of 0.05-30 mg / l, preferably from 1 mg / l.
    If the mixture of polyhalide and surfactant is unstable, it is prepared immediately before use.
    B; Table 2 shows the effect of a polyoxyethylene-polyoxypropylene block copolymer (Plutonic L-62) on the solubility of N.N-dimethyl-M-ethyl-M-propylammonium tribromide.
    In Tables 3–5, the data on the biocidal action of M.M-dimethyl-M-ethyl-E-propylammonium tribromide on bacteria, fungi, and algae in the presence of various surfactants are given.
    Thus, the presence of surfactants increases the biocidal activity of the polyhalide, possibly due to the effect of surfactants on exopolysaccharides and / or biological membranes.
    Tables 6 and 7 present data on the biocidal action. M.Y.-dimethyl-GL-ethyl-Y-propylammonium tribromide in a mixture with surfactant - alkylpolyoxyethylene ammonium chloride (Q-18-15) depending on the concentration of surfactant.
    Table 8 presents data on the biocidal activity for a series of polyhalides of tetraalkylammonium,
    The use of tetraalkylammonium polyhalides makes it possible to reduce the required amount of biocide by a factor of 10–100 compared with the prototype and increase the effectiveness of suppressing bio-accumulation in water-cooling systems, oil wells, irrigation systems, lakes and lagoons, and water supply systems enterprises, as well as various disinfection works.
    权利要求:
    Claims (1)
    [1]
    1. A method for suppressing bioagents of an aqueous system, including the introduction of a reagent, characterized in that, in order to increase the efficiency of the process, polyhalide tetraalkylamini is used as a reagent of the general formula
    TO,
    RI-N-RI
    Yats
    0
    five
    0
    five
    0
    five
    where R- | -R4 is alkyl, alkyl ether / cyclic alkyl, hydroxyethyl, polyether and halogen-substituted alkyl, not more than one of the substituents Ri-R4 is hydrogen, at least one of the substituents Ri-R contains at least 8 carbon agomes ; X - chlorine, bromine, - / yod.
    2 The method according to p. 1. about tl and h a y i and so. that before introducing into water polytetra tetraalkylammonium is mixed with a surface-active substance selected from the following series: polyoxyethylene-polyoxypropylene block copolymer, ethoxylated alkyl-phenol, ethoxylated phosphoric ester, glycol ester, alkyl salt - oxyethylene ammonium, or their mixture in the following ratio, wt.%:
    Polyhalide tetraalkylammonium 5-95 Surfactant 5-95 Priority by feature
    24.09.86 by all signs, except reflecting the use of M, M-diethyl-M, M-dimethylammonium tribromide, Y, M, M-tributylamine hydrotribromide, N.N.N.-triethylamine hydrotribromide and N.N.N-trimethylamine g of drotribromide.
    04/20/87 for all signs reflecting the use of these compounds.
    Table 1
    13
    1743353
    14 Table 2
     The concentration of free bromine.
    Table 3
    Table 4
    Table 5
    Table 6
    Table 7
    Table 8
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US91118386A| true| 1986-09-24|1986-09-24|
    US4890287A| true| 1987-04-20|1987-04-20|
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