• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Phosphonium salts such as THP and aldehydes such as formaldehyde exhibit synergistic biocidal activity.
    公开号:SU1838322A3
    申请号:SU904743363
    申请日:1990-03-02
    公开日:1993-08-30
    发明作者:Brajan Edvard；Alfred Vil Malkolm；Erik Telbot Robert；Grem Kuper Kennet；Stiven Mettz Nigel
    申请人:Albright & Wilson；
    IPC主号:
    专利说明:

    The invention relates to biocidal compositions comprising tetraorganic phosphonium salts and to biocidal treatments using them.
    Tetrahydroxymethylphosphonium (THP) salts and trishydroxymethylphosphine are described and claimed for use as biocides for water treatment, plant protection and for pharmaceutical and veterinary treatments in GB 2145708, GBA-2178960, GB-A-2182563, GB-A-2201592 and GB -2201592 and GB-A-2205310, which are incorporated herein by reference. Used as biocides of some analogues of THP, including methyl, ethyl and allytris (hydroxymethyl) phosphonium salts.
    The low molecular weight phosphonium salts described in the above patents are clearly different from the high molecular weight quaternary surfactants, which also exhibit biocidal properties. Quaternary surfactants are markedly different from low molecular weight hydroxymethylphosphonium biocides in their chemical, physical and biocidal properties. Thus, both quaternary ammonium and quaternary phosphonium salts having one long (i.e. 8-20 carbon atoms) chain are effective as biocides. Activity correlates with surface activity, decreasing as the chain length decreases to 8 carbon atoms. Quaternary ammonium salts, which are more effective as surfactants than the corresponding phosphonium salts, are likewise more effective as biocides.
    A typical quaternary biocide has one fatty alkyl group and three methyl groups, but in the case of phosphonium salts, methyl groups can be substituted with hydroxymethyl groups without significant effect on biocidal activity. They can also be substituted,
    1838322 AZ by at least one aryl group, for example, benzalkonium salts, without loss of both surface activity and biocidal activity.
    In contrast, low molecular weight hydroxymethylphosphonium salts are not surfactants and yet are highly biocidal. However, the nature of biocidal activity is completely different. They are effective against bacteria and algae at much lower concentrations than quaternary surfactants and act very quickly. In contrast to surfactants, the activity of phosphonium salts with a low molecular weight is specific to the presence of hydroxymethyl groups. Although one hydroxymethyl group can be substituted with methyl, ethyl or an alkyl group, without loss of activity, if more than one hydroxymethyl group is replaced, or if the size of the substituent increases beyond 3 carbon atoms, the biocidal activity drops sharply. Tetramethylphosphonium salts and aryltris (hydroxymethyl) phosphonium salts are inactive,
    Nitrogen analogues of low molecular weight phosphonium biocides do not exist.
    For all of the above reasons, it will be apparent to those skilled in the art that THP salts and the associated low molecular weight hydroxymethylphosphonium salts and hydroxymethylphosphine biocides form a completely different group of biocides in no way analogous to quaternary surfactants and their mechanism of action is presumably completely different.
    Various aldehydes such as formaldehyde, acrolein and glutaraldehyde are widely used as biocides. It is known that some aldehydes are synergistic in combination with quaternary surfactants.
    It was found that combinations of trishydroxymethylphosphines or low molecular weight hydroxymethylphosphonium biocides / especially THP salts, with aldehyde biocides, especially formaldehyde and also glutaraldehyde and acrolein, have synergistic biocidal properties.
    The invention provides biocidal compositions comprising (I) at least one organophosphorus biocide that has the formula (RnP (CH 2 OH) 3 ) v n + n (X) v ′ where R is hydroxymethyl, methyl, ethyl or allyl, X is is an anion such that the compound is at least sparingly soluble in water, η is 1 or 0 and represents the valency of anion X, and (II) at least one biocidal aldehyde or its polymer.
    The invention also provides a method of killing or inhibiting the growth or reproduction of microbes or other pests on a substrate or in media, which comprises contacting said substrate or medium substantially simultaneously with compounds (I) or (II) mentioned above.
    Preferred compounds for use are THP salts, especially THP sulfate (THP) and THP chloride (THPC), and Tris (hydroxymethyl) phosphine.
    Methyltris (hydroxymethyl) phosphonium salts, ethyltris (hydroxymethyl) phosphonium salts and allyltris (hydroxymethyl) phosphonium salts are also useful.
    Anion X may be any of the convenient anions that provides a salt that is preferably soluble at least to a concentration of 0.5 g per liter of water at 25 ° C. such as chloride, sulfate or phosphate, or less preferably sulfite, phosphite, bromide, nitrate, borate, acetate, format, lactate, methosulfate, citrate or carbonate. However, other anions that give salts with reduced solubility in water but soluble in organic solvents, such as alcohols or hydrocarbons, can be used.
    Another key ingredient in our synergistic compositions is a biocidal aldehyde or biocidally active polymer, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, suktsinaldegid, isobutyraldehyde, glutaraldehyde, crotonaldehyde, acrolein, chloral, glyoxal, metaldehyde, paraldehyde, metaformaldehyde or trioxane.
    The phosphonium compounds and the aldehyde can usually be present in the composition in a weight ratio of from 20: 1 to 1:20, especially 9: 1-1: 9, preferably 3: 7-7: 3.
    It should be understood that the obtained THPC and THPS solutions usually contain a small amount of by-product formaldehyde, typically about 2% or 3% by weight, based on the THP salt, which is usually distilled as light fractions to less than 1% before the product supplied for use.
    It should be understood that in the claims of the present invention, the composition is referred not to secondary formaldehyde, but to formaldehyde added to the composition in addition to the traces that are already present, to obtain a synergistically enhanced biocidal effect.
    The biocidal components of our invention are useful for treating aerobic or anaerobic water systems contaminated or susceptible to contamination by microorganisms. For example, they are effective against Pseudomonas aeruginosa and Legianella pneumophila in boiler water, cooling water, industrial water, geothermal water, in central heating and air conditioning systems, for the destruction of algae in swimming pools, lakes, streams, canals and tanks and for processing cooling water in power plants and marine engines.
    Biocides are also useful in killing sulfate-reducing bacteria such as Desulphovibrio in the systems mentioned above, and especially in oilfield water, injection water, drilling mud and hydrostatic test water. They are also useful as preservatives in water-based formulations such as bituminous and tar emulsions, paper adhesives, adhesives, paints, cellulosic pulps, including liquid feed pulp and backflow recycle liquor.
    Biocides are useful in disinfectants, including livestock disinfectants, household and surgical disinfectants. They can be used for fumigation of silos, crops and storage areas of crop products.
    Biocides are useful for killing bryophytes, including mosses and liver mosses, lichens and leafless algae in gardens and lawns, on paths, roads, highways, on walls and other structures, and on railways, airports and industrial facilities.
    Biocides are useful for protecting plants of fungi, bacteria, viruses and other microbial pathogenic organisms of plants, when applied to plants and / or to the soil to which they are grown or will be grown, or for use in seed dressing.
    Biocides can be used at higher concentrations as general herbicides to kill higher plants.
    The selective activity of biocides depends on the concentration, usually at a concentration of between 10 and 2000 ppm, preferably 20-1500, for example 301000, especially 50-500 ppm. biocides are selective against lower organisms such as bacteria, algae, mosses and fungi, but exhibit very low toxicity to higher plants, fish and mammals. At higher concentrations, for example more than 0.2% up to saturation, preferably 0.5-75%, for example 1-60%, and at doses of more than about 2 kg per ha, for example 2.5-5 kg / ha, biocides, however are effective common herbicides.
    Mixed alkyl hydroxyalkyl THP salts can be prepared by adding an aqueous base to the tetrakis (hydroxymethyl) phosphonium salt, for example sodium hydroxide, in a ratio of 0.5 to 0.75 equivalents of tris (hydroxymethyl) phosphine and reacting the latter with an alkyl halide such as methyl chloride, preferably with elevated temperature, for example 40-60 ° C. Alternatively, an improved yield can be obtained by reacting an alkyl halide with tris (acetoxymethyl) phosphine obtained by the method of Mironova et al. The reaction can be carried out by heating at temperatures up to 140 ° C, for example at 120 ° C in a suitable solvent, such as toluene, for 2-20 hours, for example 10-15 hours, or with an acid catalyst, preferably acetic acid for 1 to 8 hours, for example 3-5 hours
    The invention provides compositions containing the above biocides. In particular, for use in water treatment and in agriculture, we found that biocides are synergistic with surfactants.
    The surfactant may, for example, consist essentially of at least a slightly water soluble salt of sulfonic or monoesterified sulfuric acid, for example, alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, olefin sulfonate, alkanesulfonate, alkyl phenol sulfate, sulfate, sulfate, sulfate, amide sulfate, sulfate of alkyl ethanolamide ether, with alpha-sulfate fatty acid or its esters, each having at least one alkyl or alkenyl group from 8-22, more usually 10— 20, by aliphatic carbon atoms.
    The expression ether mentioned above refers to compounds containing one or more glyceryl groups and / or an oxyalkylene or polyoxyalkylene group, especially a group containing from 1 to 20 oxyethylene and / or oxypropylene groups. One or more groups may be present additionally or alternatively. For example, the sulfonated or sulfonated surfactant may be sodium dodecylbenzenesulfonate, potassium hexadecylbenzenesulfonate, sodium dodecyldimethylbenzenesulfonate, sodium lauryl sulfate, solid fat sodium sulfate, potassium oleyl sulfonate, sulfonammonate sulfate monoacetate sulfate.
    Other anionic surfactants useful according to the present invention include alkyl sulfosuccinates, such as sodium di-2-ethylhexyl sulfosuccinate and sodium dihexyl sulfosuccinate, alkyl ether sulfosuccinates, alkyl sulfosuccinates, alkyl sulfosuccinates, acyl sulfates, acyl sulfates, and oleates, linoleates, and alkyl ether carboxylates. Anionic phosphate esters and alkylphosphonates, alkylamino and iminomethylene phosphonates may also be used. In each case, anionic surfactants typically contain at least one aliphatic hydrocarbon chain having from 8 to 22, preferably 10-20 carbon atoms, and, in the case of ethers, one or more glyceryl and / or 1 to 20 oxyethylene and / or oxypropylene and / or oxybutylene groups.
    Preferred anionic surfactants are sodium salts. Other salts of commercial interest include potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine, alkylamines containing up to seven aliphatic carbon atoms, and alkyl / or hydroxyalkylphosphonium salts.
    Surfactants may optionally contain or consist of nonionic surfactants. The nonionic surfactant may be, for example, a C10-22 alkanolamide mono- or di-lower alkanoamine, such as coke monoethanolamide. Other non-ionic surfactants that may optionally be present include tertiary acetylene glycols, polyethoxylated alcohols, polyethoxylated carboxylic acids, polyethoxylated amines, polyethoxylated alkylolamides, polyethoxylated ethylene ethers, polyethoxylated ethers, polyethoxylated glyceryl ethers and propoxylated or ethoxylated and propo silirovannye analogues of all the above ethoxylated nonionic materials, all of which have a Ce-22 alkyl or alkenyl group and up to 20 ethyleneoxy and / or propyleneoxy groups. Also included are polyoxypropylene (polyoloxyethylene copolymers, polyoxybutylene) polyoxyethylene copolymers and polyoxybutylene (polyoxypropylene copolymers). Polyoxyethylene, polyoxypropylene and polyoxybutylene compounds may optionally be closed at the end, for example with benzyl groups, to reduce their pricing tendency.
    The compositions of our invention may contain amphoteric surfactant.
    The amphoteric surfactant may be, for example, betaine of the formula: -P3 + CH2COO ', where each P represents an alkyl, cycloalkyl, alkenyl or alkaryl group, and preferably at least one, and most preferably not more than one P group has an average of 8 to 20, for example, 10-18 aliphatic carbon atoms, and each other P has an average of 1 to 4 carbon atoms. Particularly preferred are quaternary imidazoline-betaines of the formula:
    CH 2 CH 2 N + N СН2СОСГFROM R 1 Rwhere R and R 1 are alkyl, alk
    nyl, cycloalkyl, alkaryl or alkanol groups having an average of 1 to 20 aliphatic carbon atoms, and P preferably has an average of 8 to 20, for example.
    10-18 aliphatic carbon atoms, and R 'preferably has 1-4 carbon atoms.
    Other amphoteric surfactants for use according to our invention include alkylamino ether sulfates, sulfobetaines and other quaternary amine or quaternized imidazoline sulfonic acids and their salts, and other quaternary aminyl quaternized imidazoline carboxylic acids and their salts and zwitterionic surfactants substances, for example, N-alkyl taurines, carboxylated amido amines, such as RCONH (CH2) 2 (СНгСНгСНз ^ СНгСОг, and amino acids having, in each case, hydrocarbon groups capable of imparting surfactant properties (e.g. alkyl, cycloalkyl,. alkenyl or alkaryl groups having from 8 to 20 aliphatic carbon atoms).
    Representative examples include 2-fatty alkyl, 1-fatty amidoalkyl, 2-carboxymethyl imidazoline and 2-coconut alkyl N-carboxymethyl 2- (hydroxylalkyl) imidazoline. Generally speaking, any water-soluble amphoteric or zwitterionic surfactant that includes a hydrophobic moiety comprising a Ce-20 alkyl or alkenyl group and a hydrophilic moiety containing an amine or quaternized ammonium group and a carboxylate, sulfate or sulfonic acid group can be used in our invention .
    The compositions of our invention may also include cationic surfactants.
    The cationic surfactant may be, for example, an alkyl ammonium salt having a total of at least 8, usually 10-30, for example 12-24 aliphatic carbon atoms, especially a tri- or tetra-alkylammonium salt. Typically, alkyl ammonium surfactants for use according to our invention have one or at most two relatively long aliphatic chains per molecule (for example, chains having an average of 8 to 20 carbon atoms each, usually 12-18 carbon atoms) and two or three, with a relatively short chain, alkyl groups having 1-4 carbon atoms each, for example, methyl or ethyl groups, preferably methyl groups.
    Typical examples include dodecyl trimethylammonium salts. Benzalkonium salts having one alkyl group with 8-20 carbon atoms, two alkyl groups with 1-4 carbon atoms and a benzyl group are also useful.
    Another class of cationic surfactants useful according to our invention are N-alkyl pyridinium salts, where the alkyl group has an average of 8 to 22, preferably 10 to 20 carbon atoms. Other similarly alkylated heterocyclic salts, such as N-alkyl isoquinolinium salts, may also be used.
    Useful are alkyl aryl dialkyl ammonium salts having an average of 10 to 30 aliphatic carbon atoms, for example, salts in which the alkyl aryl group represents an alkyl benzene group having an average of 8 to 22, preferably 10 to 20 aliphatic carbon atoms, and the other two alkyl groups typically have from 1 to 4 carbon atoms, for example methyl groups.
    Other classes of cationic surfactants that are used in our invention include alkylimidazoline or quaternized imidazoline salts having at least one alkyl group in a molecule having an average of 8 to 22, preferably 10-20 carbon atoms. Representative examples include alkyl methyl hydroxyethylimidazoline salts and -2-alkyl-1-alkylamidoethylimidazoline salts.
    Another class of cationic surfactant for use according to our invention includes amidoamines, such as compounds formed by the interaction of a fatty acid having 8-22 carbon atoms, or its derivative, forming an ester, glyceride or similar amide, with diyl polyamine , such as, for example, ethylenediamine or diethylenetriamine, and in such an amount as to leave at least one free amino group. Similarly, quaternized amido amines can be used.
    Alkylphosphonium and hydroxyalkylphosphonium salts having one alkyl group with 8-20 carbon atoms and three alkyl or hydroxyalkyl groups with 1-4 carbon atoms can also be used as cationic surfactants in our invention.
    Typically, the cationic surfactant can be any water-soluble compound having a positively ionized group, usually including a nitrogen atom, and / or one or two alkyl groups having an average of 8 to 22 carbon atoms each.
    The anionic part of the cationic surfactant can be any anion that imparts water solubility, such as a format, acetate, lactate, tartrate, citrate, chloride, nitrate, sulfate or alkyl sulfate ion having up to 4 carbon atoms, such as methosulfate. It is preferably a non-surface active anion such as higher alkyl sulfate or organic sulfonate.
    Polyfluorinated anionic, nonionic or cationic surfactants may also be useful in the compositions of our invention. Examples of such surfactants are polyfluorinated alkyl sulfates and polyfluorinated quaternary ammonium compounds.
    The compositions of our invention may contain a semipolar surfactant, such as amine oxide, for example amine oxide containing one or two (preferably one) alkyl group with 8-22 carbon atoms, with the rest of the substituent or substituents are preferably lower alkyl groups, for example alkyl groups or benzyl groups.
    Particularly preferred for use in accordance with our invention are surfactants that are effective as wetting agents, typically such surfactants are effective in lowering the surface tension between water and the surface of a hydrophobic solid. We prefer surfactants that do not stabilize the foam to a large extent.
    . Mixtures of two or more of the above-mentioned surfactants may be used. In particular, mixtures of nonionic surfactants with cationic and / or amphoteric and / or semipolar surfactants or with anionic surfactants can be used. Typically, we avoid mixtures of anionic and cationic surfactants, which are often less mutually compatible.
    Preferably, the organophosphorus compounds and surfactants are present in a relative weight concentration of from 1: 1000 to 1000: 1, more typically 1: 50-200: 1, typically 1: 20-100: 1, more preferably 1: 10-50: 1 for example 1: 1-20: 1, in particular 2: 1-15: 1.
    Effective doses of a mixture of an organophosphorus compound, an aldehyde and a surfactant are usually from 2 ppm. up to 2000 million dollars, more usually 20 million dollars. - 1000 million dollars, for example 50-500 million dollars, especially 100,250 million dollars.
    The composition for use in water treatment may additionally or alternatively contain other biocides, oxygen scavengers, dispersants, antifoam agents, solvents, scale inhibitors, corrosion inhibitors, and / or flocculants.
    The compositions of our invention for use in controlling bryophytes, lichens, or fungi or microbial pathogens of plants contain an effective amount of the biocide mentioned above, together with a garden or agriculturally acceptable diluent, carrier, and / or its solvent.
    Organophosphorus compounds can be presented as a solution in water at effective concentrations up to saturation. They will usually be supplied as concentrates at a weight concentration of about 50-80%, for example 75% by weight, before mixing with the aldehyde, but will usually be diluted to a concentration of 0.01 to 10% by weight before use. In order to avoid damage to higher plants, it is preferable to use concentrations below 1% w / w biocide, preferably below 0.2%. Alternatively, biocides can be mixed with or absorbed on inert, particulate, non-phytotoxic solids such as talc or dissolved in organic solvents or suspended in them or used as dispersions or emulsions. Thus, the compositions of the invention are preferably presented as emulsified concentrates in organic solvents such as hydrocarbon alcohols and amides such as dimethylformamide, including cyclic amides such as N-methylpyrrolidone, the concentrate also containing a surfactant, for example, as mentioned higher. They can be used in combination with other moss control agents or biocides, such as herbicides, fungicides, bactericides, insecticides and weed control agents, or with surfactants, wetting agents, adhesives, emulsifiers, suspending agents, thickeners, synergists, , hormones, plant growth regulators, or plant nutrients.
    The compositions of our invention can be applied to lawns, flower or vegetable beds, arable land, meadow land, orchards, or forest, or flood checks, or to seeds, roots, flowers, leaves, fruits and / or peduncles of plants, or to trails , roads, walls, wooden structures, masonry, or similar contaminated surfaces.
    The composition can be valuable, among other things, in the fight against moss or sedentary algae in lakes or on paths or walls, as a seed dresser, as a spray or to kill bacteria fungi or viral infections on leaves, flowers, and fruits, such as mildew , botrytis, rust, fusarium, mosaic disease or wilting, for application to the soil or to the roots of seedlings (e.g. cabbage seedling to inhibit cruciferous keels) and to combat numerous fungal, viral, bacterial diseases, plant lesions second, caused by protozoa, including fungal rot such as potato rot, ulcers, such as apple canker, scab, root rot, bulbs rot. The compositions are particularly effective in protecting crops, including wheat, barley, rye, oats, rice, corn, millet and sesame from a wide range of plant diseases.
    Other important crops that can be protected according to our invention include sugarcane; root crops, including carrots, parsnips, turnips, beets, sugar beets, radishes, rutabaga and chard; cabbage, including cabbage, rucola, cauliflower and Brussels sprouts; grazing land; legumes, including peas, fodder beans, ordinary beans, multi-flowered beans, Turkish beans and lentils; gourds, including cucumbers, pumpkins, zucchini and giant pumpkins, oilseed rape, wood, rubber, cotton, coffee, cocoa, jute, tomatoes, potatoes, yams, tobacco, bananas, coconut palms, olives, onions, including onions. shallots, leeks, garlic, chives and spring onions, peanuts, sorghum, oil palm, roses, hemp, flax, alfalfa, sowing alfalfa, tea and fruits, including citrus fruits, apples, plums, peaches, nectarines , mangoes, pears, cherries, grapes, berries, currants, date palm, figs, avocados, almonds and apricots.
    Mixtures of organotetrafluoro compounds and aldehydes are more effective biocides against a variety of microorganisms and pests than individual compounds. In the case of formaldehyde, the formulation can be prepared substantially in advance and stored until use. However, in the case of some other aldehydes, it is preferable to prepare the composition in place by adding the aldehyde and the organophosphorus biocide separately to the site to be processed or mix them as required for use, since the two compounds are chemically incompatible if mixed together and stored for long period.
    The invention is illustrated in the following examples in which THPS is bis / tetrakis / hydroxymethyl / phosphonium sulfate. Empigen is a registered trademark of albright Wilson Limited. Empigen BAC is a fatty alkyl dimethylbenzylammonium chloride.
    Π PRI me R 1. 1. The method.
    1.1. Biofilm generation.
    Soft steel bio-columns were given the opportunity for 3 weeks to grow enriched with microbiological mixtures of sulfate-reducing bacteria (SRB), aerobic bacteria and anaerobic bacteria from water; x injection systems of platforms for oil production in the North Sea. This was accomplished using a recycled biofilm generator specifically designed for this purpose. The device consists of a PVC pipe containing a series of mild steel columns mounted in such a way that their open surface is washed with a strong pressure jet of the internal contents of the pipe. The culture medium was circulated using a centrifugal pump and any gas that accumulated was removed from the system using a bleed valve. A sterile anaerobic fresh mixture of nutrients and sea water was supplied to the system daily to maintain biofilm growth; and every day replaced 75% of the volume of fluid in the device. The device was operated for 3 weeks to provide the opportunity for the development of a stable biofilm. The tested columns were removed regularly to confirm the stability of the resulting biofilm.
    1.2. Test modes of biocides. Tests with biocides are presented in table 1.
    Three products were used against sessile seaweed populations using standard statistical methods described in section 1.3. This test is intended to determine the concentration necessary to kill aerobic, anaerobic and SRB bacteria after a contact time of 1 hour.
    1.3. Static tests of biocides
    Individual fouling columns were suspended in separate 125 ml vessels containing sea water / biocide solution at the appropriate concentration. Biocidal solutions were prepared using sterile, anaerobic seawater and the required concentrations of biocide.
    1.4. Bacteria detection
    1 h after exposure, the columns were removed in 10 ml volumes of anaerobic diluent containing 1 g of sand. Vortex mixing was used to break the biofilm and obtain a homogeneous suspension. Initial dilution then serially diluted to 10 '8 degrees in an additional 10 ml quantity of anaerobic diluent. Control columns exposed to seawater without biocide were treated identically to ensure comparability with biocide treated columns.
    Then a series of dilutions were used to inoculate selective determination media: lactate-based broth medium to determine SRB; agar anaerobic marine yeast / peptone (under anaerobic conditions) for anaerobic bacteria; marine nutrient agar for aerobic bacteria. Series were incubated at 30 ° C. Aerobic and anaerobic bacteria were counted 5 days after incubation, and after a full incubation period of 8 days, the amount of SRB was determined.
    . 2. The results are presented in table.2.
    3. Comments
    3.1. Control levels of SRB, anaerobic and aerobic bacteria are all high, indicating the presence of a high concentration of viable bacteria in biofilms.
    3.2. All biocides contain the same total level of active substance.
    3.3. The results for biocide 3 (based on formaldehyde) show that this system is not very effective.
    3.4. Results for biocide 2 (based on THPS) show that it is quite active.
    3.5. The results for biocide 1 (based on a THPS / formaldehyde mixture) show that it is more effective than biocide 2, despite having a lower THPS content (the deficiency is made up for by less active formaldehyde). Therefore, it is obvious that there is synergy.
    Example 2. A composition comprising equal amounts of glutaraldehyde and THPS showed increased activity against bacteria compared to glutaraldehyde, and increased activity against fungi compared to THPS at equivalent concentrations of total biocide. In each case, the activity was significantly higher than the average activity of individual biocides.
    权利要求:
    Claims (7)
    [1]
    1. Biocidal composition containing a salt of tetrakis (hydroxymethyl) phosphonium (I) and water, characterized in that it additionally contains Ci-Sb mono- or dialdehyde or its polymer (II) with a mass ratio of active components from 1:20 to 20 : 1 and their total concentration in water in the range of 0.001-75 wt.%.
    [2]
    2. The composition of pop. 1, characterized in that component II is formaldehyde, glutaraldehyde, acetaldehyde, succinic aldehyde, acrolein, glyoxal, metaldehyde, paraldehyde, meta-formaldehyde or trioxane.
    [3]
    3. The composition according to claims 1 and 2, with the fact that the mass ratio of active components is from 9: 1 to 1: 9.
    [4]
    4. The composition according to claims 1 to 3, characterized in that it further comprises a synergistically effective amount of a wetting agent.
    [5]
    5. A method of suppressing the vital activity of harmful microorganisms by treating the infected lesion with a biocide, characterized in that the composition containing the tetrakis (hydroxymethyl) phosphonium salt, CrSbmono- or dialdehyde or its polymer in the mass ratio of active components from 1:20 to 20 is used as the biocide: 1 and their total concentration in water in the range of 0.001-75 wt.%.
    [6]
    6. The method according to claim 5, characterized in that the infected lesion is water.
    [7]
    7. The method according to PP.5 and 6, with the fact that the water is recycled or cooling water of industrial production or water from oil production.
    Table 1
    Biocide Component Weight FRN % active ingredient weight / weight 1 TNR 0.1551 11.63 Empigen YOU 0.0233 1.17 36.6% formaldehyde 0.2869 10.50 Water 0.5347 -Total active 23.30 2 TNR 0.2951 22.13 Empigen YOU 0.0233 1.17 Water 0.6816 -Total active 23.30 3 36.6% formaldehyde 0.6323 22.13 Empigen YOU 0.0233 1.17 Water 0.3444 -Total active 23.30
    table 2
    Biocide Concentration (ppm) Contact time (h) ' Surviving bacteria per column Srb Anaerobic Aerobic The control 0 1 1.1 x s 62.3 x 10 s2.4 χ 10 δ 1 1,1x 10 5. 3.1 χ 10 52.9 χ 10 5100 1 2.5 χ 10 52.9 χ 10 41,0 χ 10 3250 1 2.5 x 10 12.0 x 10 40 1 500 1 0 5.0 x 10 20 1000 1 0 0 0 1500 1 0 0 0 100 1 4.5 χ 10 48.5 x 10 43.5 χ 10 3250 1 2.4 χ 10 11.3 χ 10 40 2 500 1 0 4.0 χ 10 31,0 χ 10 21000 1 0 5.0 χ 10 20 1500 1 0 0 0 100 1 4,5 x 10 33.0 χ 10 41.8 χ 10 3250 1 1.1 χ 10 54.3 χ 10 41.9 χ 10 3 3 500 1 1.5 x 10 64,5 x 10 52.3 χ 10 41000 1 . 4.5 χ 10 41,0 χ 10 45.0 χ 10 21500 1 1.1 χ 10 31.7 χ 10 44.0 χ 10 2
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1838322A3|1993-08-30|Biocidic composition and a method of harmful microorganism vital activity supression
    US9955698B2|2018-05-01|Microbicidal compositions including a monochloramine and a peracid, and methods of using the same
    EP0223533B1|1990-10-31|Compounds and methods for control of bryophytes, lichens, algae and fungal and microbial plant pathogens
    EP0380359B1|1993-12-29|Biocidal compositions and treatments
    PT673197E|2001-12-28|COMPOSITION AND METHOD TO INCREASE THE EFFICIENCY OF PESTICIDES
    AU622770B2|1992-04-16|Biocidal compositions and treatments
    JP3584987B2|2004-11-04|Synergistic antimicrobial composition comprising methylene-bis | and an organic acid
    EP0774903A1|1997-05-28|Pesticidal compositions containing ethoxylated fatty amines for increasing the effectiveness of endothall and salts thereof
    US10212937B2|2019-02-26|Microbicidal aqueous solutions including a monochloramine and a peracid, and methods of using the same
    WO2017074720A1|2017-05-04|Microbicidal compositions including monochloramine and a peracid, and methods of using the same
    US20190208782A1|2019-07-11|Processing composition for controlling aquatic weeds
    同族专利:
    公开号 | 公开日
    MY105215A|1994-08-30|
    HU206178B|1992-09-28|
    AT99867T|1994-01-15|
    NO178131C|1996-01-31|
    DK0385801T3|1994-02-14|
    MX173947B|1994-04-11|
    AU622984B2|1992-04-30|
    FI95192B|1995-09-29|
    IN173868B|1994-07-30|
    CZ103790A3|1998-04-15|
    HUT54027A|1991-01-28|
    GB2228680A|1990-09-05|
    YU42490A|1991-10-31|
    EP0385801B1|1994-01-12|
    ZA901553B|1990-12-28|
    DD292362A5|1991-08-01|
    CZ283491B6|1998-04-15|
    PT93333B|1996-01-31|
    GB8904844D0|1989-04-12|
    CA2011317C|1999-12-07|
    KR900013858A|1990-10-22|
    IE900752L|1990-09-03|
    NZ232745A|1991-11-26|
    IE64406B1|1995-08-09|
    FI95192C|1996-01-10|
    US5385896A|1995-01-31|
    PT93333A|1990-11-07|
    YU47429B|1995-03-27|
    NO901004D0|1990-03-02|
    AU5060590A|1990-09-06|
    NO901004L|1990-09-04|
    PL163725B1|1994-04-29|
    HU901272D0|1990-05-28|
    KR0169476B1|1999-01-15|
    DE69005855T2|1994-06-23|
    ES2062333T3|1994-12-16|
    GB9004670D0|1990-04-25|
    DE69005855D1|1994-02-24|
    JP2510748B2|1996-06-26|
    SK279215B6|1998-08-05|
    CA2011317A1|1990-09-03|
    NO178131B|1995-10-23|
    FI901085A0|1990-03-02|
    BR9001023A|1991-02-26|
    SK103790A3|1998-08-05|
    EP0385801A1|1990-09-05|
    JPH02273605A|1990-11-08|
    GB2228680B|1992-09-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US8846732B2|2004-04-26|2014-09-30|Conocophillips Company|Inhibition of biogenic sulfide production via biocide and metabolic inhibitor combination|
    RU2555991C2|2010-12-29|2015-07-10|Юнайтед Стэйтс Джипсум Компани|Antimicrobial sizing emulsion and gypsum board obtained with its application|
    RU2648043C2|2013-09-19|2018-03-22|Италматч Кемикалс С.п.А.|Method for preparing trishydroxymethyl phosphine|
    RU2654110C2|2013-08-02|2018-05-16|ЭКОЛАБ ЮЭсЭй ИНК.|Biocide compositions|US4675327A|1977-04-11|1987-06-23|The Dodge Chemical Company|Anti-microbial compositions|
    DE3205487C1|1982-02-16|1983-10-13|Degussa Ag, 6000 Frankfurt|Use of polycondensation products from acrolein and formaldehyde as biocides|
    GB2145708B|1983-08-26|1987-02-04|Albright & Wilson|Biocidal water treatment|
    US4804685A|1984-10-12|1989-02-14|Surgikos, Inc.|Buffered glutaraldehyde sterilizing and disinfecting compositions|
    DE3439519A1|1984-10-29|1986-04-30|Henkel KGaA, 4000 Düsseldorf|METHOD FOR IMPROVING THE CORROSION BEHAVIOR OF DISINFECTANT SOLUTIONS|
    GB2178959B|1985-07-17|1989-07-26|Grace W R & Co|Biocidal mixture|
    IN166861B|1985-08-06|1990-07-28|Albright & Wilson|
    GB8527793D0|1985-11-11|1985-12-18|Albright & Wilson|Control of bryophytes lichens algae & fern|
    ES2042724T3|1987-01-16|1993-12-16|Albright & Wilson|A THERAPEUTIC OR PROPHYLACTIC COMPOSITION.|
    GB8712372D0|1987-05-26|1987-07-01|Albright & Wilson|Treating ponds aquaria & watercourses|
    GB8901881D0|1989-01-27|1989-03-15|Albright & Wilson|Biocidal compositions and treatments|GB2257043A|1991-04-10|1993-01-06|Albright & Wilson|Fungicidal wood treatment using hydroxyalkyl phosphines|
    US5128051A|1991-09-30|1992-07-07|Union Carbide Chemicals & Plastics Technology Corporation|Method for the control of biofouling|
    GB9823247D0|1998-10-24|1998-12-16|Ciba Geigy Ag|A process for the control of microbial contamination in water-based solids suspensions|
    US6001158A|1999-02-18|1999-12-14|Baker Hughes Incorporated|Dry biocide|
    JP2003500529A|1999-05-26|2003-01-07|ローディア・コンスーマー・スペシャルティーズ・リミテッド|How to tan leather|
    GB0001417D0|2000-01-22|2000-03-08|Albright & Wilson Uk Ltd|Bleaching pulp|
    ES2309049T3|2000-02-10|2008-12-16|Sakata Seed Corporation|METHOD FOR THE TREATMENT OF SEEDS.|
    US6506737B1|2000-04-05|2003-01-14|Ecolab, Inc.|Antimicrobial phosphonium and sulfonium polyhalide compositions|
    US6379720B1|2000-07-18|2002-04-30|Nalco Chemical Company|Compositions containing hops extract and their use in water systems and process streams to control biological fouling|
    US6626122B2|2001-10-18|2003-09-30|Chevron U.S.A. Inc|Deactivatable biocides in ballast water|
    US6815208B2|2001-11-14|2004-11-09|Champion Technologies, Inc.|Chemical treatment for hydrostatic test|
    US7780859B2|2003-06-20|2010-08-24|Rhodia Operations|Uncoupling agents|
    GB0314363D0|2003-06-20|2003-07-23|Thames Water Utilities|Treatment of sewage sludge|
    ES2313360T3|2004-06-21|2009-03-01|Rhodia Uk Limited|IMPROVING THE QUALITY OF A FANGO.|
    KR100727181B1|2004-07-13|2007-06-13|현대자동차주식회사|Aqueous antibacterial composition for automobiles air conditioner evaporator|
    GB2421239B|2004-12-20|2010-06-23|Rhodia Uk Ltd|Treatment of sewage sludge|
    BRPI0808221A2|2007-03-21|2014-07-08|Dow Global Technologies Inc|"WATERY HAIR CARE COMPOSITION, USE OF A HAIR CARE COMPOSITION AND METHOD TO SUPPLY HAIR OIL FORMATION BETWEEN WASHING"|
    DE102007030488A1|2007-06-30|2009-01-22|Zf Friedrichshafen Ag|Use of an active agent comprising at least one glutaraldehyde or dimethanol, for inhibiting microbial growth in industrial cool water circulation|
    BRPI0812700B1|2007-07-24|2020-04-28|Dow Global Technologies Inc|method for reducing or inhibiting the increase in the concentration of anaerobic microbes in a water-based fluid and formulation for reducing or inhibiting the increase in the concentration of anaerobic microbes in a water-based fluid or system|
    RU2479206C2|2007-07-24|2013-04-20|ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи|Methods and compositions for reducing concentration and inhibiting growth of microbes in water-based fluids and systems with use thereof|
    JP4959510B2|2007-11-07|2012-06-27|株式会社工生研|Algicide|
    US8162048B2|2008-09-09|2012-04-24|Tetra Technologies, Inc.|Method of delivering frac fluid and additives|
    US20100078393A1|2008-10-01|2010-04-01|Bei Yin|Biocidal compositions and methods of use|
    CN102469779B|2009-07-27|2013-10-23|陶氏环球技术有限公司|Synergistic antimicrobial composition|
    US20120101063A1|2009-09-09|2012-04-26|Howard Martin|Biocidal aldehyde composition|
    US9006216B2|2009-09-09|2015-04-14|Howard Martin|Biocidal aldehyde composition for oil and gas extraction|
    CN102695415B|2009-09-25|2014-03-12|陶氏环球技术有限公司|Synergistic antimicrobial composition|
    EP2695518B1|2009-10-20|2015-07-15|Dow Global Technologies LLC|Synergistic antimicrobial composition|
    AU2013242826B2|2009-10-20|2015-11-05|Dow Global Technologies Llc|Synergistic antimicrobial composition|
    AU2013242825B2|2009-10-20|2015-02-05|Dow Global Technologies Llc|Synergistic antimicrobial composition|
    US10174239B2|2010-02-09|2019-01-08|Baker Hughes, A Ge Company, Llc|Process for preventing or mitigating biofouling|
    US20120034313A1|2010-08-06|2012-02-09|Baker Hughes Incorporated|Microbiocide/Sulfide Control Blends|
    WO2012154785A2|2011-05-09|2012-11-15|Rhodia Operations|Methods for controlling depolymerization of polymer compositions|
    US8613941B1|2012-01-05|2013-12-24|Dow Global Technologies Llc|Synergistic antimicrobial composition|
    US20150308914A1|2014-04-23|2015-10-29|Clariant International, Ltd.|Hydrotesting and Mothballing Composition and Method of using Combination Products for Multifunctional Water Treatment|
    AR101211A1|2014-07-30|2016-11-30|Dow Global Technologies Llc|SYNERGIC ANTIMICROBIAL COMPOSITION|
    EP3261438B1|2015-02-27|2018-12-19|Dow Global Technologies LLC|Synergistic antimicrobial composition|
    US10213757B1|2015-10-23|2019-02-26|Tetra Technologies, Inc.|In situ treatment analysis mixing system|
    WO2018003626A1|2016-06-28|2018-01-04|株式会社クラレ|Disinfectant|
    US20200390102A1|2017-12-19|2020-12-17|DDP Specialty Electronic Materials US, Inc.|Synergistic antimicrobial composition|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB898904844A|GB8904844D0|1989-03-03|1989-03-03|Biocidal compositions and treatments|
    [返回顶部]