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WO1989010696A1 - Composition biocide - Google Patents

Composition biocide Download PDF

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Publication number
WO1989010696A1
WO1989010696A1 PCT/US1989/001700 US8901700W WO8910696A1 WO 1989010696 A1 WO1989010696 A1 WO 1989010696A1 US 8901700 W US8901700 W US 8901700W WO 8910696 A1 WO8910696 A1 WO 8910696A1
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Prior art keywords
weight
group
chloro
oxidizing biocide
set forth
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PCT/US1989/001700
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English (en)
Inventor
Edward H. Puzig
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Great Lakes Chemical Corp
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Great Lakes Chemical Corp
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Publication of WO1989010696A1 publication Critical patent/WO1989010696A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

Definitions

  • This invention relates to a novel biocide, and more particularly to a dry biocidal composition containing an oxidizing biocide and a non-oxidizing biocide.
  • Another object of this invention is the provision of such composition in a "user-friendly" form, wherein the composition is in the form of a solid agglomerate, such as a tablet, which provides an effective amount of each biocidal component and which is stable in the dry state as well as in the effluent of an erosion feeder.
  • the present invention is dir ⁇ ected to a novel dry biocidal composition, the active ingredient of which comprises an oxidizing biocide and a non-oxidizing biocide.
  • the oxidizing biocide is an N-halo organic oxidizer selected from the group consisting of 3- chloro-4,4-dimethyl-2-oxazolidinone, 3-bromo,4,-4-dimethyl- 2-oxazolidinone, l,3-dichloro-4,4,5,5-te amethyl-2- imidazolidinone, 1,3-dibromo-4, 4,5,5-tetramethyl-2- imidazolidinone, l-bromo-3-chloro-4,4,5, 5-tetramethyl- 2-imidazolidinone, 1,3,5-trichloro-s-t iazine- 2 , 4,6-trione, dichloro-s-triazine-2,4,6-trione, sodium dichloro ⁇ isocyanurate, potassium dichloroisocyanurate, N-halohydantoin compounds of the formula
  • R 1 and R2 are independently selected from the group consisting of hydrogen and lower alkyl
  • X and X 2 are independently selected from the group consisting of bromine, chlorine and hydrogen, at least one of X and
  • R and R. are each selected from the group consisting of hydrogen, lower alkyl and monocarbocyclic aryl; wherein R-, 3 , R ⁇ and R_ are each selected from the group consisting of hydrogen, chlorine and bromine; and wherein at least one of said R_, R 3 , R 4 " and R-. is chlorine and at least another of said R_, R 3 , R. and R-. is bromine.
  • the non-oxidizing biocide is selected from the group consisting of 2-chloro- 4, ⁇ -bis(ethylamino)-s-triazine (si azine), 2-(tert- butylamino)-4-chloro-6-(ethylamino)-s-triazine ( erbuthylazine) , 2-chloro-4,6-bis-(isop opylamino)- s-triazine (propazine), and 2-chloro-4 ethyl-amino- 6-isopropylamino-s-triazine (atrazine) .
  • the invention is further directed to a solid agglomerate comprising the biocidal composition of this invention.
  • the agglomerate Upon dissolution in water, the agglomerate provides an effective amount of active halogen and triazine (simazine, terbuthylazine, atrazine, propazine or a combination thereof) .
  • the tablets may optionally include one or more inert ingredient selected from among binders, hardening agents, die lubricants, stabilizers and corrosion inhibitors.
  • the invention is further directed to a method of controlling the growth of algae and bacteria in a water system. The method comprises treating the water system with an effective amount of the biocidal composition of this invention.
  • FIG. 1 is a graph showing the water temperature on the upper deck and in the basin of the cooling tower versus time as described in Example 3.
  • FIG. 2 is a graph showing the weight of the biofilm on a portion of the upper deck of the cooling tower and the concentration of algacide in the cooling water versus time as described in Example 3.
  • FIG. 3 is a graph showing the weight of the biofilm on a portion of the upper deck of the cooling tower and the concentration of algacide in the cooling water versus time as described in Example 3.
  • a biocidal product which comprises an oxidizing biocide and a non-oxidizing biocide.
  • the product thus provides effective control of bacteria and algae, at concentrations of .each component that are less than that required if either component were used alone.
  • the dry product is stable, i.e., it does not undesirably react when blended in a dry form as measured by the absence of the liberation of halogen gas for a 120 day period at a temperature of
  • the oxidizing and non-oxidizing biocides are stable in the aqueous phase, even in the effluent of erosion feeders where the concentrations of each biocidal composition are considerably greater than their respective normal use concentrations in the water system.
  • Oxidizing biocides having application in the present invention include 3-chloro-4,4-dimethyl-2- oxazolidinone, 3-bromo- 4,4-dimethyl-2-oxazolidinone, l,3-dichloro-4, 4,5,5-tetramethyl-2-imidazolidinone, 1,3-dibromo-4,4,5,5-tetramethyl-2-imidazolidinone, 1-bromo- 3-chloro-4,4, 5, 5-tetramethyl-2-imidazolidinone,
  • R 1 and R2 are independently selected from the group consisting of hydrogen and lower alkyl, and X and
  • X are independently selected from the group consisting of bromine, chlorine and hydrogen, at least one of X and
  • R and R are each selected from the group consisting of hydrogen, lower alkyl and monocarbocyclic aryl; wherein R , R , R and R are each selected from the group consisting of hydrogen, chlorine and bromine; and wherein at least one of said R_, R_, R. and R. is chlorine and at least another of said R_, R '3,' R i 4. a a"nn"d" — Rr"-5_- is bromine.
  • N-halohydantoins in general, and the N,N -dihalo- hydantoin compounds such as l-bromo-3-chloro-5,5- dimethylhydantoin, 3-bromo-l-chloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5- dimethylhydantoin, in particular, are preferred as the halogen donor.
  • the most preferred halogen donor is l-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH) .
  • Non-oxidizing biocides having application in the present invention include simazine, terbuthylazine propazine and atrazine and mixtures thereof.
  • Commercially available sources of simazine and terbuthylazine presently include a dry herbicide containing 90% simazine and 10% inert ingredients sold under the trade designation Princep Caliber 90 by Ceiba-Geigy (Greensboro, N.C.); and a dry herbicide containing 96% terbuthylazine and 4% inert ingredients sold under the trade designation Bellacide 320 by Ceiby-Geigy.
  • the biocidal product comprises about
  • the biocidal composition comprises about 1% to about 25% by weight triazine and about 75% to 99% by weight N-halo organic oxidizer, and most preferably, the biocidal composition comprises about 10% to about 20% by weight triazine and about 80% to 90% by weight N-halo organic oxidizer, based on the weight of the biologically active ingredient.
  • a product containing a blend of one of the above-identified active halogen donors and one or more of the above-identified triazines demonstrates no antagonistic effects upon the efficacy of each individual component. It has additionally been discovered that simazine, terbuthylazine, atrazine and propazine are stable to active halogen, even at relatively high levels of active halogen.
  • the dry composition of this invention is particularly well suited for tableting (or the formation of other solid agglomerates) and use in erosion feeders, where the concentration of free halogen in the erosion tank is regularly between about 25 to about 500 ppm, and on occassions will exceed 500 ppm.
  • the biocidal product may be in the form of granules, tablets or other solid agglomerates. Particularly where it is desired to "shock" the system, a granulated product is preferred.
  • Granules are conveniently prepared by blending powders of the oxidizing biocide and triazine(s), roller compacting the blend, crushing the compacted material and sieving the crushed material.
  • the granules have a sieve size of greater than 90% -10 mesh and greater than 95% +60 mesh. Co-compaction is particularly preferred because it results in a thorough and intimate mixing of the oxidizing biocide and triazine.
  • the granular product may also include inert ingredients that enhance the dissolution of the granules, such as sodium chloride, borax and sodium carbonate.
  • the biocidal product be in the ' form of a tablet (or other solid agglomerate).
  • the tablet can be designed to disintegrate at a particular rate, thus delivering the active biocidal ingredients to the system in a controlled, time-release manner.
  • Preferred hardening agents for the tablets include dry particulate alkali metal or alkaline earth salts consisting of a cation selected from among the group comprising lithium, sodium, potassium, calcium, and magnesium and an anion selected from among the group comprising carbonate, bicarbonate, borate, silicate, phosphate, percarbonate, and perphosphate.
  • the preferred binders are methyl cellulose, sodium-carboxy-methyl cellulose, polyvinyl alcohol, sodium alginate, gums, resins, zeolites, sodium silicate, starch, stearic acid, metallic stearates, glycols, carbowax and water.
  • the preferred dissolution agents are sodium chloride, borax and sodium carbonate.
  • Tablets are formed by blending dry particulate halogen donor and dry particulate triazine with additive (in a dry, particulate form) to form a mixture and transferring the mixture to a tableting machine such as a Stokes rotary press.
  • a die lubricant such as sodium stearate is included in the tableted composition.
  • Conventional blending equipment is used, a twin shell or Vee mixer being particularly preferred.
  • the amount of additive blended with the halogen donor and triazine is determined by the concentrations desired in the final product.
  • the tablets may be designed for either fast dissolution (shocking applications) or slow dissolution in an erosion tank.
  • the resulting tablets may vary in size depending upon the application. However, it has been found that tablets of about 1 3/16" diameter and of about 3" in diameter (sometimes referred to as "pucks") are preferred.
  • the density of the tablet has an effect upon its dissolution. In erosion tanks, the dissolution of low density tablets is difficult to control. Although it is less difficult to control the dissolution of higher density tablets, if the density gets too high, the dissolution rate decreases to such an extent that a larger capacity erosion tank is required. Therefore, it is preferred that the tablets have a density between about 1.2 and about 1.7 gm./cc.
  • the amount of corrosion inhibitor and stabilizers will of course, be determined by the application for the product.
  • the biocidal composition contain between about 5 to 50% by weight of the halogen stabilizer, between about 5 to 50% by weight of the ultraviolet light stabilizer, and between about 5 to 50% by weight of the corrosion inhibitor, based on the weight of the biocidal product (including additives)
  • biocide product of this invention is prepared by using one of the above-identified commercially available sources of simazine or terbuthylazine, such as Princep Caliber 90, it is particularly preferred that the product contain a halogen stabilizer.
  • the inert ingredients of Princep Caliber 90 include clays and surfactants which may cause decomposition of the N-halo organic oxidizers in the absence of halogen stabilizers.
  • the concentration of halogen and the concentration of triazine (simazine, terbuthylazine, atrazine, propazine or a combination thereof) in the water system be maintained at a level between about 0.1 to about 50 parts per million (ppm) of halogen (measured as chlorine) and between about 0.1 to about 10 ppm triazine to keep the system free of algae, bacteria and fungi.
  • ppm parts per million
  • the concentration of halogen and triazine be maintained at about 1-3 ppm and 1 ppm, respectively.
  • the relative amounts of N-halo organic oxidizer and triazine in the biocidal product are tailored so that upon regular (or continuous) treatment of the water system, the preferred levels of active halogen and triazine are maintained, taking into account loss from the system through blow down, dilution or other causes.
  • parts per million of halogen refers to the level of free halogen and not total halogen, except where indicated.
  • the number of parts per million of active halogen is determined as per AWWA chlorine method and the number of parts per million of triazine is determined by HPLC.
  • the biocidal product is in the form of a solid, shaped agglomerate such as a tablet.
  • the tablets not only provide the desired ratio of halogen and triazine (e.g., 1-3 parts halogen: 1 part triazine) but are designed to do so in a predetermined volume of water. For instance, because most spas contain a relatively small volume of water, it is preferable to use a tablet that provides 3 ppm of halogen and 1 ppm triazine per 250 gallons or 500 gallons of water.
  • a tablet that provides 3 ppm of halogen and 1 ppm of triazine per 1,000 or 10,000 gallons of water.
  • the provision of the biocidal product in tablets that provide the desired concentrations of halogen and triazine upon dissolution in a predetermined volume of water allows for relatively simple maintenance of the water system. The operator simply adds the correct number of tablets (i.e., an effective amount) at appropriate intervals to control the growth of algae, bacteria and fungi.
  • Such tablets are particularly well suited for use in erosion feeders currently being used, for example, in connection with the treatment of swimming pools and cooling towers.
  • Erosion tanks installed on a by-pass line taken from the main pumping line of the water system are filled with the biocidal composition in the form of granules or tablets.
  • a small quantity of the system water from the main pumping line is diverted to the erosion tank where the the biocidal composition is dissolved into the water, and the effluent from the erosion tank is returned to the water system.
  • the concentration of biocide in the effluent is dependant upon bed volume of solid biocide, temperature, water flow rate and density of the tablets.
  • the concentration of halogen in the effluent is about 10 to 500 ppm of halogen measured as chlorine and the concentration of triazine in the effluent is about 10 to 100 ppm.
  • the operator need only periodically refill the tank with the biocidal composition in the form of granules or tablets.
  • the biocidal composition of the present invention contains both an oxidizing and a non-oxidizing biocide, the operator need do nothing more than periodically refill the erosion tank with granules or tablets having the desired relative amounts of non-oxidizing and oxidizing biocides to effectively control bacteria, algae and fungi. No additional equipment is necessary, nor is there any need to separately add or keep records regarding any additional biocidal composition.
  • the N-halo organic oxidizing biocide is stable to both simazine and terbuthylazine when the product is in the form of granules or tablets produced from co-compacted powders of the N-halo organic oxidizing biocide and simazine or terbuthylazine. It was even more surprising that these compositions are stable to each other in erosion tanks where the concentration of halogen ranges from about 25 to 500 ppm -and the concentration of triazine ranges from about 2.5 to 50 ppm.
  • simazine and terbuthylazine are converted to N-halo derivatives which demonstrate greater efficacy as a biocide than does either simazine or terbuthylazine.
  • Tablets (20 gm) having the formulations listed below were prepared by cocompacting equimolar quantities of BCDMH, DMH and or cyanuric acid dry blending the granulated formulation ingredients and tableting on a stokes tableting press to the desired weight.
  • the tablets were stored for a 120 day period at a temperature of 120°F and monitored throughout this period for the formation of free bromine. No free bromine was detected. Also, at the conclusion of the 120 day period, each composition was analyzed for bromine content and it was found that each composition contained at least 95 wt. % of the bromine orginally contained by the composition.
  • CN 363 is a co-compacted powder compr is ing 65 wt . % BCDMH and 35 wt . . DMH .
  • bPC 90 is a herbicide sold by Ceiby-Geigy (Greensboro,
  • Aquazine is an algacide sold by Ceiby-Geigy (Greensboro,
  • _ CN 501 is a co-compacted powder comprising 60 wt.% BCDMH, 30 wt.% trichloroisocyanurate and 10 wt % cyanuric acid,
  • a Marley open double flow cooling tower with 10,000 gallon capacity and 80,000 gallons per day make up water flow was treated over a 104 day period with a formulation designated CN-530.
  • the CN-530 used in this example had two separate formulations. The first formulation contained 87% CN-363 (see Example 1), 3% sodium metasilicate pentahydrate and 10% Princep Caliber 90 (PC-90) and the second formulation contained 82% CN-363, 3% sodium metasilicate pentahydrate and 15% PC-90. In the following description, the percent of PC-90 is stated along with the compound number to distinguish the first CN-530 formulation from the second CN-530 formulation) .
  • the tower used for this test provided a perfect environment for algae *
  • CN-530 (10% PC-90).
  • the concentration of halogen was maintained at 0.5 to 1.5 ppm measured as bromine and the concentration of simazine was maintained at approximately 2.0 ppm as measured by HPLC.
  • the growth of algae stopped, turned grey, loosened and later became unattached from the tower distributor.
  • the biocide concentration in the cooling water fell below effective levels during the treatment period due to a malfunction of the chemical feed equipment, the algae mat grew back and was mechanically removed on day 48.
  • CN-530 (10% PC-90) treatment was continued at the previous levels. Chemical consumption during the period from day 21 to day 55 averaged 0.8 pounds per day CN-530 (10% PC-90).
  • MBT was slug fed starting on day 57 and concluded on day 66. During this period all remaining algae was killed.
  • the tower was treated with CN-530 (15% PC-90). However, because of the drop in temperature, less make-up water was required, resulting in a drop in the dosage of CN-530. As a result, the concentration of algacide in the cooling water dropped to less than 1 part per million and the biofilm weight increased significantly. The test was discontinued on day 104 when the water temperature fell below that which would promote the growth of algae.
  • a 10 cm I.D. pyrex glass flared pipe connector was used to sample the biofilm on the upper deck of the cooling tower.
  • the open-ended glass cylinder was placed directly on the upper deck and the biofilm was removed by scraping.
  • Three different regions were sampled: a previously fouled area, an area that was entirely clean (macroscopically) on the first day of the test, and an area that was cleaned on the day that CN-530 treatments began.
  • Two to four different areas in each region on the upper deck were scraped and the biofilm specimens were pooled. The specimens were transported to the laboratory on ice and then stored frozen until quantitative biofilm analyses were performed. 2.
  • the dry weight and ash-free weight of biofilm samples were determined essentially as described in Standard Methods for the Examination of Water and Wastewater, 15th Ed. (Method 1002H.4).
  • One to five ml aliquots of homogenized biofilm samples were added to pre-weighed crucibles and dried to constant dry weight at 105 C. Samples were then ignited at 550 C for 1 hr in order to determine ash-free weight.
  • About 0.5 ml of distilled water was added to each crucible to rehydrate the residue and then, dried to constant weight at 105 C in order to correct for the water of rehydration.
  • the difference between the dry weight and the corrected ash-free weight was used to calculate the total volatile residue (which is a measure of the organic weight).
  • Each biofilm sample was analyzed in triplicate.
  • Figure 1 shows the water temperature (°C) on the upper deck and in the basin of the cooling tower.
  • the water temperature ranged from about 26 to about 34°C on the upper deck; the microbial biofilm was consistently exposed to cooler water after about day 50.
  • FIG. 2 shows the biofilm weight (open symbols) and simazine concentration (closed symbols) of the previously fouled area, i.e., that area not cleaned of algae immediately prior to the test.
  • the data show that the biofilm weight increased dramatically when the MBT was discontinued (day 13); that the increase in biofilm weight stopped when CN-530 treatment began (day 20) and that biofilm development was inhibited until about day 37; that biofilm development began again when the concentration of simazine was consistently below about 2 ppm (day 37-48); and that after the biofilm was removed (day 48), it did not increase dramatically until the simazine concentration was consistently below about 1 ppm.
  • Figure 3 shows the biofilm weight (open symbols) and simazine concentration (closed symbols) with time for the surface that was cleaned when the test began.
  • the data show that the biofilm did not increase in weight dramatically until after the algacide concentration had been consistently below about 2 ppm (days 37-48); and that biofilm development was inhibited after cleaning the deck (day 48) until the concentration of algacide dropped to below 1 ppm.
  • the residual delivery rate behavior was relatively flat over the four-hour test period for both CN-530 and BCDMH tablets in the brominator.
  • the average free bromine residual was 84.8 ppm for the CN-530 tablets and 33.9 ppm for the BCDMH tablets.
  • the amount of product consumed by mass balance determination was 2.8 lbs for CN-530 and 0.16 lbs for BCDMH tablets.
  • the delivery rates are listed in Table 1.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
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  • Inorganic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
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  • Pest Control & Pesticides (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

On a mis au point une composition biocide sèche, dont l'ingrédient actif comprend un biocide oxydant et un biocide non oxydant organiques de N-halo, ledit biocide oxydant organique de N-halo étant sélectionné dans le groupe composé de 3-chloro-4,4-diméthyl-2-oxazolidinone, 3-bromo-4,4-diméthyl-2-oxazolidinone, 1,3-dichloro-4,4,5,5-tétraméthyl-2-imidazolidinone, 1,3-dibromo-4,4,5,5-tétraméthyl-2-imidazolidinone, 1-bromo-3-chloro-4,4,5,5-tétraméthyl-2-imidazolidinone, 1,3,5-trichloro-s-triazine-2,4,6-trione, dichloro-s-triazine-2,4,6-trione, dichloroisocyanurate de sodium, dichloroisocyanurate de potassium, de composés de N-halohydantoine de la formule (I), dans laquelle R1 et R2 sont sélectionnés indépendamment dans le groupe composé d'hydrogène et d'alkyle inférieur, et x1 et x2 sont sélectionnés indépendamment dans le groupe composé de brome, chlore et hydrogène, au moins x1 ou x2 représentant de l'halogène, et N-haloglycourils ayant la formule (II), dans laquelle R et R1 sont chacun sélectionnés dans le groupe composé d'hydrogène, d'alkyle inférieur et d'aryle monocarbocyclique, dans laquelle R2, R3, R4 et R5 sont chacun sélectionnés dans le groupe composé d'hydrogène, de chlore et de brome; et dans laquelle au moins un des quatre éléments R2, R3,R4 et R5 représente du chlore et au moins un autre de ces derniers représente du brome. Le biocide non oxydant est sélectionné dans le groupe composé de 2-chloro-4,6-bis(éthylamino)-s-triazine,2-(tert-butylamino)-4-chloro-6-(éthylamino)-s-triazine, 2-chloro-4,6-bis(isopropylamino)-s-triazine, and 2-chloro-4 éthylamino-6-isopropylamino-s-triazine.
PCT/US1989/001700 1988-05-05 1989-04-24 Composition biocide Ceased WO1989010696A1 (fr)

Applications Claiming Priority (2)

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US19039588A 1988-05-05 1988-05-05
US190,395 1988-05-05

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AU (1) AU623411B2 (fr)
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ZA (1) ZA893150B (fr)

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FR2698347A1 (fr) * 1992-11-24 1994-05-27 Bron Jean Pierre Nouvelles compositions pour le traitement de l'eau à base de glucoluryl et d'uréido hydrantoïne.
EP0686344A1 (fr) * 1991-02-15 1995-12-13 Rohm And Haas Company Compositions anti-algues comprenant des éthers diphényliques et de l'hydantoine halodialkylée
EP0666834A4 (fr) * 1992-10-30 1996-06-05 Great Lakes Chemical Corp Procedes permettant de produire des desinfectants residuels pendant l'ozonisation de l'eau.
EP0857694A3 (fr) * 1997-01-29 1998-12-16 Fmc Corporation Méthode pour stabiliser un désinfectant halogéné en milieu aqueux
WO2001053209A3 (fr) * 2000-01-18 2002-03-28 Albemarle Corp Procedes de regulation microbiologique dans des systemes aqueux
US6448410B1 (en) 2000-01-18 2002-09-10 Albemarle Corporation Production of compacted biocidal agent from particulate biocidal agent without using a binder
US6495698B1 (en) 2000-01-18 2002-12-17 Albemarle Corporation Binder-free compacted forms of 1,3-dihalo-5,5-dimethylhydantoins
US6508954B1 (en) 2000-01-18 2003-01-21 Albemarle Corporation 1,3-dibromo-5,5-dimethylhydantoin of enhanced properties
US6638959B2 (en) 2000-01-18 2003-10-28 Albemarle Corporation Microbiological control in aqueous systems
US6680070B1 (en) 2000-01-18 2004-01-20 Albemarle Corporation Particulate blends and compacted products formed therefrom, and the preparation thereof
WO2003106466A3 (fr) * 2002-06-14 2004-04-15 Univ Auburn N-halamine siloxanes utilisables dans des revetements et des materiaux biocides
US6809205B1 (en) 2000-01-18 2004-10-26 Albemarle Corporation Process for producing N-halogenated organic compounds
US6908636B2 (en) 2001-06-28 2005-06-21 Albermarle Corporation Microbiological control in poultry processing
US6965035B1 (en) 2002-07-25 2005-11-15 Albemarle Corp Compacted forms of halogenated hydantoins
US6986910B2 (en) 2001-06-28 2006-01-17 Albemarle Corporation Microbiological control in poultry processing
US7195782B2 (en) 1998-06-01 2007-03-27 Albemarle Corporation Concentrated aqueous bromine solutions and their preparation
US7371397B2 (en) 2000-01-18 2008-05-13 Albemarle Corporation Methods for microbiological control in aqueous systems
US7579018B2 (en) 2000-01-18 2009-08-25 Albemarle Corporation Microbiological control in aqueous systems
US7901276B2 (en) 2003-06-24 2011-03-08 Albemarle Corporation Microbiocidal control in the processing of meat-producing four-legged animals
US7999118B2 (en) 2000-01-18 2011-08-16 Albemarle Corporation Process for producing N-halogenated hydantoins
US8679548B2 (en) 1998-06-01 2014-03-25 Albemarle Corporation Active bromine containing biocidal compositions and their preparation

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US4659359A (en) * 1979-12-18 1987-04-21 Ciba-Geigy Corporation 2-chloro-4,6-diamino-s-triazines as algicides

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FR2698347A1 (fr) * 1992-11-24 1994-05-27 Bron Jean Pierre Nouvelles compositions pour le traitement de l'eau à base de glucoluryl et d'uréido hydrantoïne.
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US6508954B1 (en) 2000-01-18 2003-01-21 Albemarle Corporation 1,3-dibromo-5,5-dimethylhydantoin of enhanced properties
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US9029562B2 (en) 2000-01-18 2015-05-12 Albemarle Corporation Process for producing N-halogenated hydantoins
US6448410B1 (en) 2000-01-18 2002-09-10 Albemarle Corporation Production of compacted biocidal agent from particulate biocidal agent without using a binder
WO2001053209A3 (fr) * 2000-01-18 2002-03-28 Albemarle Corp Procedes de regulation microbiologique dans des systemes aqueux
US8586763B2 (en) 2000-01-18 2013-11-19 Albemarle Corporation Process for producing N-halogenated hydantoins
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US7985413B2 (en) 2000-01-18 2011-07-26 Albemarle Corporation Microbiological control in aqueous systems
US7579018B2 (en) 2000-01-18 2009-08-25 Albemarle Corporation Microbiological control in aqueous systems
US6495698B1 (en) 2000-01-18 2002-12-17 Albemarle Corporation Binder-free compacted forms of 1,3-dihalo-5,5-dimethylhydantoins
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US7172782B2 (en) 2001-06-28 2007-02-06 Albemarle Corporation Microbiological control in poultry processing
US7182966B2 (en) 2001-06-28 2007-02-27 Albemarle Corporation Microbiological control in poultry processing
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US6908636B2 (en) 2001-06-28 2005-06-21 Albermarle Corporation Microbiological control in poultry processing
CN101798323A (zh) * 2002-06-14 2010-08-11 奥本大学 用于杀生物涂层和材料的杂环卤胺硅氧烷
US6969769B2 (en) 2002-06-14 2005-11-29 Vanson Halosource, Inc. N-halamine siloxanes for use in biocidal coatings and materials
WO2003106466A3 (fr) * 2002-06-14 2004-04-15 Univ Auburn N-halamine siloxanes utilisables dans des revetements et des materiaux biocides
US6965035B1 (en) 2002-07-25 2005-11-15 Albemarle Corp Compacted forms of halogenated hydantoins
US7901276B2 (en) 2003-06-24 2011-03-08 Albemarle Corporation Microbiocidal control in the processing of meat-producing four-legged animals

Also Published As

Publication number Publication date
EP0417144A4 (en) 1992-05-13
AU623411B2 (en) 1992-05-14
ZA893150B (en) 1990-01-31
EP0417144A1 (fr) 1991-03-20
AU3735889A (en) 1989-11-29

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