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
  • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
  • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
  • C02F1/56—Macromolecular compounds
• • 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
  • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
  • A01N33/02—Amines; Quaternary ammonium compounds
  • A01N33/12—Quaternary ammonium compounds
• • 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

Definitions

• the present invention relates generally to water clarifying compositions, and more particularly to water clarifying compositions comprising combinations of two or more polymeric or non-polymeric non-oxidizing water treatment compositions.
• the clarity of recreational waters is an important aspect of overall water quality. This is especially true in residential and commercial swimming pool applications where the clarity of the water indicates to the swimmer that the water is clean and pure.
• oxidizers such as chlorine, bromine, hydrogen peroxide and potassium peroxymonopersulfate are routinely used to achieve and maintain clean water. These oxidizers are typically added as solid, slow-release formulations, powders or liquids that achieve a desired level of oxidizer concentration.
• Nonoxidizing antimicrobials such as polyquaternary ammonium compounds and PHMB are also known to be effective for controlling biofouling in various circulating water systems.
• polyquats such as Q6/6 and PDED are important microbiocides and are widely used in water treatment.
• Nonoxidizing antimicrobials are not, however, known to be effective clarifiers. Although PDED and PHMB have demonstrated some clarification properties under certain conditions, they are used primarily as antimicrobials in water treatment applications. The clarification that has been observed with these compositions has been attributed to the death of biofouling microbes and does not involve water that was repeatedly challenged by swimmer wastes. it is also known that nonoxidizing biocides may sometimes be used in combination with other nonoxidizers to more effectively deal with the great diversity of microbial populations. From the perspective of antimicrobial performance, using combinations of biocides in tandem decreases the ability of microorganisms to adapt, since microbial adaptation to individual biocides is not uncommon.
• Another important reason for using two antimicrobials simultaneously is to take advantage of synergistic effects. That is, some biocides have been shown to be more effective when ' ombined with other antimicrobials. Even if there are no biocidally synergistic interactions, one compound may act as a non lethal adjuvant or potentiator for another. Although it would be desirable to apply products such as these in a single formulation, this may not be possible due to inherent blending incompatibilities. That is, the compounds of interest may not be miscible.
• a need also exists for water treatment compositions that are preblended combinations of two or more immiscible polyquaternary a onium compounds. The present invention addresses those needs.
• non-oxidizing polymers such as polyquaternary ammonium compounds such as poly[hexamethylenedimethyl ammonium] chloride (Q6/6), Q12/6 (a homolog of Q6/6), Q4/6 (another homolog of Q6/6) , PDED and IPCP are combined to make preblended water treatment concentrates.
• Non-polymeric, non-oxidizing compositions such as ADBAC, DDAC, DIDAC, DDC and DGH may also be used in the preblended concentrates.
• two or more immiscible polymeric compounds are combined in one preblended composition by using concentrated hydrogen peroxide as a formulating aid.
• One advantage of the present invention is the provision of improved water clarifying compositions.
• Another advantage of the present invention is the provision of compositions that increase the effective life of swimming pool oxidizers.
• a third advantage of the present invention is the ability to combine two or more previously incornpatable polymeric compounds into one preblended water treatment composition.
• FIG. 1 shows a tank apparatus as used in the examples
• FIG. 2 is a graph showing the effect of polymer on .
• one aspect of the present invention deals with the non-biocidal properties of cationic polymers in aqueous systems, and specifically with their ability to enhance water quality.
• the present invention relates to water enhancement including water clarification and/or reducing the amount of oxidizer demand present in aqueous systems. These phenomena have previously not been observed with monomeric cations (e.g., monomeric quaternary ammonium salts) .
• one aspect of the present invention provides a method of formulating preblended liquid concentrates for treating water with a combination of polymeric or non-polymeric compounds.
• combinations of water treatment agents that are immiscible when blended alone may be preblended to make effective water treatment concentrates when formulated with concentrated hydrogen peroxide.
• polyquaternary ammonium compounds such as 1, 6-hexanediamine-N,N,N' ,N' -tetramethyl polymer with 1, 6-dichlorohexane (Q6/6, also identified as poly[hexamethylenedimethyl ammonium] chloride) and two of its homologs (Q12/6 and Q4/6) .
• polyquats such as 1, 6-hexanediamine-N,N,N' ,N' -tetramethyl polymer with 1, 6-dichlorohexane (Q6/6, also identified as poly[hexamethylenedimethyl ammonium] chloride) and two of its homologs (Q12/6 and Q4/6) .
• polyquaternary ammonium compound poly[oxyethylene- (dimethylimino) ethylene-(dimethyli ino) ethylene dichloride] (PDED) or polycations such as pol (iminoimidocarbonyl- iminoimidocarbonyliminohexamethylene) chloride (also called polyhexamethylene biguanide or PHMB) may be used.
• Oxidizer is defined consistent with the use of that term by persons of ordinary skill in the art of swimming pool water treatment.
• Oxidizers useful in the synergistic compositions of the present invention include chlorine, bromine, H_0 ⁇ , and other oxygen-releasing oxidizers.
• concentrated hydrogen peroxide is used as a formulating agent for concentrated, miscible or immiscible mixtures of polymeric or non-polymeric compounds such as polymeric quaternary ammonium compounds (polyquats), monomeric, dimeric or oligomeric quaternary ammonium compounds (quats), etc.
• polyquats polymeric quaternary ammonium compounds
• quats monomeric, dimeric or oligomeric quaternary ammonium compounds
• compounds such as poly(hexamethylammonium) chloride (Q6/6), isomers of Q6/6 (particularly, Q12/6 and Q4/6), poly [oxyethylene (dimethylimino) ethylene-(dimethylimino) ethylene] dichloride (PDED), dodecamethylene-dimethylimino chloride (Q6/12), 1,3-diazo-2,4-cyclopentadiene with l-chloro-2,3- epoxypropane (IPCP), dodecylguanidine hydrochloride (DGH), diisodecyldi ethyl ammonium chloride (DDC), alkyldimethylammonium chloride (ADBAC) ,
• DIDAC N-decyl-N-isononyl-N,N-dimethylammonium chloride
• DDAC didecyldimethyl ammonium chloride
• Microbes such as Pseudomonas aeruginosa, Escherichia CPU/ and Staphvlococcus aureus are some of the major bacteria which can be recovered from recreational waters after swimmer use. Mixtures of these bacteria (ca. 10 - 10 organisms) were added to 10 gallon tanks containing balanced pool water (200 ppm calcium carbonate, 120 ppm calcium sulfate, pH 7.4) . In addition, 10 ml of a synthetic insult was added to each aquarium at the time of inoculation.
• the synthetic insult used in the following examples was composed of: Components g/L
• the filter contained a 4 x 7 inch section from a standard pool cartridge filter inside a porous housing. See Fig. 1. Three tanks were used for each experiment.
• Experiment 1 was performed to determine the water clarification potential of low doses of conventional oxidizers.
• Four ten-gallon tanks were filled with balanced pool water.
• Tanks 1 and 2 contained no oxidizer.
• Tanks 3 and 4 contained H_0 2 and chlorine, respectively.
• Oxidizer was added daily to achieve a desired oxidizer concentration.
• Pieces of compressed oxidizer were placed into the water intake tube of the pump. Dissolved oxidizer traveled through the pump and filter assembly and then into the bulk water. Skimmer fed oxidizer is applied this way in actual pools. After achieving the desired residual oxidizer level, bacteria were added to tanks 2, 3 and 4. Tank 1 was the only tank which received neither bacteria nor oxidizer.
• Table 1 shows the results of experiment 1. It can be seen from Table 1 that low levels of chlorine or H_0_ had no demonstrable effect on water clarity.
• Experiments 2-4 were performed to demonstrate the effects of polymeric cations (such as polyquaternary ammonium compounds) and chlorine on water quality.
• Two ten-gallon tanks were dosed with about 5 ppm of either Q6/6, Q12/6, Q4/6 or PDED. One of these tanks and the third tank was treated with low levels of chlorine.
• Pieces of compressed chlorine (trichloroisocyanurate) were placed into the water intake tube of the pump. Dissolved chlorine traveled through the pump and filter and then into the bulk water, as typically applied in swimming pools.
• Chlorine levels were measured by titration with 0.1 N sodium thiosulfate. After achieving a chlorine residual of ca. 0.5 ppm (usually no higher than 1 ppm) or less, bacteria were added.
• Tables 2-4 show the synergistic effect that chlorine and polyquats have on water quality.
• tank #1 was dosed with compressed trichloroisocyanurate for successive days
• tank #2 was dosed with ca. 5 ppm of cationic polymer
• tank #3 contained a mixture of chlorine and cationic polymer. Bacteria were added each day. The amount of bacteria added was sufficient to give the water a cloudy appearance.
• NTU Water turbidity
• Tank #1 Water turbidity was high after the first inoculation and increased with subsequent inoculations (tank #1) .
• Tanks containing only polyquats were substantially clearer (tank #2).
• Tank #3 generally had the lowest turbidities. In actual pools, a turbidity reading of greater than 0.3 NTU is considered hazy.
• Tables 5-8 show the effect of polycations upon hydrogen peroxide stability.
• Table 9 shows the effect of a cationic monomer, alkyldimethylammonium chloride (ADBAC) , upon peroxide and water clarity.
• ADBAC alkyldimethylammonium chloride
• Table 8 demonstrates that the cationic polymer PHMB also showed clarification synergy with hydrogen peroxide. This proves that the synergistic effect between oxidizers and cationic polymers is not a property unique to polyquaternary ammonium compounds such as Q6/6 and PDED. PHMB was not tested in the presence of chlorine because it is not compatible with oxidizing halogens.
• the list of potential clarifiers included polycations (Q6/6, Q12/6, Q4/6, PDED and PHMB), the monomeric cation diisodecyl dimethyl ammonium chloride (DDAC) and H O . Each quat was dosed at 10 ppm along with 10 ppm H_0_ . The results are recorded in Table 10.
• a triple dose of H202 was used (30 ppm) , in lieu of the usual 10 ppm.
• Solutions of concentrated hydrogen peroxide (0.1-50%) are blended with compounds that may or may not be readily miscible. These non-oxidizing blends hold commercial value for treating industrial or recreational regulated waters, hard surface sanitization or for household consumer use.
• the concentrated solutions are preferably applied as a single product in waters or on hard surfaces.
• the combinations of non-oxidizing compounds are preferably added to the peroxide in concentrations ranging from 0.1-10%.
• the combination of Q6/6 and Q6/12 was determined to be immiscible when blended as concentrates.
• Concentrated (35%) hydrogen peroxide was used as a disolution agent to prepare an aqueous Q6/6:Q6/12 :hydrogen peroxide blend with a final formulation of about 5% Q6/6, about 5% Q6/12, and about 25% hydrogen peroxide.
• Blends of immiscible polymeric and non-polymeric water treatment compositions are blended.
• the combination of Q6/6, PDED and DIDAC was determined to be immiscible when blended as concentrates.
• Concentrated (35%) hydrogen peroxide was used as a disolution agent to prepare an aqueous Q6/6 :PDED:DIDAC:hydrogen peroxide blend with a final formulation of about 5% Q6/6, about 10% PDED, about 2% DIDAC and about 25% hydrogen peroxide.
• hydrogen peroxide is an effective formulating agent for compounds such as those listed in the Table above. This list is not exhaustive however, and merely identifies representative examples of compounds which one skilled in the art might use in compositions formulated with hydrogen peroxide according to the present invention.
• shelf-stable, preblended concentrates of Q6/6 and hydrogen peroxide are prepared by combining 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 95% portions of concentrated hydrogen peroxide with 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, and 5% portions, respectively, of Q6/6 to make a liquid concentrate.
• the concentrates were observed to be shelf-stable for at least about 60 days when stored at room temperature.
• shelf-stable, preblended concentrates of Q12/6 and hydrogen peroxide are prepared by combining 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 95% portions of concentrated hydrogen peroxide with 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, and 5% portions, respectively, of Q12/6 to make a liquid concentrate.
• the concentrates were observed to be shelf-stable for at least about 60 days when stored at room temperature.
• shelf-stable, preblended concentrates of Q4/6 and hydrogen peroxide are prepared by combining 5%, 10%, 20%, 30%, '.0%, 50%, 60%, 70%, 80%, 90%, and 95% portions of concentrated hydrogen peroxide with 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, and 5% portions, respectively, of Q4/6 to make a liquid concentrate.
• the concentrates were observed to be shelf-stable for at least about 60 days when stored at room temperature.
• Shelf-stable, preblended concentrates of PDED and hydrogen peroxide are prepared by combining 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 95% portions of concentrated hydrogen peroxide with 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, and 5% portions, respectively, of PDED to make a liquid concentrate.
• the concentrates were observed to be shelf-stable for at least about 60 days when stored at room temperature.

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• 1997
  • 1997-03-18 WO PCT/US1997/004129 patent/WO1997034834A1/en not_active Application Discontinuation
  • 1997-03-18 BR BR9708106A patent/BR9708106A/pt not_active Application Discontinuation
  • 1997-03-18 AU AU20794/97A patent/AU2079497A/en not_active Abandoned
  • 1997-03-18 CA CA 2249718 patent/CA2249718A1/en not_active Abandoned
  • 1997-03-18 EP EP97909045A patent/EP0888249A4/de not_active Withdrawn
  • 1997-03-18 AR ARP970101075A patent/AR006274A1/es not_active Application Discontinuation

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