Classifications

• • 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
• • 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
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
• • 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
  • C02F1/72—Treatment of water, waste water, or sewage by oxidation
  • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
• • 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
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/04—Disinfection

Definitions

• the invention relates to water treatment compositions, and more particularly to slow dissolving water treatment compositions that include at least one halogen-releasing compound and a fiuoropolymer.
• Chlorine releasing compounds have been used in a wide variety of applications as a sanitizer or disinfectant including in for many applications, including pools and spas, preventing and curing diseases in fisheries, fruits and vegetables preservation, wastewater treatment, algaecide for recycling water of industry and air conditioning, and the like.
• a sanitizer or disinfectant including in for many applications, including pools and spas, preventing and curing diseases in fisheries, fruits and vegetables preservation, wastewater treatment, algaecide for recycling water of industry and air conditioning, and the like.
• slow chlorine releasing compounds include chlorinated isocyanuric acids compounds and chlorinated hydantoins.
• Trichloroisocyanuric acid also known as TCCA, "trichlor”, and trichloro-s- triazinetrione
• TCCA is particularly useful because it imparts approximately 90% chlorine to the water, and is therefore easy to use for large pools.
• TCCA is stable and can reduce chlorine loss during sun exposure.
• TCCA TCCA in pool and spa applications
• TCCA tablets dissolve and erode over time when placed in a swimming pool skimmer basket. Erosion is the dominant mechanism when the pool pump is running and dissolution is the primary mechanism when the pool pump is turned off (static dissolution). Due to the continued dissolution of tablet under static conditions, a high concentration of chlorine is built up in the skimmer and plumbing leading to the pump. In addition to the chlorine level, this same water has a low pH and the combination of these two chemical parameters will contribute to bleaching or fading of vinyl pool liners.
• the present invention is directed to a water treatment composition, comprising: 50 - 99.9 wt.% of particulate halogen-releasing compound; and 0.1 - 10 wt.% of particulate fluoropolymer, wherein the percentages are based on the total weight of the composition.
• the invention is directed to a water treatment composition, comprising: 50 - 99 wt.% of particulate halogen-releasing compound; 1 - 10 wt.% of sodium hexametaphosphate (SHMP); 1 - 10 wt.% of aluminum sulfate; 0.5 - 15 wt.% of a sulfate salt selected from the group consisting of copper sulfate, zinc sulfate, and combinations thereof; and 0.1 - 10 wt.% of particulate polytetrafluoroethylene polymer, wherein all weight percentages are based on the total weight of the composition.
• SHMP sodium hexametaphosphate
• aluminum sulfate 0.5 - 15 wt.% of a sulfate salt selected from the group consisting of copper sulfate, zinc sulfate, and combinations thereof
• 0.1 - 10 wt.% of particulate polytetrafluoroethylene polymer wherein all
• the invention is directed to a water treatment composition, comprising: 50 - 99 wt.% of particulate halogen-releasing compound; 1 - 10 wt.% of sodium hexametaphosphate; 0.5 - 15 wt.% of a sulfate salt selected from the group consisting of copper sulfate, zinc sulfate, and combinations thereof; and 0.1 - 10 wt.% of particulate polytetrafluoroethylene polymer, wherein all weight percentages are based on the total weight of the composition.
• Figure 1 is a graph illustrating percent dissolved per hour of the compositions of the invention.
• Figure 2 is a graph illustrating percent dissolved per hour of the compositions of the invention in a static environment
• Figure 3 is a graph illustrating percent dissolved per hour of the compositions of the invention in a dynamic environment
• Figure 4 is a graph illustrating percent dissolved per hour of the compositions of the invention.
• Figure 5 is a graph illustrating percent dissolved per hour of the compositions of the invention in a static environment
• Figure 6 is a graph illustrating percent dissolved per hour of the compositions of the invention in a dynamic environment
• Figure 7 is a graph illustrating static dissolution comparison of various compositions of the invention.
• Figure 8 is a graph illustrating dynamic dissolution comparison of various
• compositions of the invention are compositions of the invention.
• Figure 9 is a graph illustrating overall dissolution comparison of various compositions of the invention.
• Figure 10 is a graph illustrating 24-hour dissolution comparison of various
• compositions of the invention [24] DETAILED DESCRIPTION OF THE INVENTION
• unitary structure is intended to be a single solid form of the particulate components.
• the unitary structure is the blend of components compacted into a single solid structure. Examples of unitary structures include sticks, tablets and other similar structures.
• the term "particulate” is intended to be particles in the form of a powder, granules, fibers and mixtures thereof. Particulates may be non-agglomerated or agglomerated.
• the term "formulated” means that the composition has additional functional ingredients in addition to the halogen-releasing compound and the fluoropolymer which are designed to treat the pool water.
• “Non-formulated” means a composition which only contains the halogen-releasing compound and the fluoropolymer and is free of other functional ingredients intended to treat the pool water.
• the invention is a water treatment composition, comprising: 50 - 99.9 wt.% of a particulate halogen-releasing compound; and 0.1 - 10 wt.% of particulate fluoropolymer, wherein all weight percentages are based on the total weight of the composition.
• a water treatment composition comprising: 50 - 99.9 wt.% of a particulate halogen-releasing compound; and 0.1 - 10 wt.% of particulate fluoropolymer, wherein all weight percentages are based on the total weight of the composition.
• the first component of the invention is a halogen-releasing compound.
• Suitable halogen-releasing compounds include chlorinated isocyanuric acids, such as,
• TCCA trichloroisocyanuric acid
• DCCA dichloroisocyanuric acid
• halogen-containing hydantoins including both chlorine-containig hydantoins and bromine- containing hydantoins such as bromochlorodimethylhydantoin (BCDMH);
• DBDMH dibromodimethylhydantoin
• DCDMH dichlorodimethylhydantoin
• dichloromethylethylhydantoin DCMEH
• DCMEH dichloromethylethylhydantoin
• trichloroisocyanuric acid also known as TCCA, "trichlor”, and trichloro-s-triazinetrione, is of particular interest.
• the halogen-releasing compound is present in the composition in an amount from 50-99.9% by weight of the composition.
• the halogen-releasing compound is generally present in higher amounts.
• the halogen-releasing compound is present in an amount from about 90-99.9% by weight of the composition, and generally from about 96% to about 99.5% by weight of the composition.
• the halogen-releasing compound is present in lesser amounts.
• the halogen-releasing compound then typically present in an amount between about 60% and about 99% by weight of the composition, more typically in amount between about 70% and about 98%) by weight of the composition and most typically between about 90% and about 96% by weight of the composition. All weight percentages are based on the total weight of all of the components of the composition.
• the halogen-releasing compound is present as a particulate material.
• the second component of the invention is a particulate polyfluorinated polymeric material or fluoropolymer.
• polyfluorinated polymeric materials that may be used as the compaction aid include: polytetrafluoroethylene (PTFE),
• fluoropolymers derived from fluoroalkyl acrylates such as poly(l,l-dihydroperfluorobutyl acrylate), poly(3 -perfluoromethoxy- 1 , 1 -dihydroperfluoropropyl acrylate),
• poly(trifluoroisopropyl methacrylate) and the condensation product of adipic acid and 2,2,3,3,4,4-hexafluoropentanediol may also be used.
• the polyfluorinated polymer may be added to the particulate halogen-releasing compound as a particulate material, such as a finely-divided dry powder, granules, fibrous material and the like.
• Polytetrafluoroethylene (PTFE) has been found to be effective in the present invention.
• the particulate fluoropolymer is present in the composition in an amount of 0.1-10% by weight, generally in an amount between about 0.2% and about 7.5% and typically between about 0.25% and about 5.0% by weight of the blend. In a particular embodiment, the fluoropolymer is present in an amount between about 0.5% and about 2.0% by weight in the blend all weight percentages being based on the total weight of the composition.
• Suitable commercially available polytetrafluoroethylene (PTFE) useable in the present invention include Zonyl® MP 1200, available commercially from DuPont
• the PTFE may be essentially non-agglomerated, as is the Zonyl® MP 1200 or may be agglomerated, as is the DongYue DF16A.
• One particularly preferred fluoropolymer is Zonyl® MP 1200, available commercially from DuPont (Wilmington, DE).
• the particulate fluoropolymer has particles having a particle size in the range of about 1.0 to about 15 micron with an average particle in the 3 to 5 micron range.
• the fluoropolymer When the fluoropolymer is agglomerated, there are more than about 50% of particles are packed together to form particle agglomerations having a particle agglomeration size in the 10-50 micron range.
• Analysis of the DongYue DF 16A found the particles are particles having a size between about 1 micron and 15 microns and particle agglomerations in the range of about 10-40 microns in size.
• the essentially non-agglomerated Zonyl® MP 1200 contained mostly loose particles having a particle size in the range of about 1-10 microns, and very few agglomerations in the range of 10-15 microns in size.
• Additional ingredients may also be included in the composition of the invention.
• additional water-treatment chemicals such as aluminum sulfate salt, copper sulfate salt, zinc oxide, and zinc sulfate salt may be added to the composition individually or in any combination.
• Further additional water treatment chemicals include sequestering agents such as citric acid, sodium hexametaphosphate, and the like, phosphate reducers, polymeric clarifiers, dichlor, cyanuric acid, and the like.
• the composition of the invention may also be included in the composition of the invention.
• additional water-treatment chemicals such as aluminum sulfate salt, copper sulfate salt, zinc oxide, and zinc sulfate salt may be added to the composition individually or in any combination.
• Further additional water treatment chemicals include sequestering agents such as citric acid, sodium hexametaphosphate, and the like, phosphate reducers, polymeric clarifiers, dichlor, cyanuric acid, and the like.
• composition of the invention includes 1 - 10 wt.% of aluminum sulfate, and more typically 0.2 - 4 wt.%) of aluminum sulfate, based on the total weight of the composition.
• the composition of the invention may include 0.5 - 15 wt.%, and more typically 1 - 4 wt.% of copper sulfate, zinc sulfate, or a combination thereof, based on the total weight of the composition.
• the composition of the invention may also include up to about 3 wt.% of cyanuric acid, based on the total weight of the composition.
• the components of the composition can be dry blended or spray coated and compacted into a unitary structure of a desired shape and/or size.
• Exemplary shapes include, for example, a stick, a tablet, a pellet, a briquette, a brick and the like.
• the size of the unitary structure is generally selected for the preferred end use. For example, if the unitary structure is intended to be used in a pool skimmer, the size and the shape should be such that it easily fits in a typical pool skimmer. Alternatively if the unitary structure is to be placed in an inline or off-line erosion feeder, or other structure such as a floater, again the size and shape for the unitary structure should be appropriate for its end use.
• the unitary structure can generally weigh up to 300 grams or more, again depending on its intended end use. Generally, the unitary structure of the composition will be around 200-250 grams.
• the fluoropolymer may also provide and advantage in forming the unitary structure from the composition.
• the fluoropolymer may alleviate the need or a mold release, such as boric acid, from being compounded with the composition of the present invention. That is, the fluoropolymer may provide mold release properties to the unitary structure.
• a mold release agent may additionally be added to the composition to aid in the release of the unitary structure from the mold used to shape and form the composition into a unitary structure.
• Boric acid is generally used as the mold release agent, and is it typically added in an amount up to 5% by weight. Typically boric acid will be added in an amount around 0.25% to 0.75% by weight.
• the components of the composition are blended together using known techniques, such as a paddle blender and the like, to form an essentially homogenous mixture. Once the components are mixed, a portion of the components are placed in a die and compressed with sufficient pressure such that the mixture of components of the composition are brought together and form a unitary structure.
• Sample A Each of the samples, except Sample A, were blended by adding the components in the amounts listed to a HDPE bottle and inverting and rolling for a minimum of 60 seconds (sec) to produce 30 g compositions. Once blended, mixed components were poured into a die, the punch was added and a stick was pressed. Samples B, E and F each contain 2 wt.%. PTFE and Samples C and G contain 1.75 wt.% PTFE. Samples A and D do not contain PTFE and are Comparative Examples. Once the compositions were pressed the weight, length, and diameter were measured. Density of each stick was required to be within +/- 0.2 of 1.75 grams per centimeter (g/cm ).
• Trichlor tablets were prepared using PTFE (Teflon) and cyanuric acid (CYA) to slow the dissolution rate. Components were weighed out, in the amounts shown in Table 2.
• each composition shown in Table 2 is blended to make 30 g blended compositions as described in Example 1 , and pressed into sticks, as described in Example 1. After initial weights and wet weights were taken, the dissolution rate of the sticks was determined using the same tank set up as in Example 1. The weights of the sticks were recorded prior to starting the filter and after the filter was turned off, giving overall, static, and dynamic dissolution rates. Different levels of PTFE and cyanuric acid were blended with one another and tested for dissolution rate. The dissolution rates are shown in Figures 4, 5, and 6. Figure 4 shows the average dissolution rate per day for each stick, and Figures 5 and 6 show the static and dynamic dissolution rates.
• compositions were tested for static, dynamic, and overall dissolution rates.
• the tested formulations include the following compositions:
• Sample Q is prepared from a blend 98.0 wt.% TCCA and 2 wt.% PTFE;
• Sample R is prepared from a blend 98.25 wt.% TCCA + 1.75 wt.% PTFE;
• Sample S is prepared from a blend containing 98.5 wt.% TCCA + 1.5 wt.% PTFE;
• Sample T which is Silk Smart Sticks® from BioGuard® (TCCA and glycoluril as described in U.S. Patents 5,888,939 and 5,670,451) (comparative example);
• Sample U is 100 wt.% TCCA (comparative example).
• Each of the Samples Q, R, S and U are made into stick having a weight of about 23 Og each, using the process as described in Example 1.
• Each of the Samples were dissolution tested, where each of the Samples were tested in different pools in order to minimize the influence the pool may have on dissolution rates and to give more representative numbers.
• Heaters were set to 85° +/- 5°C. The number of replicates, average temperatures and flow rates for each stick are listed in Table 3.
• Figure 7 shows a comparison of each of the formulations static dissolution rates over 10 days (1.75 wt.% PTFE has data for up to 14 days since more sticks were tested).
• Figure 7 illustrates that addition of PTFE slows the static dissolution of 100 wt.% trichlor.
• Figure 7 also illustrates that static dissolution rates of the sticks containing PTFE are very similar to the static dissolution rate of the BioGuard® Silk Smart Sticks®; based on the slopes of each line.
• Figure 9 shows a comparison of the overall dissolution rates of Samples R, T and U. This comparison shows that the addition of PTFE slows the overall dissolution of the trichlor to a level that is near that of the Silk Smart Sticks®.
• compositions were tested for time for a stick to dissolve in a pool skimmer.
• the tested formulations include the following compositions:
• Sample V is prepared from a blend 99.0 wt.% TCCA and 1 wt.% PTFE DF16A available from DongYue;
• Sample W is prepared from a blend 98.75 wt.% TCCA + 1.25 wt.% PTFE DF16A available from DongYue;
• Sample X is prepared from a blend containing 100 wt.% TCCA (comparative example).
• Each of the Samples V, W, and X are made into stick having a weight of about 230g each, using the process as described in Example 1.
• Each of the Samples were dissolution tested, where each of the Samples were tested in different pools in order to minimize the influence the pool may have on dissolution rates and to give more representative numbers.
• the process of example 3 was repeated to obtain 8 hour pump time run and 16 hours of static dissolution and the process of example 4 was repeated to obtain 24 hour pump run data to determine the time needed to dissolve the sticks. 23 tablets for each sample were tested and the average number of days for the sticks to dissolve are shown in Table 5.

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• 2012
  • 2012-09-20 US US13/623,626 patent/US20130178474A1/en not_active Abandoned
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