USRE29473E - Chemical composition - Google Patents
Chemical composition Download PDFInfo
- Publication number
- USRE29473E USRE29473E US05/744,113 US74411376A USRE29473E US RE29473 E USRE29473 E US RE29473E US 74411376 A US74411376 A US 74411376A US RE29473 E USRE29473 E US RE29473E
- Authority
- US
- United States
- Prior art keywords
- pyrosulfate
- hypochlorite
- chemical composition
- component
- alkaline earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000000126 substance Substances 0.000 title claims abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- -1 alkaline earth metal hypochlorites Chemical class 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims 1
- 238000009877 rendering Methods 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000012744 reinforcing agent Substances 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000000153 supplemental effect Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- JSGPSIIARHYDHW-UHFFFAOYSA-L calcium;sulfonato sulfate Chemical compound [Ca+2].[O-]S(=O)(=O)OS([O-])(=O)=O JSGPSIIARHYDHW-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- SNNVSEONCOCCRZ-UHFFFAOYSA-N C1CC=CCCC=C1[Ni]C1=CCCC=CCC1 Chemical compound C1CC=CCCC=C1[Ni]C1=CCCC=CCC1 SNNVSEONCOCCRZ-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- ABONIXOLZDCGIG-UHFFFAOYSA-N calcium;dihypochlorite;dihydrate Chemical compound O.O.[Ca+2].Cl[O-].Cl[O-] ABONIXOLZDCGIG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- NDPMPJMMNVDDLJ-UHFFFAOYSA-L dilithium sulfonato sulfate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)OS([O-])(=O)=O NDPMPJMMNVDDLJ-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012628 flowing agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3953—Inorganic bleaching agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
Definitions
- compositions well suited as a cleaning agent for example, as a dental prostheses cleaner.
- This composition comprising the combination of lithium hypochlorite, an alkali metal pyrosulfate, alkali metal bisulfate and/or mixtures thereof, preferably potassium pyrosulfate, and an alkali metal hydroxide was found to be highly effective as a cleaner because, particularly in its preferred embodiments, it combined the features of solid chemicals highly stable in admixture with outstanding and long-term cleaning ability for plastics, metals, porcelains, glass and the like.
- the present invention relates to the combination of alkali and/or alkaline earth metal hypochlorites, which are alone strong oxidizing agents, with alkali and/or alkaline earth metal pyrosulfates, which appear to act as a stabilizer and/or reinforcing agent for the hypochlorite, alone or in combination with supplemental agents such as surface active agents, pH adjusting agents and the like.
- the pyrosulfate and hypochlorite are admixed in widely varying proportions depending upon the ultimate end use desired. These proportions can range broadly from about 1 to 99 parts by weight of pyrosulfate to 99 to 1 parts by weight hypochlorite.
- alkali metal and alkaline earth metal as used herein are meant in their normal sense to include such metals as sodium, potassium, lithium, magnesium, calcium and barium. As might be expected by the chemical relationship of these metals, mixtures of two or more hypochlorites and pyrosulfates are equally possible.
- pyrosulfates of such metals are commercially available, such as potassium pyrosulfate, also known as fused potassium bisulfate. Normally this product as obtained commercially is made up of a mixture of pyrosulfate and bisulfate, the latter being the accidental hydrolysis product of the pyrosulfate since the former is obtained by driving off water from the bisulfate usually by the application of heat.
- pyrosulfate as employed herein is intended to mean the grades and purities of pyrosulfate commercially available although, in general, an assay of at least 40 percent pyrosulfate is advisable to obtain the full benefits of the invention.
- Lithium pyrosulfate can be prepared for example by the manner described by Arnold and Lehmann, Z. Anorg. Allg. Chem., 354, 56-59 (1967); Chem. Abs. 67, 104662 (1967).
- Potassium pyrosulfate can be prepared by numerous chemical methods such as described in Chem. Abs. 47, 9840 (1953); 57, 16005 (1962) and 58, 12158 (1963).
- the production of sodium pyrosulfate is described at Chem. Abs., 69, 102597 (1968) and of calcium pyrosulfate at Chem. Abs., 68, 45844 (1968).
- the pyrosulfate regardless of the specific metal, is characterized by the - S 2 O 7 ion and has the general formula M x S 2 O 7 wherein M stands for the particular metal and x stands for one or two, depending on the valency of the metal.
- the metal hypochloride is, per se, a well-known compound whose methods of manufacture were well established many years ago, such as by electrolysis of a sodium chloride solution or chlorination of a slurry of .[.line.]. .Iadd.lime .Iaddend.and caustic soda with subsequent precipitation of calcium hypochlorite dihydrate which is then dried under vacuum. Since those methods are well known in the literature, they will not be repeated here. It may be solid (such as lithium and calcium hypochlorite) or liquid (such as sodium hypochlorite which is unstable in air and is normally stored and used in solution with sodium hydroxide as a stabilizer).
- the pyrosulfate As with the pyrosulfate, it may be employed in its commercially available grades such as technical, analytical or reagent. Because of differing physical characteristics as between the metal hypochlorites, selection depends primarily on cost, intended use, stability and the liquid or solid nature desired of the ultimate product.
- hypochlorite itself a strong oxidizing agent
- the hypochlorite may be stabilized by the action of the pyrosulfate.
- the release of active oxidizing agent from the hypochlorite appears to be attenuated by the pyrosulfate to preserve and/or obtain slow release of the oxidizing power of the hypochlorite.
- This factor can be advantageously utilized to either prolong the activity of the hypochlorite in aqueous solutions or to prevent loss in potency during storing of the dry hypochlorite, that is, increase its storage stability.
- the pyrosulfate e.g., potassium pyrosulfate
- hypochlorite e.g., lithium hypochlorite
- the reaction product itself may be a new product.
- Supplemental ingredients include thickening agents, inert or even active supports (as in the case of catalysts), surface active agents (as in the case of cleaning uses), indicators, chelating agents, dyes, free-flowing agents, masking agents, perfumes, fragrances, bonding agents (as in shaping tablets) and the like.
- the product in its commercial state, may partake of liquid, powder, pellet, bread, wafer or other physical form suitable for the particular end use desired.
- agents to provide varying pH are sometimes desired.
- Such agents include alkali and alkaline earth metal hydroxides such as lithium and sodium hydroxide which can be employed to raise the pH of an aqueous solution containing the chemicals to the alkaline side, say in excess of 8, generally 9 to 14 and preferably from 10 to 12.
- the relative amounts of pyrosulfate and hypochlorite can vary widely depending on the end use intended. Broadly speaking this may vary from about 1 to 99 parts by weight hypochlorite for 99 to 1 parts by weight pyrosulfate. In cleaning applications, particularly with an alkaline pH, the proportions may vary on a weight ratio of from about 1:3.5 to 3.5:1 preferably on an equal weight basis. For other applications such as in stabilizing bulk hypochlorite used on an industrial scale or in the disinfecting and purification of water (e.g., in swimming pools where it also acts to kill algae) relatively small amounts of pyrosulfate based on hypochlorite may be employed (for illustration purposes from 0.25 to 5 percent by weight, preferably 0.5 to 2.5 percent.
- composition according to the present invention should find utility in a number of potential areas. These include as an initiator of vinyl polymerization, oxidative treatment of polyethylene film surfaces to render same printable, bactericide and algaecide in water treatment and general bleaching of paper, fabric, wood and the like.
- mixtures of metal pyrosulfate and metal hypochlorite alone or with co-catalysts, with or without suitable supports may be used in various fields such as replacing the pyrosulfate employed in admixture with bis(1,5-cyclo-octadienyl) nickel to prepare poly(butadiene) rubber with essentially cis structure as disclosed, for example, by Dawans and Teyssie, C.R. Acad. Sci., Paris, Ser. C-263 (25), 1512 (1966) (cf. Chem. Abs., 66 47063 (1967).
- a mixture consisting of 5.0 grams of potassium pyrosulfate, 5.0 grams of lithium hypochlorite, 2.0 grams of lithium hydroxide, and 1.0 gram of Duponol C (E. I. du Pont de Nemours' brand of sodium lauryl sulfate) was prepared by grinding the ingredients separately to remove lumps or large particles and mixing the resulting dry powders. The resulting mixture was a white, free-flowing powder and was packaged in various dosages for further use.
- Duponol C E. I. du Pont de Nemours' brand of sodium lauryl sulfate
- a mixture is prepared by grinding together with a mortar and pestle 5.0 grams potassium pyrosulfate, 3.0 grams lithium hypochlorite, 2.0 grams lithium chloride, 2.0 grams lithium hydroxide and 1.0 grams sodium lauryl sulfate.
- the article to be cleaned in this case a denture, is covered with about 100 ml of hot tap water (70° C.). To this is added 10 grams of the above mixture with sufficient agitation to promote dissolution.
- compositions When the above compositions are dissolved in 100 ml of water in an amount ranging from 1 to 15 grams per 100 ml, they effectively clean a variety of dentures in a short period of time without adverse effect on the denture material.
- the potassium pyrosulfate can be replaced by equivalent amounts of other pyrosulfates such as sodium, lithium and/or calcium pyrosulfate and the lithium hypochlorite can be replaced by equivalent amounts of calcium and/or sodium hypochlorite, the resulting compositions varying in physical form depending upon the liquid and solid form of the base chemicals.
- the metal pyrosulfate can be added in relatively minor amounts say from 0.5 to 50 percent by weight based on metal hypochlorite and, as illustration, in 0.5, 2.5, 5 and 10 percent by weight.
- the metal pyrosulfate should serve to preserve the activity of the metal hypochlorite during storage and after addition to aqueous liquids.
- Such admixtures, with or without the usual supplemental agents commonly used in industrial or household applications find many applications wherein prolonged stability and activity are desired.
- alkaline stable agents such as sulfates of long chain alcohols such as dodecanol up to octadecanol (e.g., sodium lauryl sulfate), sulfonated amide and ester derivatives, and alkyl aryl sulfonates (e.g., dodecyl benzene sodium sulfonate) may be used.
- dodecanol up to octadecanol e.g., sodium lauryl sulfate
- alkyl aryl sulfonates e.g., dodecyl benzene sodium sulfonate
- Both cationic and anionic agents come under consideration in the alkaline field.
- non-ionic agents if sufficiently stable may be employed.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A chemical composition comprising a mixture of alkali and/or alkaline earth metal hypochlorites and, as a stabilizing and/or reinforcing agent, alkali and/or alkaline earth metal pyrosulfates.
Description
This application is a continuation-in-part of application Ser. No. 828,710 filed May 28, 1969, now U.S. Pat. No. 3,640,879 issued Feb. 8, 1972 which in turn is a continuation-in-part of application Ser. No. 791,512, filed Jan. 15, 1969, now abandoned.
In the aforementioned applications I disclosed and claimed a chemical composition well suited as a cleaning agent, for example, as a dental prostheses cleaner. This composition, comprising the combination of lithium hypochlorite, an alkali metal pyrosulfate, alkali metal bisulfate and/or mixtures thereof, preferably potassium pyrosulfate, and an alkali metal hydroxide was found to be highly effective as a cleaner because, particularly in its preferred embodiments, it combined the features of solid chemicals highly stable in admixture with outstanding and long-term cleaning ability for plastics, metals, porcelains, glass and the like.
The present invention relates to the combination of alkali and/or alkaline earth metal hypochlorites, which are alone strong oxidizing agents, with alkali and/or alkaline earth metal pyrosulfates, which appear to act as a stabilizer and/or reinforcing agent for the hypochlorite, alone or in combination with supplemental agents such as surface active agents, pH adjusting agents and the like. The pyrosulfate and hypochlorite are admixed in widely varying proportions depending upon the ultimate end use desired. These proportions can range broadly from about 1 to 99 parts by weight of pyrosulfate to 99 to 1 parts by weight hypochlorite.
The terms alkali metal and alkaline earth metal as used herein are meant in their normal sense to include such metals as sodium, potassium, lithium, magnesium, calcium and barium. As might be expected by the chemical relationship of these metals, mixtures of two or more hypochlorites and pyrosulfates are equally possible.
Some pyrosulfates of such metals are commercially available, such as potassium pyrosulfate, also known as fused potassium bisulfate. Normally this product as obtained commercially is made up of a mixture of pyrosulfate and bisulfate, the latter being the accidental hydrolysis product of the pyrosulfate since the former is obtained by driving off water from the bisulfate usually by the application of heat. The term "pyrosulfate" as employed herein is intended to mean the grades and purities of pyrosulfate commercially available although, in general, an assay of at least 40 percent pyrosulfate is advisable to obtain the full benefits of the invention.
Methods of producing the metal pyrosulfates are well known and for a particular metal can follow the analogous procedure for preparing potassium pyrosulfate. Lithium pyrosulfate can be prepared for example by the manner described by Arnold and Lehmann, Z. Anorg. Allg. Chem., 354, 56-59 (1967); Chem. Abs. 67, 104662 (1967). Potassium pyrosulfate can be prepared by numerous chemical methods such as described in Chem. Abs. 47, 9840 (1953); 57, 16005 (1962) and 58, 12158 (1963). The production of sodium pyrosulfate is described at Chem. Abs., 69, 102597 (1968) and of calcium pyrosulfate at Chem. Abs., 68, 45844 (1968).
The pyrosulfate, regardless of the specific metal, is characterized by the - S2 O7 ion and has the general formula Mx S2 O7 wherein M stands for the particular metal and x stands for one or two, depending on the valency of the metal.
The metal hypochloride is, per se, a well-known compound whose methods of manufacture were well established many years ago, such as by electrolysis of a sodium chloride solution or chlorination of a slurry of .[.line.]. .Iadd.lime .Iaddend.and caustic soda with subsequent precipitation of calcium hypochlorite dihydrate which is then dried under vacuum. Since those methods are well known in the literature, they will not be repeated here. It may be solid (such as lithium and calcium hypochlorite) or liquid (such as sodium hypochlorite which is unstable in air and is normally stored and used in solution with sodium hydroxide as a stabilizer). As with the pyrosulfate, it may be employed in its commercially available grades such as technical, analytical or reagent. Because of differing physical characteristics as between the metal hypochlorites, selection depends primarily on cost, intended use, stability and the liquid or solid nature desired of the ultimate product.
While I do not wish to be bound by any theory underlying the action of this unique chemical combination, it appears that the hypochlorite, itself a strong oxidizing agent, may be stabilized by the action of the pyrosulfate. Particularly in the presence of water, either as a solution or ambient moisture picked up by the chemicals from the air, the release of active oxidizing agent from the hypochlorite appears to be attenuated by the pyrosulfate to preserve and/or obtain slow release of the oxidizing power of the hypochlorite. This factor can be advantageously utilized to either prolong the activity of the hypochlorite in aqueous solutions or to prevent loss in potency during storing of the dry hypochlorite, that is, increase its storage stability.
Alternatively, the pyrosulfate (e.g., potassium pyrosulfate) and hypochlorite (e.g., lithium hypochlorite) may undergo, particularly in the presence of water at ambient temperatures, the following reaction:
.sup.- SO.sub.3 --O--SO.sub.3.sup.- + .sup.- OCl → SO.sub.3 = + .sup.- SO.sub.3 --O--Cl
The reaction product itself may be a new product.
Regardless of the precise mechanism involved, the mixture of the two ingredients, alone or in combination with supplemental ingredients, later defined, provides a novel combination with many advantageous properties.
Supplemental ingredients include thickening agents, inert or even active supports (as in the case of catalysts), surface active agents (as in the case of cleaning uses), indicators, chelating agents, dyes, free-flowing agents, masking agents, perfumes, fragrances, bonding agents (as in shaping tablets) and the like. The product, in its commercial state, may partake of liquid, powder, pellet, bread, wafer or other physical form suitable for the particular end use desired. Moreover, agents to provide varying pH are sometimes desired. Such agents include alkali and alkaline earth metal hydroxides such as lithium and sodium hydroxide which can be employed to raise the pH of an aqueous solution containing the chemicals to the alkaline side, say in excess of 8, generally 9 to 14 and preferably from 10 to 12.
Supplemental agents, their nature and use are more fully described in my aforesaid-mentioned applications when the combination is intended for cleaning purposes, the disclosures of which are incorporated herein by reference.
The relative amounts of pyrosulfate and hypochlorite can vary widely depending on the end use intended. Broadly speaking this may vary from about 1 to 99 parts by weight hypochlorite for 99 to 1 parts by weight pyrosulfate. In cleaning applications, particularly with an alkaline pH, the proportions may vary on a weight ratio of from about 1:3.5 to 3.5:1 preferably on an equal weight basis. For other applications such as in stabilizing bulk hypochlorite used on an industrial scale or in the disinfecting and purification of water (e.g., in swimming pools where it also acts to kill algae) relatively small amounts of pyrosulfate based on hypochlorite may be employed (for illustration purposes from 0.25 to 5 percent by weight, preferably 0.5 to 2.5 percent.
The composition according to the present invention should find utility in a number of potential areas. These include as an initiator of vinyl polymerization, oxidative treatment of polyethylene film surfaces to render same printable, bactericide and algaecide in water treatment and general bleaching of paper, fabric, wood and the like.
In the catalytic field, mixtures of metal pyrosulfate and metal hypochlorite alone or with co-catalysts, with or without suitable supports, may be used in various fields such as replacing the pyrosulfate employed in admixture with bis(1,5-cyclo-octadienyl) nickel to prepare poly(butadiene) rubber with essentially cis structure as disclosed, for example, by Dawans and Teyssie, C.R. Acad. Sci., Paris, Ser. C-263 (25), 1512 (1966) (cf. Chem. Abs., 66 47063 (1967). Other catalytic uses for the mixture according to the claimed invention may be obtained by replacement of pyrosulfate in various processes such as those disclosed in French Pat. No. 1,447,472, July 29, 1966 (Chem. Abs. 66 P 66051 (1967); Netherlands application 6,406,764 (Chem. Abs. 64 PC 17432 (1966); Chem. Abs., 68, 117462 (1963); Chem. Abs. 69, 70633 (1968); Chem. Abs., 65, P 20068 (1966); Chem. Abs., 55, 18033 (1961) and Chem. Abs. 64, 6488 (1966), all of which references are incorporated herein by reference.
The following examples serve to further illustrate the nature of the invention and are not intended to impliedly or expressly restrict the nature thereof.
A mixture consisting of 5.0 grams of potassium pyrosulfate, 5.0 grams of lithium hypochlorite, 2.0 grams of lithium hydroxide, and 1.0 gram of Duponol C (E. I. du Pont de Nemours' brand of sodium lauryl sulfate) was prepared by grinding the ingredients separately to remove lumps or large particles and mixing the resulting dry powders. The resulting mixture was a white, free-flowing powder and was packaged in various dosages for further use.
An 8.0 gram quantity of the mixture described above was disclosed in 100 milliliters of hot water (approximately 140° F. tap water). With slight swirling of the mixture, solution was rapid and complete, giving a pH of 11. A solid denture (complete upper or lower plate) was immersed in the solution for 15 minutes. Upon removal and rinsing with water, all tar and nicotine stains had been removed together with the calculus, food debris, and other solid materials. The porecelain, acrylic, and metal portions of the denture were bright and shining and resembled those of a freshly manufactured, unused denture.
A mixture is prepared by grinding together with a mortar and pestle 5.0 grams potassium pyrosulfate, 3.0 grams lithium hypochlorite, 2.0 grams lithium chloride, 2.0 grams lithium hydroxide and 1.0 grams sodium lauryl sulfate. The article to be cleaned, in this case a denture, is covered with about 100 ml of hot tap water (70° C.). To this is added 10 grams of the above mixture with sufficient agitation to promote dissolution.
Soaking is accomplished for 30 minutes and the denture is then removed, rinsed with warm water and dried. The denture is restored to a clean, lustrous, tasteless condition.
In a manner similar to Example 1, the following dry formulations are prepared:
______________________________________
Ingredients, percent by
Example
weight 3 4 5 6 7 8 9
______________________________________
Potassium pyrosulfate
40 45 42 30 38 25 30
Lithium hypochlorite
40 35 33 44 25 55 20
Lithium chloride
-- -- -- 15 -- 5 20
Lithium hydroxide
14 7 17 -- 25 10 20
Surface active agent
.sup.1 6
.sup.2 6
.sup.1 8
.sup.2 2
.sup.2 12
.sup.1 5
.sup.1 10
Sodium hydroxide
-- 7 -- 9 -- -- --
______________________________________
.sup.1 Sodium lauryl sulfate.
.sup.2 Sodium dodecyl benzene sulfonate.
When the above compositions are dissolved in 100 ml of water in an amount ranging from 1 to 15 grams per 100 ml, they effectively clean a variety of dentures in a short period of time without adverse effect on the denture material.
A mixture consisting of 4.0 grams of potassium pyrosulfate, 5.5 grams of lithium hypochlorite, 2 grams of lithium hydroxide and 2 grams of sodium lauryl sulfate is ground together and the resulting dry composition is added in an amount of 5 grams to 100 milliliters of tap water (room temperature).
Various articles such as small gold jewelry pieces, a heating aid ear piece and a denture when immersed in the resulting solution are cleaned and restored to a bright and shining appearance after from 25 to 60 minutes of soaking.
In the above formulations, the potassium pyrosulfate can be replaced by equivalent amounts of other pyrosulfates such as sodium, lithium and/or calcium pyrosulfate and the lithium hypochlorite can be replaced by equivalent amounts of calcium and/or sodium hypochlorite, the resulting compositions varying in physical form depending upon the liquid and solid form of the base chemicals.
In other applications, such as the use of metal hypochlorite in bulk form for industrial (e.g., bleaching) and sterilization purposes, the metal pyrosulfate can be added in relatively minor amounts say from 0.5 to 50 percent by weight based on metal hypochlorite and, as illustration, in 0.5, 2.5, 5 and 10 percent by weight. In such instances, the metal pyrosulfate should serve to preserve the activity of the metal hypochlorite during storage and after addition to aqueous liquids. Such admixtures, with or without the usual supplemental agents commonly used in industrial or household applications (e.g., common household bleaching and washing applications) find many applications wherein prolonged stability and activity are desired.
In the above-mentioned uses it is sometimes advisable to incorporate surface active agents which may vary widely depending upon the use, acidity and alkalinity of the ultimate product. When employed as an alkaline cleaning agent, alkaline stable agents such as sulfates of long chain alcohols such as dodecanol up to octadecanol (e.g., sodium lauryl sulfate), sulfonated amide and ester derivatives, and alkyl aryl sulfonates (e.g., dodecyl benzene sodium sulfonate) may be used. Both cationic and anionic agents come under consideration in the alkaline field. Of course, non-ionic agents, if sufficiently stable may be employed.
Claims (4)
1. A chemical composition consisting essentially of a mixture of (a) a member selected from the group consisting of an alkali metal pyrosulfate, an alkaline earth metal pyrosulfate or mixtures thereof.Iadd., .Iaddend..[.and.]. (b) a member selected from the group consisting of an alkali metal hypochlorite, an alkaline earth metal hypochlorite or mixtures thereof .Iadd.and (c) an agent rendering the pH of the chemical composition alkaline.Iaddend., component (a) being present in from about 1 to about 99 parts by weight.Iadd., .Iaddend..[.and.]. component (b) being present in from about 99 to 1 parts by weight.Iadd., and component (c) being present in an amount sufficient to render the pH of the composition in excess of 8.Iaddend..
2. The chemical composition according to claim 1 wherein component (b) is an alkali or alkaline earth metal hypochlorite and component (a) is present in an amount of from about 0.5 to 50 percent by weight.
3. The chemical composition according to claim 1 wherein component (b) is an alkali or alkaline earth metal hypochlorite.
4. An aqueous medium containing the composition according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/744,113 USRE29473E (en) | 1969-01-15 | 1976-11-22 | Chemical composition |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79151269A | 1969-01-15 | 1969-01-15 | |
| US97151269A | 1969-01-15 | 1969-01-15 | |
| US82871069A | 1969-05-28 | 1969-05-28 | |
| US12032771A | 1971-03-02 | 1971-03-02 | |
| US05/744,113 USRE29473E (en) | 1969-01-15 | 1976-11-22 | Chemical composition |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US82871069A Continuation-In-Part | 1969-01-15 | 1969-05-28 | |
| US12032771A Reissue | 1969-01-15 | 1971-03-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE29473E true USRE29473E (en) | 1977-11-15 |
Family
ID=27537573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/744,113 Expired - Lifetime USRE29473E (en) | 1969-01-15 | 1976-11-22 | Chemical composition |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE29473E (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367155A (en) | 1981-05-07 | 1983-01-04 | Coustic-Glo International, Inc. | Low-residue brightening compositions and methods for using them |
| US4431559A (en) | 1981-10-06 | 1984-02-14 | Texize, Division Of Mortonthiokol | Dishwashing composition and method |
| US4780216A (en) | 1986-11-19 | 1988-10-25 | Olin Corporation | Calcium hypochlorite sanitizing compositions |
| WO1997023681A1 (en) * | 1995-12-22 | 1997-07-03 | The Procter & Gamble Company | Hypochlorite bleaching compositions |
| US6042817A (en) | 1997-12-11 | 2000-03-28 | Polunsky; Melvin S. | Polyurethane foam lithium hypochlorite composition |
| US6207201B1 (en) * | 1993-06-03 | 2001-03-27 | Amuchina International, Inc. | Sodium hypochlorite based disinfectant and sterilizer for medical-surgical instruments |
| US20060040843A1 (en) * | 2004-08-19 | 2006-02-23 | Kinnaird Michael G | Sodium-free, lithium-containing concrete cleaning compositions and method for use thereof |
| US20080234145A1 (en) * | 2004-07-15 | 2008-09-25 | Heinz Mueller | Use of Lithium Salts of Fatty Alcohol Sulphates for Cleaning Boreholes, Boring Devices and Borings |
| US20100140544A1 (en) * | 2008-12-09 | 2010-06-10 | Smith William L | Solid-Layered Bleach Compositions |
| US20110027194A1 (en) * | 2008-12-09 | 2011-02-03 | The Clorox Company | Hypochlorite denture compositions and methods of use |
| US20110052726A1 (en) * | 2008-12-09 | 2011-03-03 | The Clorox Company | Solid-layered bleach compositions and methods of use |
| US20110059882A1 (en) * | 2008-12-09 | 2011-03-10 | The Clorox Company | Solid-layered bleach compositions and methods of use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3171814A (en) * | 1962-02-20 | 1965-03-02 | Lithium Corp | Preparation of dry lithium hypochlorite compositions |
| US3257450A (en) * | 1963-02-28 | 1966-06-21 | Guardian Chemical Corp | Organic hypochlorous acid derivatives and a process for their manufacture |
| US3491028A (en) * | 1969-06-03 | 1970-01-20 | Grace W R & Co | Chlorine stable machine dishwashing composition |
-
1976
- 1976-11-22 US US05/744,113 patent/USRE29473E/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3171814A (en) * | 1962-02-20 | 1965-03-02 | Lithium Corp | Preparation of dry lithium hypochlorite compositions |
| US3257450A (en) * | 1963-02-28 | 1966-06-21 | Guardian Chemical Corp | Organic hypochlorous acid derivatives and a process for their manufacture |
| US3491028A (en) * | 1969-06-03 | 1970-01-20 | Grace W R & Co | Chlorine stable machine dishwashing composition |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367155A (en) | 1981-05-07 | 1983-01-04 | Coustic-Glo International, Inc. | Low-residue brightening compositions and methods for using them |
| US4431559A (en) | 1981-10-06 | 1984-02-14 | Texize, Division Of Mortonthiokol | Dishwashing composition and method |
| US4780216A (en) | 1986-11-19 | 1988-10-25 | Olin Corporation | Calcium hypochlorite sanitizing compositions |
| US6207201B1 (en) * | 1993-06-03 | 2001-03-27 | Amuchina International, Inc. | Sodium hypochlorite based disinfectant and sterilizer for medical-surgical instruments |
| WO1997023681A1 (en) * | 1995-12-22 | 1997-07-03 | The Procter & Gamble Company | Hypochlorite bleaching compositions |
| US6042817A (en) | 1997-12-11 | 2000-03-28 | Polunsky; Melvin S. | Polyurethane foam lithium hypochlorite composition |
| US20080234145A1 (en) * | 2004-07-15 | 2008-09-25 | Heinz Mueller | Use of Lithium Salts of Fatty Alcohol Sulphates for Cleaning Boreholes, Boring Devices and Borings |
| US7959743B2 (en) * | 2004-07-15 | 2011-06-14 | Cognis Oleochemicals Gmbh | Lithium salts of fatty alcohol sulphates for cleaning boreholes, boring devices and borings |
| US20060040843A1 (en) * | 2004-08-19 | 2006-02-23 | Kinnaird Michael G | Sodium-free, lithium-containing concrete cleaning compositions and method for use thereof |
| US20080127995A1 (en) * | 2004-08-19 | 2008-06-05 | Chemtek, Inc. | Sodium-free, lithium-containing concrete cleaning compositions and method for use thereof |
| US7828902B2 (en) | 2004-08-19 | 2010-11-09 | Chemtek, Inc. | Sodium-free, lithium-containing concrete cleaning compositions and method for use thereof |
| US20110028368A1 (en) * | 2008-12-09 | 2011-02-03 | The Clorox Company | Hypochlorite denture compositions and methods of use |
| US20110027194A1 (en) * | 2008-12-09 | 2011-02-03 | The Clorox Company | Hypochlorite denture compositions and methods of use |
| US20110052726A1 (en) * | 2008-12-09 | 2011-03-03 | The Clorox Company | Solid-layered bleach compositions and methods of use |
| US20110059882A1 (en) * | 2008-12-09 | 2011-03-10 | The Clorox Company | Solid-layered bleach compositions and methods of use |
| US20100140544A1 (en) * | 2008-12-09 | 2010-06-10 | Smith William L | Solid-Layered Bleach Compositions |
| US8287755B2 (en) | 2008-12-09 | 2012-10-16 | The Clorox Company | Solid-layered bleach compositions |
| US8361945B2 (en) | 2008-12-09 | 2013-01-29 | The Clorox Company | Solid-layered bleach compositions and methods of use |
| US8361944B2 (en) | 2008-12-09 | 2013-01-29 | The Clorox Company | Solid-layered bleach compositions and methods of use |
| US8361943B2 (en) | 2008-12-09 | 2013-01-29 | The Clorox Company | Hypochlorite denture compositions and methods of use |
| US8361942B2 (en) | 2008-12-09 | 2013-01-29 | The Clorox Company | Hypochlorite denture compositions and methods of use |
| US8475678B2 (en) | 2008-12-09 | 2013-07-02 | The Clorox Company | Method of using solid-layered bleach compositions |
| US8481471B2 (en) | 2008-12-09 | 2013-07-09 | The Clorox Company | Method of using solid-layered bleach compositions |
| US8486879B2 (en) | 2008-12-09 | 2013-07-16 | The Clorox Company | Hypochlorite denture compositions and methods of use |
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