WO1991007184A1 - SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP and H2O¿2? - Google Patents
SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP and H2O¿2? Download PDFInfo
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- WO1991007184A1 WO1991007184A1 PCT/US1990/005846 US9005846W WO9107184A1 WO 1991007184 A1 WO1991007184 A1 WO 1991007184A1 US 9005846 W US9005846 W US 9005846W WO 9107184 A1 WO9107184 A1 WO 9107184A1
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- A61Q17/005—Antimicrobial preparations
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- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
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- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
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- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
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- 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
- C02F1/722—Oxidation by peroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/20—Oxides; Hydroxides
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
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- 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
- C11D3/39—Organic or inorganic per-compounds
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- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/30—Characterized by the absence of a particular group of ingredients
- A61K2800/31—Anhydrous
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Definitions
- anhydrous H 2 0 solution is slowly added to the cooled PVP suspension in an anhydrous solvent in an amount corresponding to the desired molar ratio of PVP and H 2 0 2 .
- a small excess of the H 2 0 2 solution over the desired stoichiometric ratio is used.
- a PVP-H 0 2 complex with a 1:1 molar ratio
- about 111 g. PVP and 100 g. of a 42% H 2 0 2 and 300 ml of anhydrous solvent is used, providing a small excess, e.g. about 5%, over the required stoichiometric amount of 34 g. H 2 0 .
- This excess H 2 0 2 is recoverable from the mother liquor.
- Example 1 The process of Example 1 was followed using 50 g. of the H 2 0 2 solution in anhydrous ethyl acetate.
- the resultant complex contained 13.2% H 2 0 2 and 0.5% water.
- Example 6 The procedure of Example 6 is followed using PVP-CI 160 g.; ethylacetate 450 g.; and 85% H 2 0 2 56 g. 197 g. of a PVP-H 2 0 2 complex with 19.2% H 2 0 2 containing 1.56% H 2 0 is obtained. Further drying at 40-50°C. in vacuo will reduce the water content to 0.5% H 2 0.
Abstract
What is provided herein are substantially anhydrous complexes of PVP and H2O2 in molar ratios of between about 2:1 and 1:1, respectively, which corresponds to between about 13 % and about 23 % by weight H2O2. The complexes of the invention are substantially uniform, free-flowing, fine white powders. The complexes herein are prepared by reacting PVP and H2O2 in substantially the molar ratio predetermined for the complex. In one suitable process for preparing such complexes the reaction is carried out between the reactants in an anhydrous organic solvent such as ethyl acetate. A method is provided herein for reducing the microbial content of surfaces which comprises contacting said surface with a microbiocidal amount of said free-flowing, substantially anhydrous complex of PVP and H2O2.
Description
- 1 -
SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP AND H?Q
This invention relates to substantially anhydrous complexes of polyvinylpyrrolidone (PVP) and hydrogen peroxide (H 02) which are, free-flowing, uniform, fine white powders containing a predetermined amount of H20 therein.
Stabilized H202 compositions have found wide utility in commercial and industrial applications, e.g. as disinfectants, sterilization agents, as bleaching materials, washing concentrates, etchants, in cosmetic preparations, as clarification agents for alcoholic and fermented beverages, and as a catalyst in polymerizations requiring a free radical source. In biological applications which require a disinfectant or sterilization agent, such H20 compositions require release of an effective amount of oxygen at a controlled rate without storage decomposition caused by interaction with organic matter, light and/or heat.
Shiraeff, in U.S. Patents 3,376,110 and 3,480,557, discloses a solid, stabilized hydrogen peroxide composition of hydrogen peroxide and a polymeric N-vinyl heterocyclic compound prepared in an aqueous solution of the components. These compositions generally were prepared by mixing various weights of PVP and aqueous H202, and evaporating the solution to dryness. The Shiraeff composition, which was believed to be a solid, dry complex, was described as not necessarily anhydrous due to the hydrophilic nature of the PVP and the water present in the reaction solution. Shiraeff further stated that such amounts of water could be tolerated, however, if it did not affect the solid dry characteristics of the complexes. The H202 content of the composition was given as being at least 2%, and preferably 4.5 to 70% by weight. Prolonged
drying to remove water from such compositions, however, resulted in loss of H202 forming a brittle, transparent, gummy, amorphous product. In U.S. 3,480,557, the aqueous PVP-H202 complexes, upon heating to dryness, produced hard, brittle chips which had a variable
H202 content ranging from about 3.20 to 18.07% by weight, depending upon the drying times.
In accordance with the invention, substantially anhydrous PVP-H202 complexes are provided having a predetermined molar ratio of PVP to H 02 ranging from between about 2:1 to about 1:1, corresponding to a H202 content of about 13% to about 23%. The substantially anhydrous PVP-H202 complexes are prepared by reaction of PVP and H202 in a substantially anhydrous organic solvent and are obtained by filtration of the suspension as a uniform, free-flowing, fine white powder.
The PVP polymeric starting material used in the present invention is available commercially as a solid of varying molecular weight, water solubility and water content. A typical PVP polymer is water soluble PVP-K30 (GAF Corp.) which contains less than 5% water. Other PVP polymers of different molecular weight, water solubility and water content also may be used, as for example, K-90 and K-120; Polyclar AT; Crospovidone; and the like. Both water soluble and water insoluble PVP polymers may be used.
In this process, the PVP powder is suspended in a suitable anhydrous organic solvent, such as a carboxylie acid ester, an alkyl ether, e.g. t-butyl methyl ether, or a hydrocarbon, e.g. cyclohexane. Preferably, however, an alkyl or cycloalkyl ester of a saturated aliphatic carboxylic acid is used, as for example, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and ethyl propionate. The PVP suspension in ethyl acetate, for example, then is cooled, preferably to about 0°C. , at which temperature precipitation of the desired complex as a fine powder may suitably occur.
An anhydrous H202 solution in an anhydrous organic solvent, preferably the same carboxylic acid ester used to form the PVP suspension, then is prepared according to the process of U.S. 4,564,514. In this step, an aqueous H202 solution (e.g. a 50% solution) is treated with the ester and then subjected to azeotropic distillation at a predetermined low pressure, e.g. at 200 mm Hg and 55βC. The resultant product is an anhydrous H202 solution in the ester having a H202 concentration in the range of about 20 to 50% H202.
Thereafter the thus-prepared anhydrous H20 solution is slowly added to the cooled PVP suspension in an anhydrous solvent in an amount corresponding to the desired molar ratio of PVP and H202. Preferably, however, a small excess of the H202 solution over the desired stoichiometric ratio is used. For example, to prepare a PVP-H 02 complex with a 1:1 molar ratio, about 111 g. PVP and 100 g. of a 42% H202 and 300 ml of anhydrous solvent is used, providing a small excess, e.g. about 5%, over the required stoichiometric amount of 34 g. H20 . This excess H202 is recoverable from the mother liquor.
Upon mixing the PVP and H20 , a fine white powder is obtained which is filtered and dried at about 40-50°C. in vacuo to remove residual solvent. The product is a stable, anhydrous complex in the form of a uniform, free-flowing, fine white powder having a H202 content between about 13% (2:1 molar ratio) and 23% H20 (1:1 molar ratio) . iβ water content of the product generally is equal to or less than the amount present in the PVP starting material, and usually is less than 1%, preferably about 0.5%.
An alternative process for preparing the substantially anhydrous complexes of the invention uses a water-insoluble PVP polymeric starting material which is available commercially as a solid of varying molecular
weight and water content. A suitable water-insoluble PVP polymer is Crospovidone, sold by GAF Chemicals Corp., which contains about 4% water. These PVP powders preferably are dried at about 105°C. in vacuo for about 2 hours to reduce the water content to less than about 1%.
The dried PVP powders then are suspended at about 5-10°C. under agitation in a substantial quantity of an anhydrous organic solvent, such as a carboxylic acid ester, a dialkyl ether, e.g. t-butyl methyl ether, or a hydrocarbon e.g. hexane or cyclohexane. Preferably an alkyl or cycloalkyl ester of a saturated aliphatic carboxylic acid is used, as for example, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and ethyl propionate. Ethyl acetate is preferred.
A 70-85% aqueous H202 solution then is added to the cooled PVP suspension under continued agitation during a period of about 30 minutes to about 1 hour. The amounts of PVP starting material and H202 solution used correspond to the desired molar ratio of PVP and H 02 in the complex. Preferably, however, a small excess of the H202 solution over the desired stoichiometric ratio is used. This excess H202 is recoverable from the mother liquor.
Upon mixing the PVP and H20 , a uniform, free-flowing, fine, white powder precipitate is obtained which is filtered and dried at about 40-50°C. in vacuo to remove residual solvent and water. The product is a stable, anhydrous complex in the form of a uniform, free-flowing, fine, white powder having a H202 content between about 18 and 22% H202. The water content of the product generally is about 2% or less, and usually can be dried to less than about 1%.
Continued drying under these low temperature and vacuum conditions reduces the final water content in the complex to a substantially anhydrous powder with no loss of H202.
EXAMPLE .1
Preparation of Substantially Anhydrous 1:1 PVP-H2O2 Complex
PVP K-30 (GAF Corp.) (4.5% water). 111 g., was suspended in 200 ml. of anhydrous ethyl acetate (0.01% H20) , and the suspension was cooled to 0°C. An anhydrous hydrogen peroxide solution in ethyl acetate was prepared by treating 200 g. of 50% aqueous hydrogen peroxide with 6 1. of ethyl acetate and azeotroping in a rotary evaporator to remove 100 g. of water. A 42.7% H202 solution in anhydrous ethyl acetate was obtained. Then 100 g. of this solution was added slowly over a period of about 1-1/2 hours to the PVP suspension. A fine white precipitate formed which was filtered and dried in vacuo. The resultant water soluble complex contained 23.4% by weight H202 and 0.5% by weight water, upon drying at 50βC. in vacuo for 2 hours.
EXAMPLE 2
Preparation of Anhydrous 2:1 PVP-H2O Complex
The process of Example 1 was followed using 50 g. of the H202 solution in anhydrous ethyl acetate. The resultant complex contained 13.2% H202 and 0.5% water.
EXAMPLE 3
200 g. of PVP-CI (K-30) was suspended in 300 g. of anhydrous ethyl acetate. Then H202, 424 g., 19.6% H 02 and 0.84% H 0 was added slowly to the cooled (5βC.) suspension of PVP/ethyl acetate. The addition required 45 minutes. The suspension then was stirred for
another 45 minutes, filtered, and washed with anhydrous ethyl acetate. The fine powder was dried at 40-50°C. for 2 hours under vacuum to recover ethyl acetate. The yield was
258.8 g. of water soluble PVP-H 02 containing 23.1%
H202 and 0.4% H20 as a free flowing white powder.
The mother liquor of ethyl acetate, 485 g. contained 4.51%
H202-
EXAMPLE 4
35 g. of crospovidone was suspended in 100 ml. of anhydrous ethyl acetate. Then H202, 27.5 g. as a 42.7% H202 solution was added with cooling at 5-10βC. The mixture was stirred for l hour. The precipitated complex was filtered to provide 46.1 g. of a water insoluble PVP-H 02 complex containing 24.9% H202, after drying at 40-50°C. for 2 hours.
COMPARATIVE EXAMPLE
Preparation of Aqueous PVP-H2O Complex According to U.S. 3,480,557
6 g. of PVP-CI (K-30) (GAF Corp.) (4.5% water) was dissolved in 50 ml. of methanol. Then 7 g. of a solution of H202 in water (50%) was added, followed by heating at 45βC. for 2 hours, and evaporation of methanol for 12 hours. A gummy, amorphous residue was obtained which contained 12.92% H202 and 5% H 0.
EXAMPLE 5
Stability of Anhydrous Complex of Example 1
After 43 days at 60°C. the complex lost only 15% of its H202 activity, which shows excellent stability toward decomposition. At room temperature, decomposition was only 1.5% after 60 days.
EXAMPLE 6
Preparation of Free-Flowing, Fine, White Powders of PVP-H2O2 Complex
PVP-CI (K-30) (GAF Corporation) (4.5% water) was dried at 105°C. in vacuo for 2 hours until it contained only 1.1% water. 160 g. of the dried, water-insoluble PVP was suspended in 450 g. of anhydrous ethyl acetate (0.01% water) , and the suspension was cooled to 5°-10°C. while agitating the suspension. Then 55 ml. of 70% hydrogen peroxide solution in water (71 g. H20 ) was added slowly over a period of 35 minutes to the agitated suspension keeping the temperature at 5°-10°C. A fine, white precipitate was formed which was filtered to yield 312 g. of a wet product which was dried at 40°-50°C. in vacuo for 4 hours. 200 g. of a free-flowing fine, white powder was obtained which contained 19.5% H 02 and 2.9% water. Further drying under the same conditions for an additional 6 hours reduced the water content to 0.5% while maintaining the H202 content at 18.5% and without affecting the physical properties of the powder.
In the drying step above, 77.9 g. of mostly ethyl acetate was collected in the vacuum trap which also contained 0.2% H202 and 3.78% water in the upper layer and 8.0 g. of mostly water (92%) with 0.63% H202.
The filtrate (363 g.) obtained above contained 2.75% H202 and 1.54% H20, the rest being ethyl acetate, which was recycled as described in Example 2 below.
EXAMPLE 7
The procedure of Example 6 is followed using PVP-CI 160 g.; ethylacetate 450 g.; and 85% H202 56 g. 197 g. of a PVP-H202 complex with 19.2% H202 containing 1.56% H20 is obtained. Further drying at 40-50°C. in vacuo will reduce the water content to 0.5% H20.
EXAMPLE 8
Preparation of Free-Flowing, Fine, White Powders of PVP-H O Complex by Recycling the Filtrate of Example 1
To the filtrate from Example 6, 363 g., was added 90 g. of fresh, anhydrous ethyl acetate followed by cooling to 5°-10°C. Then 170 g. of dried PVP-CI was added at once whereupon the exothermic reaction increased the temperature to 12βC. The suspension was cooled to 5°C. with an ice-water bath. Then 58 g. of a 70% H20 solution was added over a period of 2 hours with good agitation, a fine, white precipitate was formed and filtered to provide 320 g. of a wet cake which was dried at 40°-50°C. under vacuo for 4 hours to yield 202 g. of a free-flowing, fine, white powder containing 18.9% H202 and 3.1% H20. Further drying under the same conditions for an additional 6 hours lowered the water content to 0.6%, and the H202 content to 18.3%, without affecting the physical characteristics of the powder.
The filtrate weighed 358 g. , and was mostly ethyl acetate with 2.58% H202 and 1.49% water.
COMPARATIVE EXAMPLE 2
Preparation of Aqueous PVP-H 02 Complex according to U.S. 3,480,557
To 6 g. of PVP-CI (K-30) (GAF Corporation) (4.5% water) was dissolved in 50 ml. of methanol was added 7 g. of a solution of H202 in water (50%) , followed by heating at 45βC. for 2 hours, and evaporation of methanol for 12 hours. The gummy, amorphous residue contained 12.92% H202 and 5% H20.
EXAMPLE 9
Stability of Anhydrous Complex of Example 6
After 43 days at 60°C. the complex lost only 15% of its H202 activity, which shows excellent stability toward decomposition. At room temperature, decomposition was only 1.5% after 60 days.
EXAMPLE 10
Stability of Aqueous Solutions of Anhydrous Complex of Example 6
An aqueous solution of the complex of Example 6 containing 3.75% H20 was heated at 58°C. for 96 hours. At the end of this period, the solution analyzed for 2.75% H20, which indicated excellent stability for aqueous solutions of the complex of the invention.
COMPARATIVE EXAMPLE 3
Stability of Aqueous Solutions of (a) Urea/H2 Q 2 and (b) HQOQ
(a) Under the same conditions as in Example 10, a urea/H 02 solution, after only 36 hours, was reduced in H202 content from 3.5% to 0.6% H202. (b) An H202 solution itself lost all of its 3.0% H202 content after 36 hours.
Antimicrobial formulations of the complexes of the invention are prepared using a microbiocidal amount of the substantially anhydrous PVP-H202 complex, and an acceptable diluent and/or other active and inactive ingredients in the form of a suspension, solution, dispersion gel, powder, paste, suppository, aerosol, ointment, tablet, etc. The formulation may also be impregnated into or applied onto a suitable support, such as a gauze, cotton swab, sponge, etc. Generally, the complex will be activated by water present on the surface containing the microbes, the water functioning to release the active H202 from the complex.
- 11 -
FORMULATION 1
The suppository dissolves completely in about 1 ml of water in about 10 minutes at a temperature of about 37βC. Upon contact with water, a slight development of foam starts with simultaneous dissolution of the suppository. The foam development increases constantly until the dissolution is complete. The foam which forms has fine pores, is even and remains as such over an extended period of time. The nonoxynol-9 is a spermaticide, and the amphoteric-19 and PVP-peroxide are microbiocides.
FORMULATION 2
EFFERVESCENT MOUTHWASH TABLET
Ingredient Percent Wt. (grams)
Anhydrous PVP-H202
(23.1%) (Ex.l) Sodium bicarbonate (granular) Sodium carbonate, anhydrous Citric acid, anhydrous (granular) Aminoacetic acid Flavorants (spray dried) Color
100% 447 mg.
The tablets are compressed with 3/4-in. diameter, flat-faced, bevel-edge tooling. The tablet ingredients, other than the anhydrous PVP-peroxide complex, are mixed, lightly dampened, and granulated. To the slightly dampened granules the anhydrous PVP-peroxide complex is added, and the well-mixed, slightly-moist ingredients are compressed, then immediately thereafter placed in a 70°C. forced draft oven for 1 hour to drive off any residual water. The cooled tablets are immediately packaged in air tight aluminum foil pouches.
The tablets are added to 60 cc (2 oz.) of water for use as an effervescent mouthwash and gargle.
FORMULATION 3
NON-AQUEOUS OINTMENT
Ingredient Percent wt.(g.) Anhydrous PVP-H202 15 150
(23%) (Ex.l) Sorbitan Monopalmitate 10
(Span* 40-Atlas) Polyethylene Glycol 400 14 140
Monostearate Polyethylene Glycol 400 35 350 Polyethylene Glycol 4,000 35 350
100% 1,000 g.
The polyethylene glycols and the sorbitan monopalmitate are warmed on a water bath to 70βC. and the complex is added to the well-stirred molten mass. Stirring is continued until the ointment is well-solidified.
FORMULATION 4
ANTIBACTERIAL LIPSTICK
100% 2.00 g.
The formulation is prepared as in 3 above.
- 14 -
FORMULATION 5
POLYETHYLENE GLYCOL-CONTAINING OINTMENT
Ingredient Anhydrous PVP-H202
Heat the polyethylene glycol 4000 and 400 with constant stirring on a water bath at 65°C. Slowly add the micronized anhydrous sodium carbonate and PVP-H202 complex with constant stirring. Cool until the mass is well mixed and congealed.
FORMULATION 6
100.0%
All D items in formula above should be micropulverized and blended. Sprinkle the xanthum gum into glycerin with constant agitation until uniform (Phase A) . Add the polyethylene glycol 400 (Phase B) to Phase A with continued agitation. Sprinkle in Povidone K-90 until uniform and with constant stirring add the well mixed micronized ingredients of Phase D. Seal unit with cover and apply 28 or more inches of vacuum for 30-45 minutes with continuous agitation. Add all ingredients of phase E, starting with the hydrogen peroxide complex (item 1) , under continued agitation and mix until uniform. Mix under vacuum (28 inches or more) for 5 additional minutes.
- 16 -
FORMULATION 7
Blend micronized powders of the above two ingredients until homogeneous. Add ethyl alcohol to the well blended powder until a thick homogeneous paste is achieved. Lay a homogeneous layer of 700 mg plus the ethyl alcohol used for dispersion on 1 sq. inch of bandage. Place the coated bandage material under vacuum and heat until the ethyl alcohol is completely evaporated. The resultant mixture of the H202 complex and povidone K-90, evenly spread on 1 square inch of bandage will yield about 3% of available H 02 from the solid povidone mixture.
If substantive icrobicide activity is desired, 0.1% of cetyl pyridinium chloride can be mixed into the above blend before evaporation of the ethyl alcohol.
FORMULATION 9
EAR DROPS SOLUTION
Ingredient Percent Wt. (q.) Anhydrous PVP-H202 6.5 6.5 (23%) (Ex. 1) Anhydrous glycerol 93.5 93.5 100% 100g.
FORMULATION 10
SOFT LENS DISINFECTION TABLET
Ingredient Anhydrous PVP-H202
(23%) (Ex. 1) Sodium bicarbonate (granular) Sodium carbonate, anhydrous Citric acid, anhydrous granular Sodium benzoate (fine powder)
100% 1.84 g.
The tablet ingredients, other than the anhydrous PVP-H202 and sodium benzoate are mixed, lightly dampened to form a damp granule. To the slightly dampened granules the povidone peroxide and sodium benzoate are added so that granules with a damp feel are compressed using 1-1/4" flat-faced, bevel-edge punches. Immediately
after compression the damp tablets are placed in a 70°C. forced draft oven for 1 hour to drive off any residual water. The cooled tablets are immediately packaged in air-tight aluminum foil pouches.
FORMULATION 11
H202 Activity 3% 3.5% 5.0%
The above powders were mixed together to provide the desired composition.
FORMULATION 12
WOUND DRESSING
Ingredient Anhydrous PVP-H202
(22.8% H202) Absolute Ethanol
A 1% H202 solution of the above composition is applied to a wound. A film is formed which is effective to disinfect the wound.
FORMULATION 13
COLD WATER LAUNDRY TABLET
Ingredient Percent Wt. (g.)
PVP-H202 (23%) (EX. 1) 81.5 1.50
Sodium benzoate (fine powder) 1.64 0.03
100% 1.84 g.
These anhydrous PVP-H202 tablets are an effective cold water bleach-disinfectant for cleaning clothes, etc. In use, the PVP portion of the complex can chelate with inorganic ions (e.g. Ca++, Mg++) in the water to reduce water hardness. It can also provide laundry detergents with the properties of antiredeposition or suspension of dirt, anti-dye transfer, along with its bleaching and disinfectant action.
FORMULATION 14
WATER DISINFECTANT TABLET
Ingredient Sodium bicarbonate Sodium carbonate, anhydrous Citric Acid, anhydrous granules Povidone-H202 (20%) Sodium benzoate (fine powder)
100.0% 1.59 g.
This tablet should be dissolved in one quart of water and allowed to remain for 5 minutes after the tablet is dissolved before the water is ready to drink. To prepare the tablet, follow the same directions as given in Formulation 10 except use a 1 inch flat-faced, bevel-edge punch.
The above formulations and applications illustrate methods of reducing the bacterial content of surfaces using the anhydrous PVP-H202 complex of the invention.
Claims
1. A stable complex of PVP and H202 in a molar ratio of between about 2:1 and about 1:1, respectively, which is obtained as a uniform free-flowing, fine, white powder by direct reaction between suspended PVP and H202 in substantially the molar ratio predetermined for the complex.
2. A complex according to claim 1 wherein the complex contains essentially little or no water or free hydrogen peroxide therein.
3. A process of preparing a stable, uniform free-flowing powder complex of PVP and H202 which comprising suspending PVP powders in an anhydrous medium and reacting H 02 therewith.
4. A process according to claim 2 wherein the H202 is reacted in substantially the same molar ratio as desired in the complex.
5. A process according to claim 3 in which PVP is suspended in anhydrous ethyl acetate.
6. A suspension process for preparing uniform, free-flowing fine, white powders of a substantially anhydrous complex of PVP and H 02 having an H20 content between about 18 and about 22% H 0 which comprises:
(a) forming a suspension of water-insoluble PVP containing less than about 1% water in an anhydrous organic solvent,
(b) slowly adding a predetermined amount relative to the PVP of an aqueous H202 solution containing about
70 to about 85% by weight H202, at a temperature of about 0β-10°C. under agitation to precipitate a PVP-H202 complex in the form of a uniform, free-flowing, fine, white powder,
(c) filtering, and
(d) drying the wet precipitate to form the desired powders.
7. A suspension process according to claim 6 wherein said organic solvent is anhydrous ethyl acetate.
8. A process according to claim 6 wherein the filtrate is recycled for use in step (a) .
9. A process according to claim 6 wherein drying is carried out at about 50°-60βC. in vacuo.
10. A method for reducing the microbial content of surfaces which comprises contacting said surface with a microbiocidal amount of a substantially anhydrous complex of PVP and H202 in the form of a free-flowing powder having an H202 content of about 3 to 24% by weight, wherein said complex is present in a formulation in an amount of about 0.1 to 15% by weight.
11. A method according to claim 10 wherein said complex is present on a support.
12. A method according to claim 11 wherein said support is a gauze, cotton swab or sponge.
13. A method according to claim 10 wherein said complex is present in a non-aqueous formulation.
14. A method according to claim 10 wherein said surface comes into contact with living tissue.
15. A formulation for reducing the microbial content of surfaces which include a microbiocidal amount of an anhydrous PVP and H20 complex, having an H202 content of about 3 to 24% by weight.
16. A method according to claim 1 further characterized in that said surface is contacted in the presence of water.
17. A formulation according to claim 16 wherein the complex has a molar ratio of PVP and H202 between about 2:1 and about 1:1.
18. A formulation according to claim 16 which also includes one or more of an acceptable diluent, and an active or inactive ingredient.
19. A formulation according to claim 16 which is in the form of a suspension, solution, suppository, gel, powder, paste, ointment, or tablet, optionally, on a support.
20. A formulation according to claim 16 which is a non-aqueous composition.
21. A formulation according to claim 16 which is a vaginal suppository, an effervescent mouthwash, a non-aqueous ointment, a polyethylene glycol-containing ointment, an anhydrous toothpaste, a tooth powder, a medicated bandage, an ear drop solution, a soft lens disinfectant tablet, a medicated powder, a wound dressing, a cold water laundry tablet, or a water disinfectant tablet.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US434,943 | 1989-11-08 | ||
US07/434,943 US5008093A (en) | 1989-11-08 | 1989-11-08 | Anhydrous complexes of PVP and hydrogen peroxide |
US450,695 | 1989-12-14 | ||
US07/450,695 US5008106A (en) | 1989-12-14 | 1989-12-14 | Method for reducing the microbial content of surfaces with a microbiocidal, anhydrous complex of PVP-H2 O2 |
US07/533,749 US5066488A (en) | 1988-12-01 | 1990-06-06 | Semi-anhydrous, suspension process for preparing uniform, free-flowing, fine, white powders of substantially anhydrous complexes of PVP and H2 O2 containing about 18 to about 22% H2 O2 |
US533,749 | 1990-06-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991007184A1 true WO1991007184A1 (en) | 1991-05-30 |
Family
ID=27411865
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1990/005846 WO1991007184A1 (en) | 1989-11-08 | 1990-10-15 | SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP and H2O¿2? |
Country Status (2)
Country | Link |
---|---|
CA (1) | CA2028354A1 (en) |
WO (1) | WO1991007184A1 (en) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0605690A1 (en) * | 1992-06-29 | 1994-07-13 | Edward Shanbrom | Povidone hydrogen peroxide preservation of blood, tissues and biological fluids |
WO1994015648A1 (en) * | 1992-12-30 | 1994-07-21 | Bausch & Lomb Incorporated | Treating of contact lenses with compositions comprising pvp-h2o¿2? |
WO1997020867A1 (en) * | 1995-12-05 | 1997-06-12 | Basf Aktiengesellschaft | Powdery complexes of hydrogen peroxide and polymers |
EP0832846A2 (en) * | 1996-09-30 | 1998-04-01 | Basf Aktiengesellschaft | Complexes of polymer and hydrogen peroxide |
WO1998014199A1 (en) * | 1996-09-30 | 1998-04-09 | Basf Aktiengesellschaft | Topical products as prophylactic or curative agents for bacterial skin infections |
EP1041138A1 (en) * | 1999-04-02 | 2000-10-04 | Unilever Plc | Household cleaning compositions |
US6235318B1 (en) | 1999-01-21 | 2001-05-22 | Charles M. Lombardy, Jr. | Effervescent chewing gum |
WO2003053481A1 (en) * | 2001-12-20 | 2003-07-03 | Kimberly-Clark Worldwide, Inc. | Products for reducing microbial organic compounds |
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