US3847830A - Stabilizing peroxygen compounds by enveloping in a water-dispersible layer - Google Patents

Stabilizing peroxygen compounds by enveloping in a water-dispersible layer Download PDF

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Publication number
US3847830A
US3847830A US00218574A US21857472A US3847830A US 3847830 A US3847830 A US 3847830A US 00218574 A US00218574 A US 00218574A US 21857472 A US21857472 A US 21857472A US 3847830 A US3847830 A US 3847830A
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peroxygen
layer
weight
compound
enveloping
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US00218574A
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S Williams
J Leaver
D Abbott
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Evonik LIL Ltd
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Laporte Industries Ltd
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • 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
    • C01B15/005—Stabilisation of the solid compounds subsequent to the preparation or to the crystallisation, by additives or by coating
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Definitions

  • This invention relates to particulate peroxygen compounds for example alkali metal percarbonates and perphosphates, and to detergent mixes containing such compounds.
  • peroxygen compounds can be employed in a detergent mix as bleaching compounds.
  • domestic heavy duty detergents usually employ sodium perborate tetrahydrate as a bleaching compound because it is relatively stable to decomposition in a detergent environment. It is becoming more common to use cool washing and soaking techniques and sodium perborate tetrahydrate has the disadvantage of a relatively low solution rate at C.
  • base detergents with many other inorganic peroxygen compounds, including adducts of alkali metal salts often present in base detergent compositions, such as alkali metal carbonates and phosphates, with hydrogen peroxide, which adducts do have suitable rates of solution. Decomposition of such adducts however, is accentuated at ambient temperatures, by relative humidities of greater than about 40% which humidities are often generated by commercially available base detergents, thereby lowering the bleaching effect of the detergent mix.
  • the present invention provides a peroxygen containing composition
  • a peroxygen containing composition comprising a particulate normally unstable peroxygen compound and a water-dispersible layer consisting of less than 15% by weight, based on the weight of the layer and of the peroxygen compound, of a water ted States Patent Oil ice Patented Nov. 12, 1974 insoluble agent, the layer enveloping the particles of peroxygen compound and at least partially stabilising them to decomposition.
  • water dispersible layer a layer which is sufficiently dispersible, under the conditions of the following test, to allow the peroxygen compound which has been enveloped to dissolve to the extent of by weight in not more than 30 minutes and preferably in less than 15 minutes.
  • the test comprises placing 2 g. of enveloped peroxygen compound in 1 litre of water maintained at 15 C. and stirring continuously. The time for 75% by weight solution is measured by known means.
  • Dissolution times of an enveloped peroxygen compound in water bears a close relationship to the dissolution times of the same enveloped peroxygen compound in the aqueous phase of many commonly-used washing media.
  • the agent from which the layer is formed is compatible with the peroxygen compounds in solution, does not affect the performance of other components present in detergent compositions and absorbs little or zero water in atmospheres of high humidity.
  • the agent is a compound which could advantageously be incorporated in detergent mixes.
  • suitable agents are fatty acids, and glycerol esters and alkanolamide derivatives of such acids.
  • the fatty acids which can be either natural or synthetic, contain from 8 to 26, particularly 10 to 24 especially 12 to 22 carbon atoms.
  • the fatty acids are hydrogenated, and particularly have an iodine number lower than 30. Mixtures of hydrogenated fatty acids derived from coconut oil, tallow oil, castor oil or groundnut oil are especially suitable.
  • alkanolamide derivatives are monoalkanolamide derivatives, or those dialkanolamide derivatives having a melting point at not less than 35 C. preferably of not less than 40 C.
  • the alkanolamide radical contains not more than 6 carbon atoms, for example, ethanolamide or propanolamide.
  • Long chain aliphatic alcohols for example cetyl alcohol or stearyl alcohol or polyvinyl alcohols, or paraflin waxes may be used as enveloping agents, according to other embodiments of the invention.
  • normally unstable peroxygen compounds solid organic peroxygen compounds, inorganic peroxymonosulphates, and adducts of inorganic salts with hydrogen peroxide, which have poor stability to decomposition at ambient temperatures when in admixture with a solid base detergent composition containing at least 10% by weight water based on the composition, this often being sufficient water to generate in a sealed container a relative humidity of at least approximately 40%.
  • a detergent composition containing, by weight, based on the composition, at least 2.0% of an active linear alkyl benzene sulphonate, at least 30% sodium tripolyphosphate and at least 10% water may suitably be used.
  • at least 15 to 20% of the peroxygen compound may decompose after storage for one year under the above stated conditions, in comparison with sodium perborate tetrahydrate, which, under similar conditions, has a decomposition of about 1 to 3%.
  • percentages of decomposition are by weight based upon the weight of the peroxygen compound, and excluding the weight of the agent.
  • the invention is particularly suitable for treating solid peroxygen compounds which suffer at least 30% decomposition after storage for 1 year at ambient temperatures in admixture with a major proportion of a synthetic base detergent containing at least by weight water, 20%- 25%, by weight active linear alkyl benzene sulphonate and 30%-35% sodium tripolyphosphate, and which admixture has an active oxygen content of 1%
  • the active oxygen content of an admixture is dependent upon the active oxygen content of the peroxygen compound in the admixture.
  • Admixtures of peroxygen compounds with synthetic base detergents often have active oxygen contents of from to 3% by Weight based on the admixture.
  • the adducts of inorganic salts with hydrogen peroxide may be adducts of alkali metal salts with hydrogen peroxide.
  • alkali metal salts are salts often present in many detergent compositions such as alkali metal carbonates or phosphates, particularly sodium salts.
  • the adduct of a salt is referred to herein as a persalt.
  • Especially preferred persalts are sodium percarbonate (Na CO A H O sodium perpyrophosphate and sodium pertripolyphosphate.
  • the inorganic peroxymonosulphate is that of an alkali metal, especially potassium.
  • the organic peroxygen compound may be an organic peroxyacid, preferably having a melting point above 50 C., for example, a peroxyphthalic acid or a substituted peroxybenzoic acid.
  • inorganic peroxygen compounds which have a high active oxygen content, for example sodium percarbonate having approximately 13.5% by weight, and those which have good solubilities in detergent solutions, are used.
  • the rate of solution of a peroxygen compound enveloped in a layer of water insoluble agent according to the invention is slower than that rate of the unenveloped peroxygen compound of corresponding particle shape, size range and chemical constitution, surprisingly it has been found that a suitable rate of solution at ambient temperatures can be obtained, provided that the weight percent of water insoluble agent applied is according to the invention. Surprisingly it has been found that such a layer is readily dispersed in aqueous washing media at temperatures below its melting point. Enveloping the peroxygen compounds in such a layer can both protect against decomposition induced by humid air, and also release the peroxygen compound in aqueous washing media at ambient temperatures. An inverse relationship exists between the rate of solution at a temperature of for example C.
  • each particulate peroxygen compound an optimum range or ranges of levels of envelopment within which the apparently contradictory conditions of much enhanced stability and thereby longer packet life, and also a suitable rate of solution at ambient temperatures are fulfilled, depending upon which method of application of the envelopment is empl y
  • Suitably particles having any shape or size may be enveloped, but particles having a higher ratio of surface area to volume require a higher level of envelopment to produce a layer allowing similar rates of solution and similar packet stability of the enveloped peroxygen compound. As the particles become less regular, or become smaller their surface area/volume ratio rises.
  • particles to be enveloped have a fairly narrow range of particle sizes, or have a similar iregularity of shape.
  • the particle size range may be from approximately to about 1000 especially suitably the particles may be approximately spherical.
  • the layer contains from 1% to 10% by weight based on the enveloped peroxygen compound of a water insoluble agent.
  • a particularly preferred range of levels of envelopment depend upon how evenly the envelopment is applied, the more even the envelopment, in general, the lower the preferred range.
  • the preferred level of envelopment is from 1% to 5% by weight based on the enveloped peroxygen compound. If the layer is applied by contacting molten agent with the particulate peroxygen compound the preferred level of envelopment is from 4% to 10% by weight based on the enveloped peroxygen compound. Use of an improved molten agent application technique might lower the preferred range.
  • one or more layers of enveloping agent may be applied, or a mixture of agents may be applied, provided that the total level of envelopment does not exceed 15% by weight. Successive layers may be applied using similar or different methods.
  • Particles to be enveloped may be produced by, for example, a solution process or a fluidised bed method, and may or may not have been classified.
  • the flow properties, packet stability and solution rate of the enveloped particles of similar shape and size may vary.
  • Method 1 The particles are immersed in a bulk solution of an enveloping agent in an organic solvent, for example, a paratlin wax in carbon tetrachloride, followed by filtration, and evaporation of the solvent. In a variation the filtration step may be omitted.
  • an organic solvent for example, a paratlin wax in carbon tetrachloride
  • Method 2. A solution of enveloping agent in a solvent, for example, tallow acid monoalkanolamide in methanol is sprayed onto the particles agitated in a fluidised bed, the bed being supplied continuously with enough hot air to evaporate off the solvent.
  • a solvent for example, tallow acid monoalkanolamide in methanol
  • molten enveloping agent for example, molten lauric acid monoalkanolamide is sprayed onto the particles agitated in a non-heated fluidised bed, and allowed to cool.
  • Method 4 Hot molten enveloping agent is sprayed onto the particles agitated in a fluidised bed heated to a temperature of at least that of the melting point of the enveloping agent. After agitation the bed is cooled by the use of a cool fluidising gas.
  • Methods 1, 2 and 3 For enveloping peroxygen compounds whose melting points are lower than those of the enveloping agents Methods 1, 2 and 3 are preferable, Method 2 yielding a particularly suitable product.
  • Methods 2, 4 and 5 For enveloping peroxygen compounds whose melting points are higher than those of the enveloping agents, Methods 2, 4 and 5 are particularly suitable, Methods 2 and 5 preferable.
  • the peroxygen compound used in Examples 1 to 12 was particulate sodium percarbonate, unenveloped and having a range particle size of from 120 to 1000 prepared by a fluidised bed process as described in copending British application 32,640/70 followed by granulation.
  • the enveloped peroxygen compound used in Examples 2-12 was prepared by enveloping the particulate sodium percarbonate in a water-insoluble fatty acid alkanolamide at a level of envelopment indicated in the following table.
  • the sodium percarbonate particles were enveloped in Empilan CME, in Examples 5, 6, 7 and 9 in Ethylan LM, in Example 10 in Empilan TME, and in Examples 11 and 12 in Ethylan LMP.
  • Example 8 the enveloping agent was melted and then sprayed onto sodium percarbonate particles agitated in a fluidised bed through which air at ambient temperatures was forced.
  • Example 10 the enveloping agent was melted and then sprayed onto sodium percarbonate particles agitated in a fluidised bed through which air, maintained at a temperature of a few degrees above the melting point of the enveloping agent was forced.
  • Example 12 the enveloping agent was applied in two layers. The first layer was applied using the method used in Example 11, the level of envelopment being 9% by weight. The second layer, by weight, was applied using the same method used in Example 10.
  • the peroxygen compound was a different sample of particulate sodium percarbonate prepared by a fluidised bed process as described in German Oifenlegungsschrift No. 2,060,971, followed by granulation.
  • the peroxygen compounds were two samples of particulate sodium percarbonate prepared by a fixed bed process, in which sodium carbonate and aqueous hydrogen peroxide and suitable stabilisers are mixed, and sodium chloride added to the resultant solution with cooling to precipitate out sodium percarbonate granules which are centrifuged, and then dried in a rotary drier.
  • Examples 14 and 16 the persalt particles were enveloped in Empilan CME by adding molten Empilan CME in bulk to a bed of persalt particles having the temperature of about 65 C., and agitating mechanically in a Lodige-Morton mixer for about 8 minutes, and then allowed to cool.
  • Example 18 the peroxygen compound was enveloped in paraffin wax by immersion of the peroxygen compound in a bulk solution of paraflin wax in carbon tetrachloride, followed by evaporation of the carbon tetrachloride.
  • Ethylan LM is a trademark for a commercial preparation of lauric acid monoethanolamide (M.P. 55.5 C.) made by Lankro Chemicals Limited.
  • Ethylan LMP is a trademark for a commercial preparation of lauric acid monoethanolamide (M.P. 55.5 C.) made by Lankro.
  • TEST FOR PACIQET STABILITY To determine the packet stability in a detergent environment, of the enveloped peroxygen compounds prepared above, a portion of each peroxygen compound was blended with a synthetic base detergent which had been pre-equilibrated at 44% relative humidity at 30 C. for at least 3 days and contained then 10% by weight of water, by passing the mixture through a Pascal Rotary Sample divider.
  • the enveloped percarbonate particles contained initially approximately 12% by weight available oxygen, and the blend of detergent base and enveloped percarbonate contained 8% by weight of enveloped percarbonate.
  • each of the blends contained approximately 1% by weight available oxygen initially, which percentage was determined accurately by dissolving completely a known weight of detergent in a dilute aqueous sulphuric acid solution and titrating the resulting solution against a potassium permanganate solution of known normality.
  • the blend used in Example 1 contained unenveloped sodium percarbonate particles and pre-equilibrated base detergent, and the blend used in Examples 2 to 7 contained base detergent and sodium percarbonate particles enveloped at a level shown in the table.
  • the blends were sealed in glass jars and stored at ambient temperatures, which varied between 19 C. and 28 C. but usually between 19 and 24 C.
  • a peroxygen-containing composition consisting essentially of a particulate normally unstable peroxygen compound and a water dispersible layer of from 1% to less than 15% by Weight, based on the weight of the layer and of the peroxygen compound, of a solid waterinsoluble compound selected from the group consisting of (1) fatty acids of greater than 8 carbon atoms, (2) alkanolamides of fatty acids of at least 8 carbon atoms, (3) glycerol esters of fatty acids of at least 8 carbon atoms, (4) long-chain aliphatic hydrocarbon alcohols, and (5) paraffin waxes, the layer enveloping the particles of peroxygen compound and at least partially stabilising them to decomposition.
  • a peroxygen containing composition as claimed in claim 1 wherein the water-insoluble compound is a fatty acid containing from 8 to 26 carbon atoms.
  • a peroxygen containing composition as claimed in claim 1 wherein the water-insoluble compound is an alkanolamide of a fatty acid of at least 8 carbon atoms, said alkanolamide having a melting point of not less than 35 C.
  • a method of at least partially stabilising a normally unstable particulate peroxygen compound comprising at least partially enveloping the particles in a water-dispersible layer of a solid water-insoluble compound selected from the group consisting of 1) fatty acids of greater than 8 carbon atoms, (2) alkanolamides of fatty acids of at least 8 carbon atoms, (3) glycerol esters of fatty acids of at least 8 carbon atoms, (4) long-chain aliphatic hydrocarbon alcohols, and (5) paraffin waxes, said compound comprising from 1 to less than 15% by weight based on the weight of the enveloped particulate peroxygen compound.
  • the layer is deposited from solution and consists of from 1% to 5% by weight of water-insoluble agent, based on the enveloped peroxygen compound.
  • the layer is prepared by contacting molten agent with the particulate peroxygen compound, and consists of from 4% to 10% by weight based on the enveloped peroxygen compound of agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
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US00218574A 1971-01-27 1972-01-17 Stabilizing peroxygen compounds by enveloping in a water-dispersible layer Expired - Lifetime US3847830A (en)

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GB324071A GB1370626A (en) 1971-01-27 1971-01-27 Coated peroxygen compounds

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US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
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US8846107B2 (en) 2010-12-29 2014-09-30 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US8889900B2 (en) 2010-12-29 2014-11-18 Ecolab Usa Inc. Sugar ester peracid on site generator and formulator
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9518013B2 (en) 2014-12-18 2016-12-13 Ecolab Usa Inc. Generation of peroxyformic acid through polyhydric alcohol formate
US9845290B2 (en) 2014-12-18 2017-12-19 Ecolab Usa Inc. Methods for forming peroxyformic acid and uses thereof
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10031081B2 (en) 2013-03-05 2018-07-24 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
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US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11040902B2 (en) 2014-12-18 2021-06-22 Ecolab Usa Inc. Use of percarboxylic acids for scale prevention in treatment systems
US11260040B2 (en) 2018-06-15 2022-03-01 Ecolab Usa Inc. On site generated performic acid compositions for teat treatment
US12058999B2 (en) 2018-08-22 2024-08-13 Ecolab Usa Inc. Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions

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FR2123476B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1976-06-18
GB1370626A (en) 1974-10-16
ES399222A1 (es) 1975-06-01
BE778578A (fr) 1972-07-27
AU3812672A (en) 1973-07-26
FR2123476A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1972-09-08
DE2203885A1 (de) 1972-08-17
IT948338B (it) 1973-05-30
CH557875A (fr) 1975-01-15
ZA72373B (en) 1973-03-28

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