CN1231599A - Process for forming a peracid and composition comprising said peracid - Google Patents
Process for forming a peracid and composition comprising said peracid Download PDFInfo
- Publication number
- CN1231599A CN1231599A CN97198352A CN97198352A CN1231599A CN 1231599 A CN1231599 A CN 1231599A CN 97198352 A CN97198352 A CN 97198352A CN 97198352 A CN97198352 A CN 97198352A CN 1231599 A CN1231599 A CN 1231599A
- Authority
- CN
- China
- Prior art keywords
- acid
- mixture
- preferred
- alkyl
- monoalkylation
- 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.)
- Pending
Links
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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
-
- 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
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
Abstract
The present invention relates to a process for forming a peracid which comprises the step of reacting in aqueous medium an alpha mono alkylated carboxylic acid and/or an alpha mono alkoxylated carboxylic acid with hydrogen peroxide or a water-soluble source thereof. Further disclosed are compositions comprising an alpha mono alkylated percarboxylic acid and/or alpha mono alkoxylated percarboxylic acid and compositions comprising an alpha mono alkylated carboxylic acid and/or alpha mono alkoxylated carboxylic acid and hydrogen peroxide or a water-soluble source thereof.
Description
Technical field
The compositions that the present invention relates to prepare the method for peracid (percarboxylic acids) and contain described peracid or its precursor.Compositions of the present invention is particularly useful for various application, for example is generally used for doing washing, is used as hard surface cleaner, is used as carpet cleaner, is used as artificial tooth cleaning agent, is used as cleaning compositions or is used as sanitizing composition.
Background technology
Various cleaning compositions have been described in the prior art.In fact, contain hydrogen peroxide and/or its water-soluble sources, the compositions that comprises peracid is known.For obtaining containing the compositions of this peracid, usual way is to use peracid precursors to replace peracid.Peracid normally can not obtain commercial, and if obtain, described peracid uses unsatisfactorily, because described peracid is in storage process, even before in adding compositions, is unsettled, and trends towards a large amount of decomposition.The compositions that contains this peracid can adopt hydrogen peroxide or its water-soluble sources and corresponding peracid precursors, and promptly the whole bag of tricks of the reaction of corresponding acid obtains.Yet the method that obtains peracid with tangible content comprises makes corresponding acid and high-load hydrogen peroxide or the reaction of its source.Therefore, the improvement method and the Aquo-composition that contains peracid that need the preparation peracid.The makers-up especially seeks the method that higher peracid yield is provided.
Therefore, the purpose of this invention is to provide the improvement method for preparing peracid.
We find that now this purpose reaches by make hydrogen peroxide or its water-soluble sources and α monoalkylation or α monoalkoxy carboxylic acid reaction in water-bearing media.In fact, we find, compare with corresponding unsubstituted carboxylic acid, when using α monoalkylation or α monoalkoxy carboxylic acid as peracid precursors, have obtained the peracid of high yield.In other words, we find to be included in and make α monoalkylation or α monoalkoxy carboxylic acid and the method for preparing peracid of the step of hydrogen peroxide or the reaction of its water-soluble sources cause preparing the superacid composite that contains that contains the comparatively high amts peracid by a certain amount of peracid precursors in the water-bearing media.
An advantage of method of the present invention is big motility to be provided and to provide to be suitable for the compositions that contains peracid that consumer uses with effective means in process for preparation.In fact, this compositions that contains peracid can be a feedstock composition, maybe can be to contain annexing ingredient, for example at the composition of detergent of the full preparation of the normally used component of detergent applications.
Another advantage of the present invention is to provide the cost that adds the high level peracid effectively to contain superacid composite by a certain amount of corresponding precursor.Also have, a relevant advantage of the compositions that obtains with method of the present invention is a said composition, when especially preparing with form of emulsion, the peracid that not only adds high level by the precursor of a specified rate, and the end product that has improvement stability when storing is provided, the decomposition rate of promptly contained peracid reduces.
It is known preparing peracid by hydrogen peroxide and organic carboxyl acid in the prior art.WO93/0516 discloses the method for preparing the dilute aqueous solution that contains the hydroxyl aliphatic series peroxycarboxylic acid that is no more than 7 carbon atoms, wherein in first step, described peroxycarboxylic acid precursors, the fortified aqueous that is the hydroxyl aliphatic carboxylic acid is mixing with strong hydrogen peroxide solution in the presence of the strong acid catalyst as required, stores mixture and reach maximum until the concentration of described peroxycarboxylic acid in second step; Dilute with water mixture then.It can be monocarboxylic acid or preferred dicarboxylic that WO93/0516 discloses described hydroxyl aliphatic carboxylic acid.Unexposed α monoalkylation or α monoalkoxy carboxylic acid.
EP-A-024219 discloses the method by the diluted composition of the concentrated solution of dicarboxylic acids that makes 3-5 carbon atom and hydrogen peroxide (60%-90%) prepared in reaction aliphatic series carboxyl peracid.Unexposed α monoalkylation or α monoalkoxy carboxylic acid.
WO91/13058 discloses the method for the dilute solution of preparation lower aliphatic peracid, wherein the initial concentration of lower aliphatic acid in reactant mixture (for example acetic acid) is preferably 25%-70% by weight, and the initial concentration of the hydrogen peroxide in described medium is preferably 15%-30% by weight.Unexposed α monoalkylation or α monoalkoxy carboxylic acid.
BE-A-864135 discloses the continuation method of preparation peracid, and it is included in and contains mineral acid, and as making hydrogen peroxide and carboxylic acid reaction in the vitriolic water-bearing media, described hydrogen peroxide adds in the reactant mixture to limit the concentration of hydrogen peroxide everywhere at several stages.BE-A-864135 mentions employed carboxylic acid and preferably contains at least 2 but be less than the unsubstituted monocarboxylic acid of 6 carbon atoms.Unexposed α monoalkylation or α monoalkoxy carboxylic acid.
EP-A-700902 discloses the method for preparing the Aquo-composition that contains peracid, and wherein said method comprises by making corresponding acid anhydride and the step that contains the described peracid of strong hydrogen peroxide solution prepared in reaction of 3 moles of described hydrogen peroxide of the described corresponding acid anhydride of every molar equivalent at least.
Summary of the invention
The present invention includes the method for preparing peracid, described method is included in the step that makes α monoalkylation carboxylic acid and/or α monoalkoxy carboxylic acid and hydrogen peroxide or the reaction of its water-soluble sources in the water-bearing media.In preferred embodiments, described method also comprises provides at least a annexing ingredient, described hydrogen peroxide or its water-soluble sources in addition and the step of described α monoalkylation and/or α monoalkoxy carboxylic acid of dewatering.
The present invention also comprises the compositions that contains peracid that obtains by method of the present invention, and it contains α monoalkylation percarboxylic acids and/or α monoalkoxy percarboxylic acids and contains α monoalkylation carboxylic acid and/or the aqueous mixture of α monoalkoxy carboxylic acid and hydrogen peroxide or its water-soluble sources.
The detailed description of invention prepares the method for peracid
Method of the present invention is the method for preparing peracid, and described method is included in the step that makes α monoalkylation carboxylic acid and/or α monoalkoxy carboxylic acid and hydrogen peroxide or the reaction of its water-soluble sources in the water-bearing media.
As first solvent, method of the present invention need be used α monoalkylation or α monoalkoxy carboxylic acid or their mixture.The mono-substituted carboxylic acid of this α is a peracid precursors, and it obtains required peracid with hydrogen peroxide or the reaction of its water-soluble sources in water-bearing media.Cross hydrolysis and be when peracid precursors at water-containing reacting medium, the reaction of generation when mixing with hydrogen peroxide or its water-soluble sources in the preferred acidic water-bearing media.In reaction, the hydroxyl of carboxyl functional group is replaced the corresponding peracid of formation by hydroperoxides anion (OOH-).
Being crossed α monoalkylation/monoalkoxy carboxylic acid that hydrolysis obtains corresponding peracid in the present invention can be α monoalkylation or α monoalkoxy monocarboxylic acid, α monoalkylation or α monoalkoxy polycarboxylic acid, as α monoalkylation or α monoalkoxy dicarboxylic acids or their mixture.
" α monoalkylation or α monoalkoxy carboxylic acid " of the present invention is meant on respect to the carbon atom of the alpha position of carboxyl by alkyl or the mono-substituted carboxylic acid of alkoxyl.Under polycarboxylic situation, acid at least one carboxyl functional group on its alpha position by alkylation or alkoxylate.
Suitable be used for α monoalkylation of the present invention or α monoalkoxy monocarboxylic acid has following formula:
Wherein R1 is 1-26, preferred 2-18, more preferably the alkyl of 2-14 carbon atom and wherein R2 be 1-14, the preferably alkyl or the alkoxyl of 1-8 carbon atom.
Be used for preferred α monoalkylation of the present invention or α monoalkoxy monocarboxylic acid and be that 2 Methylpropionic acid, 2-propionic acid ethyl, 2 methyl caproic acid, 2-methyloctanoic acid, 2-methoxyl group are sad, 2-methyl lauric acid, 2-ethyl lauric acid, 2-ethyoxyl lauric acid, 2-propyl group lauric acid or their mixture.
Be used for suitable α monoalkylation of the present invention or α monoalkoxy polycarboxylic acid and have following formula:
Wherein R1 and R3 are each H or 1-26 naturally, and preferred 2-18, the more preferably alkyl of 2-14 carbon atom, R2 are hydrogen or 1-14, the alkyl of preferred 1-8 carbon atom or alkoxyl and wherein n be 2-20, the preferred integer of 2-12; Y is H or carboxyl, wherein when in given molecular formula, repeating, Y and R2 each have identical or different implication and wherein in molecule at least two Y be carboxyl and be the alkyl or the alkoxyl of 1-14 carbon atom with respect at least one R2 on the alpha position of at least one described carboxyl.
Being used for α monoalkylation of the present invention or the polycarboxylic example of α monoalkoxyization is α monoalkylation or α monoalkoxy succinic acid, α monoalkylation or α monoalkoxy 1,3-propanedicarboxylic acid, α monoalkylation or α monoalkoxy adipic acid and α monoalkylation or α monoalkoxy 1,5-pentanedicarboxylic acid..
Being used for preferred α monoalkylation of the present invention or α monoalkoxy polycarboxylic acid is 2-methyl adipic acid, 2-methylsuccinic acid, 2-methoxyl group succinic acid, 2,3-dimethyl succinate, 2-methyl 1,5-pentanedicarboxylic acid., 2-ethyoxyl 1,5-pentanedicarboxylic acid., 2,6-dimethyl-g diacid, 2 ethyl glutaric acid, 2-methylglutaric acid, 2,4-dimethylated pentanedioic acid or their mixture.
As second solvent, method of the present invention need be used hydrogen peroxide or its water-soluble sources or their mixture.
The used hydrogen peroxide source of the present invention is meant any chemical compound that produces hydrogen peroxide when described chemical compound contacts with water.Be used for suitable hydrogen peroxide water solublity source of the present invention and comprise percarbonate, perborate and persulfate and their mixture.Hydrogen peroxide most preferably is used for the present invention.
" water-bearing media " is meant that this is reflected at water and carries out under existing among the present invention.The amount of employed water depends on required end product, and technological operation person handles at one's discretion.Usually the water that directly provides the water of aequum when peracid precursors contacts with hydrogen peroxide or its water-soluble sources or aequum is provided in step subsequently is to obtain containing as defined above the Aquo-composition by the mistake acid concentration of general composition weight meter 0.005%-50%.The dilution step that may need is carried out in room temperature or under about room temperature.Dilute aqueous solution has 5 ℃-25 ℃ temperature usually.In preferred embodiments, be desirably in reach maximum peracid concentration point or neighbouring after dilute immediately.The compositions that method of the present invention obtains can as mentioned belowly be monitored.In fact the method according to this invention can obtain maximum or approaching maximum mistake acid concentration in 5-48 hour the mono-substituted carboxylic acid of α mixes beginning with the solution of hydrogen peroxide or its water-soluble sources after.
Usually α monoalkylation carboxylic acid and/or α monoalkoxy carboxylic acid and hydrogen peroxide or its water-soluble sources are reacted, wherein the described precursor of peracid (being α monoalkylation carboxylic acid and/or α monoalkoxy carboxylic acid) is 0.5-20 with the molar ratio of described hydrogen peroxide or its water-soluble sources, preferred 1-10, more preferably 1-5.
Use in the method for the invention in the embodiment of hydrogen peroxide or its water-soluble sources solution, described solution contains 0.5%-90% hydrogen peroxide or its water-soluble sources or its mixture by weight, preferred 1%-70%, more preferably 2%-40%.
In the method for the invention, peracid precursors reacts with hydrogen peroxide or its water-soluble sources in the presence of the aqueous solution of strong acid or its mixture usually." strong acid " is meant that initial pka is lower than 3 herein, preferably is lower than 2, the acid more preferably less than 1.The aqueous solution of described strong acid is as reaction water-bearing media and catalyst.Described strong acid comprises mineral acid and/or organic sulfonic acid.Being used for preferred strong acid of the present invention is sulphuric acid, phosphoric acid and/or methanesulfonic acid.
In the method for the invention, the aqueous solution of described strong acid or its mixture contains 90%-98% by weight, more preferably 95%-98%, the most preferably described strong acid of 97%-98%.Therefore, method of the present invention is lower than 8 at pH usually, preferred 0-6, and more preferably 0-4 most preferably carries out in the acid range of 0-2.
By the aqueous solution that uses strong acid reaction is carried out with conventional speed, and do not used high reaction temperature.The temperature of carrying out method of the present invention depends on the concentration of employed hydrogen peroxide or its water-soluble sources solution.For example, if use hydrogenperoxide steam generator, react preferably in room temperature, for example 25 ℃ or above carrying out with 36% concentration.Be convenient and security consideration, reaction temperature remains on 0 ℃-40 ℃ in many embodiments, and preferred 5 ℃-30 ℃, more preferably 20 ℃-25 ℃ of room temperatures.
Even the advantage of method of the present invention is not adopt high reaction temperature can obtain higher peracid yield.
" yield " is interpreted as with respect to corresponding peracid precursors herein, i.e. the peracid percent of the acquisition of α monoalkylation or α monoalkoxy carboxylic acid calculating.Following equation is used to calculate described yield:
(crossing acid concentration/corresponding peracid precursors concentration) * 100=yield %
In this equation, concentration can be represented with mol.
The suitable test method of estimating peracid available oxygen (being abbreviated as Avox usually) is at " (measure the gas-liquid chromatography of peracid " (Gas-liquid chromatographymethod for determination of peracid) as F.Di.Furia etc., Analyst, vol.109, in August, 1984, the 985-987 page or leaf; Or ibidem vol.113, in May, 1988, the chromatography of describing in the 793-795 page or leaf.
In fact, we be surprised to find with employed peracid precursors wherein be that substituted carboxylic acid (for example 1,3-propanedicarboxylic acid or succinic acid) rather than described α monoalkylation or α monoalkoxy carboxylic acid (for example are not respectively 2 to corresponding α, 4-dimethylated pentanedioic acid or 2-methylsuccinic acid) same procedure compare, use method of the present invention by the α monoalkylation of a specified rate or α monoalkoxy carboxylic acid begins and itself and hydrogen peroxide or its water-soluble sources solution reaction are obtained higher peracid yield.
Method of the present invention not only allows to prepare the compositions that only contains peracid, i.e. raw material Aquo-composition, and can prepare the aqueous detergent compositions of full preparation, promptly also be added in the compositions of using component in the detergent applications usually.
Therefore, the annexing ingredient, hydrogen peroxide or its water-soluble sources that provide beyond at least a the dewatering and the step of described α monoalkylation carboxylic acid and/or α monoalkoxy carboxylic acid also can be provided the method for preparing described peracid.
The annexing ingredient that is provided is selected from surfactant, soil suspender, builder, chelating agen, bleach-activating, radical scavenger, pigment, enzyme, dye transfer inhibitor, solvent, buffer agent, foam inhibitor, optical white, brightening agent, dyestuff, spice etc. and their mixture.According to the final required purposes of the Aquo-composition of the inventive method, can add the various combination of these optional ingredients in the method for the invention.Suitable preferred optional ingredient is described hereinafter in more detail.
In one embodiment of the invention, the compositions that contains peracid can provide with form of emulsion.Therefore, the method that is used to prepare the method for peracid of the present invention also can contain additional step to obtain the Aquo-composition that contains peracid of form of emulsion.Peracid is by at least two kinds of different surfaces activating agents in these Aquo-compositions, and promptly at least a HLB is lower than the surfactant system emulsifying that 11 hydrophobic surfactant and at least a HLB are higher than 11 hydrophilic surfactant.In fact, two kinds of different surfactants must have different HLB values (hydrophile-lipophile balance), and the HLB difference of preferred described two kinds of surfactants is at least 1, and preferably at least 3, to obtain stable emulsion.
Therefore, the present invention includes the method for preparing the Aquo-composition that contains peracid, wherein peracid is contained at least a HLB and is higher than the surfactant system emulsifying that 11 hydrophilic surfactant and at least a HLB are lower than 11 hydrophobic surfactant, and described method comprises the steps:
In a step, prepare peracid according to the method for the invention described above, promptly in water-bearing media, make the reaction of α monoalkylation carboxylic acid and/or α monoalkoxy carboxylic acid and hydrogen peroxide or its water-soluble sources.
In another step, preparation contains the hydrophobic mixture of at least a described hydrophobic surfactant.Hydrophobic mixture preferably also contains other and is formulated in hydrophobic components in the compositions, for example spice, solvent, enzyme, bleach-activating, polymer and hydrophobic peracid.
In another step, preparation contains the hydrophilic mixture of water and described hydrophilic surfactant at least.Hydrophilic mixture preferably also contains other and is formulated in hydrophilic component in the compositions, for example dyestuff, hydrophilic fluorescent whitening agent, builder, chelating agen, buffer agent and hydrophilic peracid.
In fact, in the method for the invention, the peracid of formation is according to its characteristic separately, and is promptly hydrophilic or hydrophobic, mixes in hydrophobic mixture or hydrophilic mixture.
These three steps can any order be carried out naturally.
At last, in the later step of method of the present invention, hydrophobic mixture and described hydrophilic mixture are mixed.
The preferred surfactant that obtains aqueous emulsions is hydrophobic non ionic surfactants and hydrophilic nonionic surfactant.Be used for hydrophobic non ionic surfactants of the present invention and have and be lower than 11, preferably be lower than 10, the HLB more preferably less than 8, hydrophilic surfactant have greater than 11, are preferably greater than 12, the HLB more preferably greater than 13.
Be used for suitable ionic surfactant pack of the present invention and draw together alkoxy fatty alcohols, preferred fat alcohol ethoxylate and/or propoxylate.In fact, at the commercial various alkoxy fatty alcohols that obtain having very different HLB values (hydrophile-lipophile balance).The HLB value of this alkoxy-based non-ionic surface active agent depends primarily on chain length, alkoxylate character and the extent of alkoxylation of aliphatic alcohol.Hydrophobic non ionic surfactants trends towards having high alkoxy degree and short chain fatty alcohol, and hydrophobic surfactant trends towards having low-alkoxy degree and long-chain fatty alcohol.The surfactant catalogue is available, and it has listed various surfactants, comprises non-ionic surface active agent and they HLB value separately.
The suitable chemical method that preparation is used for non-ionic surface active agent of the present invention comprises with the corresponding pure and mild alkylene oxide of required ratio condensation.This method is the known to the skilled of prior art, and is described widely in the art.In addition, be applicable to various alcohol alcoxylates of the present invention commercial from various suppliers.It is 6 hydrophobic non ionic surfactants that the example of suitable nonionic surfactant system will contain HLB for example, and for example Dobanol 23-2 and for example HLB are 15 hydrophilic nonionic surfactant, for example Dobanol 91-10.Other suitable nonionic surfactant system contains Dobanol 23-6.5 (HLB about 12) and Dobanol 23 (HLB is lower than 6).
Except being the hydrophobic and hydrophilic surfactant of non-ionic surface active agent, the surfactant that is known in the art and can form any other type of emulsion can be used among the present invention.
Being used for other suitable hydrophilic surfactant of the present invention can be anion surfactant, especially sulfonate and sulfate surfactant.Same anion surfactant is as known in the art, and having found has extensive use in the commercial laundering agent.These anion surfactants comprise C8-C22 alkylbenzenesulfonate (LAS), C8-C22 alkyl sulfate (AS), unsaturated sulfate, for example oleyl sulfate, C10-C18 alkyl alkoxy sulfate (AES) and C10-C18 alkyl alkoxy carboxylate.The neutralizing cation of anion synthesising sulfonate and/or sulfate represents that by conventional cation these conventional cationes are widely used in the detergent technology, for example sodium, potassium or alkanol ammonium.
Other surfactant can be used among the present invention, yet they should obviously not change the weight average HLB value of total emulsion.According to their HLB value, described surfactant will add in the hydrophilic mixture or hydrophobic mixture of the inventive method.The compositions that contains described peracid
The present invention also comprises the Aquo-composition that contains the peracid that can obtain by method of the present invention.
Therefore, compositions of the present invention contains α monoalkylation or α monoalkoxy percarboxylic acids or their mixture.
Being used for α monoalkylation of the present invention/monoalkoxy percarboxylic acids can be the single percarboxylic acids of α monoalkylation or α monoalkoxyization, α monoalkylation or the many percarboxylic acids of α monoalkoxyization, or their mixture.
Suitable be used for α monoalkylation of the present invention or the single percarboxylic acids of α monoalkoxyization has following formula:
Wherein R1 is 1-26, preferred 2-18, more preferably the alkyl of 2-14 carbon atom and wherein R2 be 1-14, the preferably alkyl or the alkoxyl of 1-8 carbon atom.
Be used for the single percarboxylic acids of preferred α monoalkylation of the present invention or α monoalkoxyization and be that 2-methyl perpropionic acid, 2-ethyl perpropionic acid, 2-methyl are crossed caproic acid, the 2-methyl is sad excessively, the 2-methoxyl group is sad excessively, the 2-methyl is crossed lauric acid, the 2-ethyl is crossed lauric acid, the 2-ethyoxyl is crossed lauric acid, the 2-propyl group is crossed lauric acid or their mixture.
Be used for suitable α monoalkylation of the present invention or the many percarboxylic acids of α monoalkoxyization and have following formula:
Wherein R1 and R3 are each H or 1-26 naturally, and preferred 2-18, the more preferably alkyl of 2-14 carbon atom, R2 are H or 1-14, the alkyl or the alkoxyl of preferred 1-8 carbon atom, and wherein n is 2-20, preferably the integer of 2-12; Y is H or crosses carboxyl (COOOH), wherein when in given molecular formula, repeating, Y and R2 have separately identical or different implication and wherein in molecule at least two Y be carboxyl and be the alkyl or the alkoxyl of 1-14 carbon atom with respect at least one R2 at least one described alpha position of crossing carboxyl.
Be used for preferred α monoalkylation of the present invention or the many percarboxylic acids of α monoalkoxyization and be the 2-methyl and cross that adipic acid, 2-methyl are crossed succinic acid, the 2-methoxyl group is crossed succinic acid, 2, the 3-dimethyl crosses that succinic acid, 2-methyl are crossed 1,5-pentanedicarboxylic acid., the 2-ethyoxyl is crossed 1,5-pentanedicarboxylic acid., 2, the 6-dimethyl crosses that 1,5-pentanedicarboxylic acid., 2-ethyl are crossed 1,3-propanedicarboxylic acid, the 2-methyl is crossed 1,3-propanedicarboxylic acid, 2, and the 4-dimethyl is crossed 1,3-propanedicarboxylic acid or their mixture.
Compositions of the present invention contains by general composition weight meter 0.005%-50% monoalkylation or α monoalkoxy percarboxylic acids or their mixture, preferred 0.01%-30%, more preferably 0.01%-20%.Compositions of the present invention therein is that when excessive adding, described compositions also can contain hydrogen peroxide or its source of unreacted to form corresponding peracid in the embodiment that obtains according to said method.Common compositions of the present invention can contain by general composition weight meter 0.5%-90%, preferred 1%-70%, more preferably 2%-40% hydrogen peroxide or its water-soluble sources or their mixture.Described compositions can be in following application, and for example hard surface cleaning, water closet cleaning, carpet cleaning, laundry applications, artificial tooth cleaning and/or sterilization are used as feedstock composition in using.
Compositions of the present invention can be to add the raw material Aquo-composition of described peracid or the aqueous detergent compositions of full preparation, promptly further is added in the compositions of normally used component in the detergent applications.
Therefore, compositions of the present invention can contain optional ingredient, for example surfactant, soil suspender, builder, chelating agen, bleach-activating, radical scavenger, pigment, enzyme, dye transfer inhibitor, solvent, buffer agent, foam inhibitor, optical white, brightening agent, dyestuff, spice etc. and their mixture.
Compositions of the present invention provides good detergency ability, especially the spot to bleaching.In fact, described compositions is particularly useful for laundry detergent, laundry pretreating agent, promptly disperses before washing and is retained in the compositions on the fabric or uses to strengthen the laundry additive of its performance with detergent.The dish washing compositions that described compositions also is particluarly suitable for using in table-ware washing machine or the hand washing, as the carpet cleaner that directly is applied on the carpet or in carpet cleaner, use, as cleaning agent for flush toilet, as hard surface cleaner, as artificial tooth cleaning agent or as sterile products.
In one embodiment, the present composition is a form of emulsion.Contained at least a HLB and be higher than the surfactant system emulsifying that 11 hydrophilic surfactant and at least a HLB are lower than 11 hydrophobic surfactant by above-mentioned at α monoalkylation described in the described emulsion or alkoxylate percarboxylic acids.
The emulsion advantages associated that obtains with said method according to the present invention be described emulsion contain high level from the α monoalkylation of a specified rate or the peracid of α monoalkoxy carboxylic acid, and reduced the decomposition rate of described peracid when storing, promptly obtained the stability of improving." stability of improvement " is meant that reaching half the required time that crosses acid concentration at first in the compositions of given form of emulsion spends the required time of acid concentration greater than reaching at first in the same combination that is not form of emulsion herein.Crossing acid concentration can measure according to above-mentioned article.
Therefore, emulsion of the present invention preferably contains by the hydrogen peroxide of emulsion gross weight 0.5%-20% or its water-soluble sources, more preferably 2%-15%, most preferably 3%-10%.Preferred emulsion of the present invention contains by the described peracid of emulsion gross weight 0.005%-15% or their mixture, more preferably 0.01%-10%, most preferably 0.01%-5%.
Emulsion of the present invention contains hydrophilic and hydrophobic surfactant or their mixture by emulsion gross weight 1%-50%, preferred 2%-40%, more preferably 3%-30%.Emulsion contains the hydrophobic surfactant by emulsion gross weight at least 0.1%, and preferably at least 1%, more preferably at least 2% and, preferably at least 1%, more preferably at least 2% at least by the hydrophilic surfactant of emulsion gross weight 0.1%.
In the preferred embodiment of emulsion of the present invention, emulsification system satisfies equation:
With
Weight %A+ weight %B=100% wherein HLB (X) is meant the HLB that wants emulsive component, want emulsive several components if exist, X be meant they all (the weight average % of each component in formula), HLB (A) is meant the HLB of hydrophilic surfactant or its mixture, and HLB (B) is meant the HLB of hydrophobic surfactant or its mixture.Contain compositions as the α monoalkylation or the α monoalkoxy carboxylic acid of peracid precursors
The present invention also comprises the compositions that contains aforesaid α monoalkylation or α monoalkoxy carboxylic acid or their mixture and hydrogen peroxide or its water-soluble sources.
Described compositions of the present invention contains usually by general composition weight meter 0.01%-60% α monoalkylation or α monoalkoxy carboxylic acid or their mixture, preferred 0.1%-40%, more preferably 0.5%-30%, most preferably 2%-25%.
The known any hydrogen peroxide source of those skilled in the art can be used among the present invention.The suitable source of hydrogen peroxide comprises percarbonate, perborate, peroxide/hydroperoxides, persilicate, persulfate and their mixture.
Be used for suitable organic and inorganic peroxide/hydroperoxides of the present invention and comprise diacyl and dialkyl peroxides/hydroperoxides, for example dibenzoyl peroxide, tert-butyl hydroperoxide, two Laurel acyl peroxides, dicumyl peroxide and their mixture.
Be applicable to that prefabricated peroxy acid of the present invention comprises diperoxy dodecanedioic acid DPDA, crosses magnesium phthalate, crosses lauric acid, benzylhydroperoxide, diperoxyazelaic acid and their mixture.
Compositions of the present invention contains usually by general composition weight meter 0.%-90% hydrogen peroxide or its water-soluble sources or their mixture, preferred 1%-70%, more preferably 2%-40%.
With present composition advantages associated is owing to form corresponding to the peracid that is used for carboxylic acid of the present invention on the spot, they provide good detergency ability, the spot to bleaching especially is as coffee, tea etc.In fact, compositions of the present invention has good detergency ability under low peracid precursors content.
Compositions can contain the known any optional ingredient of those skilled in the art, those for example above-mentioned components.Optional ingredient
Compositions of the present invention can contain by general composition weight meter the most nearly 50% surfactant or their mixture, preferred 0.01%-30%, more preferably 0.1%-25%.It is as known in the art being used for surfactant of the present invention, and it comprises anion, nonionic, both sexes, amphion and cationic surfactant and their mixture.Be applicable to that surfactant of the present invention and hydrogen peroxide are compatible with its source.They also help to contain the scourability of the compositions of described mixture.
Be used for especially suitable anion surfactant of the present invention and comprise formula ROSO
3The water soluble salt of M or acid, wherein R C preferably
6-C
24Alkyl, preferred alkyl or contain C
10-C
20The hydroxy alkyl of moieties, more preferably C
12-C
18Alkyl or hydroxy alkyl, with M be H or cation, for example the ammonium of alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement (for example, methyl-, dimethyl-and trimethyl-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine cation and by alkylamine, quaternary ammonium cation of obtaining of ethamine, diethylamine, triethylamine and their mixture etc. for example).
Be used for other suitable anion surfactant of the present invention and comprise alkyl-diphenyl ether sulfonate and alkyl carboxylate.Other anion surfactant can comprise soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C
9-C
20Linear alkylbenzene sulfonate (LAS), C
8-C
22Uncle or secondary paraffin sulfonate, C
8-C
24Sulfonation polycarboxylic acid, the C of alkene sulfonate, the sulfonation preparation of the thermal decomposition product that passes through alkaline earth metal citrate of description in Britain's special trip description 1082179
8-C
24Alkyl polyglycol ether sulfate (containing up to 10 moles of ethylene oxide); Alkyl ester sulfonate, for example C
14-C
16Methyl ester sulfonate, acylglycerol sulfonate, fatty oil acylglycerol sulfate, alkylphenol oxirane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate; for example, acyl isethinate, N-acyl taurine salt, alkyl succinate and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C
12-C
18Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C
6-C
14Diester), the sulfate of acyl sarcosinates, alkyl polysaccharide, alkyl polyglucoside sulfate (nonionic non-sulfuric acid chemical compound described below) for example, chain primary alkyl sulfate, alkyl polyethoxy carboxylate, for example formula RO (CH
2CH
2O)
k-CH
2COO
-M
+, wherein, R is C
8-C
22Alkyl, k are the integers of 0-10, and M is the cation that forms water soluble salt.Resinic acid and hydrogenated resin acid also are suitable, for example Colophonium, Foral and the resinic acid and the hydrogenated resin acid that are present in or are obtained by tall oil.Other example provides in " surfactant and detergent " (I and II volume, Schwartz, Perry and Berch).Various these class surfactants also general description licensed to the US3929678 of Laughlin etc. on the 30th at December in 1975, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row (being incorporated herein by reference).
The preferred anionic surfactant that is used for compositions of the present invention is alkylbenzenesulfonate, alkyl sulfate, alkyl alkoxy sulfate and their mixture.
Being used for suitable non-ionic surface active agent of the present invention is alcohol ethoxylate and/or propoxylate, and they obtain with various aliphatic alcohol chain length and various degree of ethoxylation commercial.In fact, the HLB value of this alkoxy-based non-ionic surface active agent depends primarily on the chain length of aliphatic alcohol, oxyalkylated character and extent of alkoxylation.The surfactant catalogue is obtainable, and it has listed various surfactants, comprises non-ionic surface active agent, and their HLB values separately.
The appropriate chemical method that preparation is used for non-ionic surface active agent of the present invention comprises with the corresponding pure and mild alkylene oxide of required ratio condensation.This method is known to those skilled in the art and extensively describes in the art.In addition, be applicable to that various alcohol alcoxylates of the present invention derives from various suppliers commercial.
Therefore, being used for suitable non-ionic surface active agent of the present invention is Dobanol
R91-2.5 (HLB=8.1; R is C
9And C
11The mixture of alkyl chain, n be 2.5 and m be 0), or Lutensol
RTO3 (HLB=8; R is C
13Alkyl chain, n be 3 and m be 0), or Lutensol
RAO3 (HLB=8; R is C
13And C
15The mixture of alkyl chain, n be 3 and m be 0), or Tergitol
R25L3 (HLB=7.7; R is C
12-C
15Alkyl chain, n be 3 and m be 0) or Dobanol
R23-3 (HLB=8.1; R is C
12And C
13The mixture of alkyl chain, n be 3 and m be 0), or Dobanol
R23-2 (HLB=6.2; R is C
12And C
13The mixture of alkyl chain, n be 2 and m be 0), or Dobanol
R45-7 (HLB=11.6; R is C
14And C
15The mixture of alkyl chain, n be 7 and m be 0), Dobanol
R23-6.5 (HLB=11.9; R is C
12And C
13The mixture of alkyl chain, n be 6.5 and m be 0), or Dobanol
R25-7 (HLB=12; R is C
12And C
15The mixture of alkyl chain, n be 7 and m be 0), or Dobanol
R91-5 (HLB=11.6; R is C
9And C
11The mixture of alkyl chain, n be 5 and m be 0), or Dobanol
R91-6 (HLB=12.5; R is C
9And C
11The mixture of alkyl chain, n be 6 and m be 0), or Dobanol
R91-8 (HLB=13.7; R is C
9And C
11The mixture of alkyl chain, n be 8 and m be 0) or Dobanol
R91-10 (HLB=14.2; R is C
9-C
11The mixture of alkyl chain, n be 10 and m be 0) or their mixture.The present invention is Dobanol preferably
R91-2.5 or Lutensol
RT03 or Lutensol
RAO3 or Tergitol
R25L3 or Dobanol
R23-3 or Dobanol
R23-2 or their mixture.These Dobanol
RSurfactant is provided by SHELL commercial.These Lutensol
RSurfactant can be obtained and these Tergitol by BASF commercial
RSurfactant can be obtained by UNIONCARBIDE commercial.
Other ionic surfactant pack is drawn together fatty acid C
6-C
24The Polyethylene Glycol of alkanolamide, C6-20 polyglycol ether, molecular weight 1000-80000 and glucamide and alkyl pyrrolidone.
Be used for suitable amphoteric surfactant of the present invention and comprise betanin and sulfobetaines surfactant, their derivant or their mixture.Being used for suitable betanin of the present invention and sulfobetaines surfactant is betanin/sulfobetaines and betaines detergent, wherein molecule contains alkalescence and acidic-group, it forms inner salt, obtains the cation in wide ph range and the molecule of anionic hydrophilic group.Some of these detergents embodiment commonly used describe in US2082275,2702279 and 2255082, are incorporated herein by reference.Preferred betanin and sulfobetaines surfactant are the materials of following formula:
Wherein R1 contains about 24 carbon atoms of the 1-that has an appointment; preferred 8-18; the more preferably alkyl of 12-14 carbon atom, wherein R2 and R3 contain 1-3 carbon atom, preferred 1 carbon atom; wherein n is the integer of 1-10; preferred 1-6, more preferably 1, Y is selected from carboxyl and sulfonyl; wherein the summation of R1, R2 and R3 group is the 14-24 carbon atom, or their mixture.
The example of especially suitable beet alkali surface activator comprises C12-C18 alkyl dimethyl betanin, for example Cortex cocois radicis betanin and C10-C16 alkyl dimethyl betanin, for example lauryl betaine.The Cortex cocois radicis betanin is obtained with trade name Amonyl 265 by Seppic commercial.Lauryl betaine commercial by Albright ﹠amp; Wilson obtains with trade name EmpigenBB/L .
Be used for other suitable amphoteric surfactant of the present invention and comprise having formula R
1R
2R
3The amine oxide of NO, wherein each R1, R2 and R3 independently are 1-30 carbon atoms, preferred 6-30 carbon atom, more preferably 10-20 carbon atom, the most preferably saturated replacement of 8-18 carbon atom or not substituted straight chain or branched alkyl.Being used for preferred amine oxide of the present invention is natural mixed C 8-C10 amine oxide and the C12-C16 amine oxide that is for example obtained by Hoechst.The suitable short chain amine oxide of the present invention that is used for is to have formula R
1R
2R
3The amine oxide of NO, wherein R1 is the C6-C10 alkyl, preferred C8-C10 alkyl and wherein R2 and R3 be 1-4 carbon atom independently, the preferably replacement of 1-3 carbon atom or not replacement, the straight or branched alkyl is more preferably methyl.R1 can be saturated straight chain or branched alkyl.Being used for preferred short chain amine oxide of the present invention is the natural mixed C 8-C10 amine oxide that is for example obtained by Hoechst.
Be used for the derivant that suitable cationic surfactants of the present invention comprises quaternary ammonium, phosphorus, imidazoles and sulfonium compound.Cationic surfactant preferred for the present invention is a quaternary ammonium compound, one or two alkyl that wherein is connected in nitrogen is a 6-30 carbon atom, preferred 10-25 carbon atom, the more preferably saturated straight chain of 12-20 carbon atom or branched alkyl, other alkyl that wherein is connected in nitrogen (is three when an alkyl is aforesaid long chain hydrocarbon groups promptly, when two alkyl are aforesaid long chain hydrocarbon groups, be two) be 1-4 carbon atom independently, the replacement of preferred 1-3 carbon atom or not replacement, the straight or branched alkyl is more preferably methyl.The counter ion counterionsl gegenions that are used for described quaternary ammonium compound are selected from Methylsulfate or metilsulfate etc.
Being used for especially preferred cationic surfactant of the present invention is the QAE chemical compound, as myristyl trimethyl sulfate, cetyl trimethyl sulfate and/or tallow base trimethyl sulfate.This QAE chemical compound can be obtained by Hoechst commercial, or by Albright ﹠amp; Wilson obtains with trade name EMPIGEN CM .
Suitable zwitterionic surfactant pH with relative wide region in identical molecule contains cation and anionic hydrophilic group simultaneously.Typical cation group is a quaternary ammonium group, though also can use other positively charged group, as phosphorus, imidazoles and sulfonium group.Typical anionic hydrophilic group is carboxylate and sulfonate, though also can use other group, as sulfate, phosphonate etc.The general formula of some preferred zwitterionic surfactant is:
R
1-N
+(R
2) (R
3) R
4X
-R wherein
1It is hydrophobic group; R
2And R
3Each is C naturally
1-C
4The alkyl of alkyl, hydroxy alkyl or other replacement, they can also connect to form ring structure with N; R
4Be that the cationic nitrogen atom is connected to part on the hydrophilic group, normally contain alkylidene, hydroxy alkylidene or the poly-alkoxyl of 1-4 carbon atom; With X be hydrophilic group, it is carboxylate or sulfonate groups preferably.Preferred hydrophobic group R
1Be to contain 8-22, preferably be less than 18, more preferably less than the alkyl of 16 carbon atoms.Hydrophobic group can comprise unsaturated bond and/or substituent group and/or linking group, for example aryl, acylamino-, ester group etc.Since cost and stability, preferred usually simple alkyl.
Other concrete zwitterionic surfactant has following general formula:
R
1-C(O)-N(R
2)(C(R
3)
2)
n-N(R
2)
2 (+)-(C(R
3)
2)
n-SO
3 (-)
Or R
1-C (O)-N (R
2) (C (R
3)
2)
n-N (R
2)
2 (+)-(C (R
3)
2)
n-COO
(-)Each R wherein
1Be alkyl, for example contain 8-20, preferably most reach 18, more preferably reach most the alkyl of 16 carbon atoms, each R
2Be hydrogen (when being connected in acylamino-nitrogen), contain the short-chain alkyl or the substituted alkyl of 1-4 carbon atom, be preferably selected from methyl, ethyl, propyl group, the ethyl of hydroxyl replacement or the group of propyl group and their mixture, preferable methyl, each R
3Be selected from hydrogen and hydroxyl, each n is 1-4, preferred 2-3, and more preferably 3 numerical value, it is at any (C (R
3)
2) have no more than one hydroxyl in the group.R
1Group can be a side chain and/or undersaturated, R
2Group can also connect to form ring structure.This class surfactant is C
10-C
14Fatty acyl group acylamino-propylidene (hydroxy propylidene) sulfobetaines, it is obtained with trade name " Varion CAS sulfobetaines " by Sherex Company.
The known any dirt suspension multi-carboxylate polymer of those of skill in the art can be used in the compositions of the present invention, and for example the polycarboxylic acid of homopolymerization or copolymerization or their salt comprise polyacrylate and maleic anhydride and/or acrylic acid copolymer etc.In fact, these dirt suspensions multi-carboxylate polymer can be by polymerization or the suitable unsaturated monomer of copolymerization, the preferably unsaturated monomer of sour form preparation.Can comprise acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, equisetic acid, mesaconic acid, citraconic acid and methylene malonic acid through the suitable multi-carboxylate polymer's of polymerization preparation unsaturated monomer acid.In multi-carboxylate polymer of the present invention, exist and contain the monomer segment that does not have carboxylate groups, as vinyl methyl ether, styrene, ethylene etc. are fit to, as long as this part is no more than about by weight 40%.
What especially be fit to is used for multi-carboxylate polymer of the present invention and can obtains from acrylic acid.Such acrylic acid based polymer that uses among the present invention is the water soluble salt of polymeric acrylic acid.The mean molecule quantity of this base polymer of acid form is preferably about 2000-10000, and more preferably about 4000-7000 most preferably is about 4000-5000.The water soluble salt of such acrylate copolymer comprises, for example, and alkali metal salt, ammonium salt and substituted ammonium salt.Such polymer soluble is known.The application of such polyacrylate in composition of detergent disclosed among the US3308067 of the Diehl that on March 7th, 1967 authorized.
The copolymer of acrylic acid/maleic also can be used as preferred dirt suspension multi-carboxy acid copolymer.This class material comprises the water soluble salt of acrylic acid and maleic acid.The mean molecule quantity of this analog copolymer of acid form is preferably about 2000-100000, and more preferably about 5000-75000 most preferably is about 7000-65000.The acrylates part was generally more preferably from about 10: 1 to 2: 1 about 30: 1 to about 1: 1 with the ratio of maleate part in this analog copolymer.The water soluble salt of this class acrylic acid/maleic acid can comprise, for example, and alkali metal salt, ammonium salt and substituted ammonium salt.This class water soluble acrylate/maleate copolymer is a known substances, and it is described in the nineteen eighty-two December disclosed european patent application 66915 on the 15th.Maleic acid/acrylic acid copolymer of especially preferred mean molecule quantity about 70000.This copolymer is obtained with trade name SOKALAN CP5 by BASF commercial.
Any dirt suspension polyamine polymer well known by persons skilled in the art can also be used for the present invention.Being used for especially suitable polyamine polymer of the present invention is the poly-alkoxylation polyamine.These materials can be easily by the branch subrepresentation of experience structure with following repetitive:
With
The R alkyl of 2-6 carbon atom normally wherein; R
1Can be C
1-C
20Alkyl; Alkoxyl is that ethyoxyl, propoxyl group etc. and y are 2-30, most preferably 10-20; N is at least 2 integer, preferred 2-20, most preferably 3-5; With X-is to obtain anion by quaterisation, for example halogenide, Methylsulfate.
Being used for topnotch preferred polyamine of the present invention is so-called ethoxylation polyvinylamine, i.e. the following oxirane of general formula and the polymeric reaction product of Ethylenimine:
Y=2-30 wherein.The ethoxylation polyvinylamine especially is preferred among the present invention, especially the hexamethylene diamine of ethoxylation tetren and quaternized ethoxylation.
Compositions of the present invention can contain by general composition weight meter 5% dirt suspension multi-carboxylate's polymer and/or polyamine polymer at the most, preferred 0.01%-2%, more preferably 0.1%-1%.
The suitable chelating agen that is used for the present composition comprises any chelating agen well known by persons skilled in the art.Suitable chelating agen comprises, fragrant chelating agent, aminocarboxylate chelating agen, other chelating agen of replacing of phosphine acid salt chelator, polyfunctional group for example, and as ethylenediamine N, N '-disuccinic acid and their mixture.
Be used for suitable phosphine acid salt chelator of the present invention and can comprise Etidronic Acid (ethydronic acid), alkali metal ethane 1-hydroxyl diphosphate and aminophosphonic acid salt compound, comprise that amino alkylidenyl gathers (alkylene phosphonic acids salt), alkali metal ethane 1-hydroxyl diphosphate, nitrilo-trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid salt.Phosphonate compounds can their sour form or the different cationic salt on its some or all of acid functional groups exist.Being used for preferred phosphine acid salt chelator of the present invention is diethylenetriamine pentamethylenophosphonic acid salt (DETPMP).This phosphine acid salt chelator is all obtained with trade name DEQUEST by Meng Shan commercial.
The fragrant chelating agent that polyfunctional group replaces also can be used in the present composition.Referring to the US3812044 that licensed to Connor etc. on May 21st, 1974.The preferred compound of this class acid form is the dihydroxy disulfobenzene, for example 1, and 2-dihydroxy-3,5-disulfobenzene.
Being used for preferred biodegradable cheating agent of the present invention is ethylenediamine N, the ammonium salt of N '-disuccinic acid or its alkali metal or alkaline-earth metal, ammonium or replacement or their mixture.Ethylenediamine N, N '-disuccinic acid, especially (S, S) isomer is described in detail in licensing to the US4704233 of Hartman and Perkins on November 3rd, 1987.Ethylenediamine N, N '-disuccinic acid are commercial available, are for example obtained with trade name ssEDDS by Palmer Research Laboratories.
Be used for suitable aminocarboxylate chelating agen of the present invention and comprise edetate, diethylentriamine pentacetate (DTPA), N-Oxyethylethylenediaminetriacetic acid salt, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid salt, triethylenetetraaminehexaacetic acid salt, ethanol-Diglycocol, trimethylen-edinitrilo-tetraacetic acid (PDTA) and methylglycine oxalic acid (MGDA), be their the sour form or the ammonium salts of their alkali metal, ammonium and replacement.Especially the suitable aminocarboxylate of the present invention that is used for is diethylene-triamine pentaacetic acid (DTPA).
Compositions of the present invention can contain by general composition weight meter 5% chelating agen or its mixture at the most, preferred 0.01%-3%, more preferably 0.05%-1.5%.
Compositions of the present invention also can further contain solvent or their mixture.Be applicable to that solvent of the present invention can be capryl alcohol, isopropyl alcohol, propanol, ethoxylated propoxylated alcohols, butoxy propoxyl group alcohol and/or furfuryl alcohol.
Compositions of the present invention also can contain as the bleach-activating of another kind of optional ingredient or their mixture." bleach-activating " used herein is meant the chemical compound except that carboxylic acid of the present invention, it can with the hydroperoxidation that exists to form peracid.So the peracid of formation has constituted active bleaching agent.Be used for suitable bleach-activating of the present invention and comprise the material that belongs to ester, amide, acid imide or acid anhydride class.The example of such suitable combination thing is disclosed in GB1586769 and GB2143231, and the method that they are prepared into the bead form is described in EP-A-62523.The suitable example that is used for this chemical compound of the present invention is a tetra acetyl ethylene diamine (TAED), 3; 5,5-trimethyl acetyl base sodium sulfocarbolate., as the pelargonamide and the positive pelargonyl group phenolsulfonate (NOBS) of the diperoxy dodecylic acid described among the US4818425 and the peroxide adipic acid in US4259201 for example, described.Same suitable is the N-acyl caprolactam, and it is selected from and replaces or unsubstituted benzoyl caprolactam, caprylyl caprolactam, pelargonyl group caprolactam, caproyl caprolactam, capryl caprolactam, hendecene acyl caprolactam, formoxyl caprolactam, acetyl group caprolactam, propiono caprolactam, bytyry caprolactam, valeryl caprolactam or their mixture.The interested bleach-activating of Special Category is open in EP624154, and especially preferred at this apoplexy due to endogenous wind is acetyl triethyl citrate (ATC).Acetyl triethyl citrate has advantage, because it finally is degraded into citric acid and alcohol, is favourable to environment promptly.In addition, acetyl triethyl citrate has good hydrolytic stability when compositions is stored, and it is effective bleach-activating.
Compositions of the present invention can contain by composition weight meter 30% described bleach-activating or their mixture at the most, preferred 1%-20%, more preferably 2%-10%.
Compositions of the present invention also can contain builder system, and the builder system of any routine is applicable to the present invention.The suitable builder of the present invention that is used for comprises citric acid, is preferably water soluble salt form, formula RCH (COOH) CH
2The derivant of succinic acid (COOH), wherein R is C
10-20Alkyl or alkenyl, preferred C
12-16, or wherein R can be replaced by hydroxyl, sulfo group time sulfenyl or sulfone substituent group.Instantiation comprises lauryl succinate, myristyl succinate, cetyl succinate, 2-laurylene base succinate, 2-tetradecene base succinate.The succinate builder comprises sodium, potassium, ammonium and the use of alkanol ammonium salts form preferably with their water soluble salt form.
Other suitable builder is the oxo disuccinate for example described in US4663071 and the mixture of tartrate monosuccinic acid and tartrate disuccinic acid.
Being used for other suitable builder of the present invention is the fatty acid builder, comprises saturated or unsaturated C
10-C
18Fatty acid, and corresponding soap.Preferred saturate contains 12-16 carbon atom in alkyl chain.Preferred unsaturated fatty acid is an oleic acid.
Compositions of the present invention can contain by general composition weight meter 5% builder or their mixture at the most, preferred 0.1%-3%, more preferably 0.1%-2%.
The present invention will be further specified by following embodiment.
The following composition the method according to this invention of embodiment obtains; And contain following component with following ratio: component (by weight %) I II III IV V VI Dobanol91-10 1.2----7Dobanol91-2.5 4.8-----hydrogen peroxide 7.0 45 10 7 35 62-methyl are crossed glutaric acid 1.8-----2-methylglutaric acid-30 55 20 3 citric acid 6--1-1 sulfuric acid 1.9 20 1-15-spices 0.5-0.2 0.2-0.2LAS--2 2-2 water, and-----------------------------------component (by weight %) VII VIII IX X XI XII Dobanol 91-10 1.2----7Dobanol 91-2.5 4.8-----hydrogen peroxide 7.0 45 10 7 35 62-methyl are crossed butanedioic acid 1.8-----2-methylsuccinic acid-30---32, the 4-dimethylated pentanedioic acid, and-------------------------------------LAS is C to aequum to 5--citric acid 6--1-1 sulfuric acid 1.9 20 1-15-spices 0.5-0.2 0.2-0.2LAS--2 2-2 water to 5-20-2-methyl pimelic acid to aequum12Linear alkylbenzene sulfonate (LAS) the method according to this invention prepares peracid
Following method obtains peracid such as the 2-methyl is crossed succinic acid, 2 by implementing, and 4-dimethyl two crosses 1,3-propanedicarboxylic acid or the 2-methyl is crossed 1,5-pentanedicarboxylic acid..With 0.02mol2-methylsuccinic acid, 2,4-dimethylated pentanedioic acid or 2-methyl 1,5-pentanedicarboxylic acid. are dissolved in the 18g concentrated sulfuric acid aqueous solution (by weight 95%).Then under agitation with every kind of solution be added to the hydrogen peroxide concentrated solution excessive (by weight 36%) by dropping and contact with respect to peracid precursors 100%.Behind the solution that adds described hydrogen peroxide, reactant mixture stirred 50 minutes in room temperature (about 30 ℃).The yield that the 2-methyl is crossed succinic acid is 26%.2, the yield that 4-dimethyl two is crossed 1,3-propanedicarboxylic acid is 20%.The yield that the 2-methyl is crossed 1,5-pentanedicarboxylic acid. is 65%.
Claims (16)
1. method for preparing peracid, described method are included in the step that makes carboxylic acid and hydrogen peroxide or the reaction of its water-soluble sources in the water-bearing media, it is characterized in that described carboxylic acid is α monoalkylation carboxylic acid and/or α monoalkoxy carboxylic acid.
2. according to the process of claim 1 wherein that described carboxylic acid is α monoalkylation or α monoalkoxy monocarboxylic acid or their mixture with following formula:
Wherein R1 is 1-26, and preferred 2-18 is individual, more preferably the alkyl of 2-14 carbon atom, wherein R2 is 1-14, the alkyl or the alkoxyl of preferred 1-8 carbon atom, and/or have the α monoalkylation or the α monoalkoxy polycarboxylic acid of following formula or their mixture:
Wherein R1 and R3 are H or 1-26, and preferred 2-18, the more preferably alkyl of 2-14 carbon atom, R2 are hydrogen or 1-14, preferably the alkyl or the alkoxyl of 1-8 carbon atom; Wherein n is 2-20, the integer of preferred 2-12; Y is H or carboxyl, wherein when in given molecular formula, repeating, Y and R2 have separately identical or different implication and wherein in molecule at least two Y be carboxyl and be the alkyl or the alkoxyl of 1-14 carbon atom with respect at least one R2 on the alpha position of at least one described carboxyl.
3. according to the method for claim 2, wherein said carboxylic acid is that 2 Methylpropionic acid, 2-propionic acid ethyl, 2 methyl caproic acid, 2-methyloctanoic acid, 2-methoxyl group are sad, 2-methyl lauric acid, 2-ethyl lauric acid, 2-ethyoxyl lauric acid, 2-propyl group lauric acid, 2-methyl adipic acid, 2-methylsuccinic acid, 2-methoxyl group succinic acid, 2,3-dimethyl succinate, 2-methyl 1,5-pentanedicarboxylic acid., 2-ethyoxyl 1,5-pentanedicarboxylic acid., 2,6-dimethyl-g diacid, 2 ethyl glutaric acid, 2-methylglutaric acid, 2,4-dimethylated pentanedioic acid or their mixture.
4. according to the method for above-mentioned arbitrary claim, wherein said carboxylic acid is 0.5-20 with described carboxylic acid than described hydrogen peroxide or its source with described hydrogen peroxide or its water-soluble sources, preferred 1-10, and more preferably the molar ratio of 1-5 reacts.
5. according to the method for above-mentioned arbitrary claim, up to 8, preferred 0-6 more preferably carries out under the 0-4 under 0 ℃-40 ℃ temperature and at pH for it.
6. according to the method for above-mentioned arbitrary claim, it also comprises the step that at least a annexing ingredient, described hydrogen peroxide or its water-soluble sources and the described carboxylic acid in addition that dewater is provided.
7. according to the method for claim 6, wherein said annexing ingredient is selected from surfactant, soil suspender, builder, chelating agen, bleach-activating, radical scavenger, pigment, enzyme, dye transfer inhibitor, solvent, buffer agent, foam inhibitor, optical white, brightening agent, dyestuff, spice and their mixture.
8. the method that contains the Aquo-composition of peracid according to each preparation among the aforesaid right requirement 1-7, wherein said peracid is higher than 11 hydrophilic surfactant containing at least a HLB, preferred HLB is lower than 11 hydrophobic surfactant above 12 non-ionic surface active agent and at least a HLB, preferred HLB is lower than emulsifying in the surfactant system of 10 non-ionic surface active agent, and described method comprises the steps:
1-prepares peracid according to each method among the claim 1-7;
The 2-preparation contains the hydrophobic mixture of at least a described hydrophobic surfactant;
3-preparation contains the hydrophilic mixture of water and described hydrophilic surfactant at least;
If the described peracid of 4-is hydrophilic, in described hydrophilic mixture, if or described peracid be hydrophobic, the compositions that in described hydrophobic mixture, obtains in the blend step 1;
5-mixes described hydrophobic mixture and described hydrophilic mixture then,
Wherein step 1,2 and 3 can any order be carried out.
9. compositions, it contains α monoalkylation or α monoalkoxy percarboxylic acids or their mixture.
10. according to the compositions of claim 9, wherein said percarboxylic acids is α monoalkylation or single percarboxylic acids of α monoalkoxyization or their mixture with following formula:
Wherein R1 is 1-26, and preferred 2-18 is individual, more preferably the alkyl of 2-14 carbon atom, wherein R2 is 1-14, the alkyl or the alkoxyl of preferred 1-8 carbon atom, and/or have the α monoalkylation or the many percarboxylic acids of α monoalkoxyization of following formula or their mixture:
Wherein R1 and R3 are that H or 1-26 are individual, and preferred 2-18 is individual, more preferably the alkyl of 2-14 carbon atom; R2 is that hydrogen or 1-14 are individual, the alkyl or the alkoxyl of preferred 1-8 carbon atom; Wherein n is 2-20, the integer of preferred 2-12; Y is H or crosses carboxyl, wherein when in given molecular formula, repeating, Y and R2 have separately identical or different implication and wherein in molecule at least two Y be carboxyl and be the alkyl or the alkoxyl of 1-14 carbon atom with respect at least one R2 at least one described alpha position of crossing carboxyl.
11. require among the 9-10 each compositions according to aforesaid right, it contains by the described α monoalkylation of general composition weight meter 0.005%-50% or α monoalkoxy percarboxylic acids or their mixture, preferred 0.01%-30%, more preferably 0.01%-20%.
12. require among the 9-11 each compositions according to aforesaid right, it is a form of emulsion, wherein said α monoalkylation or α monoalkoxy percarboxylic acids or their mixture are preferably contained at least a HLB and are higher than 11 hydrophilic surfactant, preferred HLB is higher than 12 non-ionic surface active agent and at least a HLB and is lower than 11 hydrophobic surfactant, and preferred HLB is lower than the surfactant system emulsifying of 10 non-ionic surface active agent.
13. a compositions, it contains α monoalkylation or α monoalkoxy carboxylic acid or their mixture and hydrogen peroxide or its water-soluble sources.
14. compositions according to claim 13, it contains by the described α monoalkylation of general composition weight meter 0.01%-60% or α monoalkoxy carboxylic acid or their mixture, preferred 0.1%-40%, more preferably 0.5%-30%, with the hydrogen peroxide of pressing general composition weight meter 0.5%-90% or its water-soluble sources or their mixture, preferred 1%-70%, more preferably 2%-40%.
15. according to each compositions among the claim 13-14, wherein said carboxylic acid is α monoalkylation or α monoalkoxy monocarboxylic acid or their mixture with following formula:
Wherein R1 is 1-26, and preferred 2-18 is individual, more preferably the alkyl of 2-14 carbon atom, wherein R2 is 1-14, the alkyl or the alkoxyl of preferred 1-8 carbon atom, and/or have the α monoalkylation or the α monoalkoxy polycarboxylic acid of following formula or their mixture:
Wherein R1 and R3 are that H or 1-26 are individual, and preferred 2-18 is individual, more preferably the alkyl of 2-14 carbon atom; R2 is that hydrogen or 1-14 are individual, the alkyl or the alkoxyl of preferred 1-8 carbon atom; Wherein n is 2-20, the integer of preferred 2-12; Y is H or carboxyl, wherein when in given molecular formula, repeating, Y and R2 have separately identical or different implication and wherein in molecule at least two Y be carboxyl and be the alkyl or the alkoxyl of 1-14 carbon atom with respect at least one R2 on the alpha position of at least one described carboxyl.
16. require among the 9-15 each compositions according to aforesaid right, wherein said compositions also contains annexing ingredient, and it is preferably selected from surfactant, soil suspender, builder, chelating agen, bleach-activating, radical scavenger, pigment, enzyme, dye transfer inhibitor, solvent, buffer agent, foam inhibitor, optical white, brightening agent, dyestuff, spice and their mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96202168.9 | 1996-07-31 | ||
| EP96202168A EP0822183A3 (en) | 1996-07-31 | 1996-07-31 | A process for forming a peracid and a composition comprising said peracid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1231599A true CN1231599A (en) | 1999-10-13 |
Family
ID=8224253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198352A Pending CN1231599A (en) | 1996-07-31 | 1997-07-22 | Process for forming a peracid and composition comprising said peracid |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0822183A3 (en) |
| JP (1) | JPH11514040A (en) |
| CN (1) | CN1231599A (en) |
| AU (1) | AU3808497A (en) |
| BR (1) | BR9710911A (en) |
| CA (1) | CA2261745A1 (en) |
| CZ (1) | CZ29699A3 (en) |
| PL (1) | PL331414A1 (en) |
| TR (1) | TR199900176T2 (en) |
| WO (1) | WO1998004659A2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105443A (en) * | 2008-03-28 | 2011-06-22 | 埃科莱布有限公司 | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| CN101448925B (en) * | 2006-05-22 | 2011-09-28 | 宝洁公司 | Liquid detergent composition for improved grease cleaning |
| US9242879B2 (en) | 2012-03-30 | 2016-01-26 | 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 |
| US9288992B2 (en) | 2013-03-05 | 2016-03-22 | Ecolab USA, Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
| US9290448B2 (en) | 2008-03-28 | 2016-03-22 | Ecolab USA, Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US9540598B2 (en) | 2008-03-28 | 2017-01-10 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
| US9585397B2 (en) | 2013-03-05 | 2017-03-07 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| CN107530457A (en) * | 2014-12-18 | 2018-01-02 | 艺康美国股份有限公司 | Peroxyformic acid is produced by polyalcohol formic acid esters |
| US9902627B2 (en) | 2011-12-20 | 2018-02-27 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4455591B2 (en) | 2004-12-22 | 2010-04-21 | 富士フイルム株式会社 | Disinfectant composition containing ω-alkoxyperoxycarboxylic acid |
| JP5132930B2 (en) * | 2006-12-27 | 2013-01-30 | 花王株式会社 | Liquid detergent composition |
| US9752105B2 (en) | 2012-09-13 | 2017-09-05 | Ecolab Usa Inc. | Two step method of cleaning, sanitizing, and rinsing a surface |
| AU2015364492B2 (en) | 2014-12-18 | 2018-08-09 | Ecolab Usa Inc. | Methods for forming peroxyformic acid and uses thereof |
| US10172351B2 (en) | 2015-09-04 | 2019-01-08 | Ecolab Usa Inc. | Performic acid on-site generator and formulator |
| WO2017044806A1 (en) | 2015-09-10 | 2017-03-16 | Ecolab Usa Inc. | Self indicating antimicrobial chemistry |
| CN112312769A (en) | 2018-06-15 | 2021-02-02 | 埃科莱布美国股份有限公司 | On-site generated performic acid composition for teat treatment |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2813896A (en) * | 1952-12-12 | 1957-11-19 | Bayer Ag | Process for preparing organic peracids |
| NL93455C (en) * | 1955-12-23 | |||
| DE1170926B (en) * | 1962-02-01 | 1964-05-27 | Degussa | Process for the production of solutions of pure low molecular weight perfettic acids |
| FR1492059A (en) * | 1966-03-29 | 1967-11-22 | Electrochimie Soc | Improvements in the preparation of percarboxylic acids |
| GB1216999A (en) * | 1968-04-05 | 1970-12-23 | Petrocarbon Dev Ltd | Improvements in or relating to the production of percarboxylic acids |
| BE808108A (en) * | 1972-12-22 | 1974-05-30 | Degussa | PROCESS FOR THE PREPARATION OF SOLUTIONS OF PERCARBOXYLIC ACID IN ORGANIC SOLVENTS |
| FR2421168A1 (en) * | 1978-03-28 | 1979-10-26 | Propylox Sa | PROCESS FOR THE MANUFACTURE OF CARBOXYLIC PERACIDS |
| US4487723A (en) * | 1982-01-04 | 1984-12-11 | Monsanto Company | Substituted-butanediperoxoic acids and process for bleaching |
| DE3468861D1 (en) * | 1983-06-02 | 1988-02-25 | New Japan Chem Co Ltd | Process for preparing carboxylic acid |
| DE3681973D1 (en) * | 1985-06-14 | 1991-11-21 | Procter & Gamble | DIPERCARBONIC ACIDS AND BLENDER. |
| DE3539036A1 (en) * | 1985-11-04 | 1987-05-07 | Degussa | DIPEROXYGLUTARIC ACIDS SUBSTITUTED IN 2-POSITION, A METHOD FOR THE PRODUCTION AND THEIR USE |
| US4988451A (en) * | 1989-06-14 | 1991-01-29 | Lever Brothers Company, Division Of Conopco, Inc. | Stabilization of particles containing quaternary ammonium bleach precursors |
| GB9225609D0 (en) * | 1992-12-08 | 1993-01-27 | Unilever Plc | Detergent composition |
-
1996
- 1996-07-31 EP EP96202168A patent/EP0822183A3/en not_active Withdrawn
-
1997
- 1997-07-22 CZ CZ99296A patent/CZ29699A3/en unknown
- 1997-07-22 JP JP10508934A patent/JPH11514040A/en active Pending
- 1997-07-22 TR TR1999/00176T patent/TR199900176T2/en unknown
- 1997-07-22 CA CA002261745A patent/CA2261745A1/en not_active Abandoned
- 1997-07-22 BR BR9710911-8A patent/BR9710911A/en not_active Application Discontinuation
- 1997-07-22 CN CN97198352A patent/CN1231599A/en active Pending
- 1997-07-22 WO PCT/US1997/012824 patent/WO1998004659A2/en not_active Application Discontinuation
- 1997-07-22 AU AU38084/97A patent/AU3808497A/en not_active Abandoned
- 1997-07-22 PL PL97331414A patent/PL331414A1/en unknown
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101448925B (en) * | 2006-05-22 | 2011-09-28 | 宝洁公司 | Liquid detergent composition for improved grease cleaning |
| US10323218B2 (en) | 2008-03-28 | 2019-06-18 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US10017720B2 (en) | 2008-03-28 | 2018-07-10 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US10669512B2 (en) | 2008-03-28 | 2020-06-02 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| CN102105443A (en) * | 2008-03-28 | 2011-06-22 | 埃科莱布有限公司 | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US9290448B2 (en) | 2008-03-28 | 2016-03-22 | Ecolab USA, Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US9359295B2 (en) | 2008-03-28 | 2016-06-07 | Ecolab USA, Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US9540598B2 (en) | 2008-03-28 | 2017-01-10 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
| US10077415B2 (en) | 2008-03-28 | 2018-09-18 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
| US9676711B2 (en) | 2008-03-28 | 2017-06-13 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US11015151B2 (en) | 2008-03-28 | 2021-05-25 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US11827867B2 (en) | 2008-03-28 | 2023-11-28 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US9253978B2 (en) | 2008-03-28 | 2016-02-09 | Ecolab USA, Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US9902627B2 (en) | 2011-12-20 | 2018-02-27 | Ecolab Usa Inc. | Stable percarboxylic acid compositions 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 |
| US9242879B2 (en) | 2012-03-30 | 2016-01-26 | 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 |
| US10023484B2 (en) | 2012-03-30 | 2018-07-17 | 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 |
| US10017403B2 (en) | 2012-03-30 | 2018-07-10 | Ecolab Usa Inc. | Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water |
| US11939241B2 (en) | 2012-10-05 | 2024-03-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| US11180385B2 (en) | 2012-10-05 | 2021-11-23 | Ecolab USA, Inc. | Stable percarboxylic acid compositions and uses thereof |
| US9585397B2 (en) | 2013-03-05 | 2017-03-07 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| 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 |
| US11026421B2 (en) | 2013-03-05 | 2021-06-08 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
| US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
| US11206826B2 (en) | 2013-03-05 | 2021-12-28 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
| US9288992B2 (en) | 2013-03-05 | 2016-03-22 | Ecolab USA, Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
| CN107530457A (en) * | 2014-12-18 | 2018-01-02 | 艺康美国股份有限公司 | Peroxyformic acid is produced by polyalcohol formic acid esters |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998004659A2 (en) | 1998-02-05 |
| CZ29699A3 (en) | 1999-07-14 |
| EP0822183A2 (en) | 1998-02-04 |
| WO1998004659A3 (en) | 1998-05-14 |
| EP0822183A3 (en) | 1998-07-29 |
| JPH11514040A (en) | 1999-11-30 |
| CA2261745A1 (en) | 1998-02-05 |
| PL331414A1 (en) | 1999-07-19 |
| AU3808497A (en) | 1998-02-20 |
| BR9710911A (en) | 2000-05-02 |
| TR199900176T2 (en) | 1999-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1231599A (en) | Process for forming a peracid and composition comprising said peracid | |
| CN1101464C (en) | Detergent compositions comprising multiperacid-foaming bleach activators | |
| CN1265135A (en) | Laundry pretreatment process and bleaching compsns. | |
| CN1073714A (en) | Detergent bleach compositions | |
| CN1208364A (en) | Stable emulsions comprising a hydrophobic liquid ingredient | |
| JP2000505136A (en) | Peracids, stable aqueous compositions containing peracids, and methods of forming peracids | |
| CA2352140C (en) | Peroxycarboxylic acid containing bleach compositions | |
| ES2249044T3 (en) | WHITENING COMPOSITIONS. | |
| CN102471725A (en) | Liquid cleaning compositions | |
| SK32999A3 (en) | Laundry pretreatment process and bleaching compositions | |
| CN1379807A (en) | Bleaching compositions | |
| CN1738844A (en) | Partially esterified copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, vinylaromatic compounds and other monoethylenically unsaturated monomers containing heteroatoms | |
| CN1252093A (en) | Liquid aqueous cleaning compositions | |
| JP3874832B2 (en) | Liquid bleach composition | |
| CN1237202A (en) | Laundry bleaching processes and compositions | |
| CN1337994A (en) | Bleaching compositions | |
| MXPA02000106A (en) | Bleaching compositions. | |
| JP2003306699A (en) | Specific polymer-including detergent composition | |
| CN1242798A (en) | Liquid aqueous bleaching compositions and pretreatment process | |
| JPH07305094A (en) | Liquid bleaching agent composition | |
| JP3382338B2 (en) | Liquid bleach composition | |
| JP3330230B2 (en) | Bleach detergent composition | |
| JP3330226B2 (en) | Liquid bleach composition | |
| JP3408306B2 (en) | Bleach composition | |
| JP3499065B2 (en) | Liquid bleach composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1022852 Country of ref document: HK |