CN1057971A - The common sulphating method of ethoxylated alcohol and unsaturated fatty alcohol - Google Patents
The common sulphating method of ethoxylated alcohol and unsaturated fatty alcohol Download PDFInfo
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- CN1057971A CN1057971A CN 91101809 CN91101809A CN1057971A CN 1057971 A CN1057971 A CN 1057971A CN 91101809 CN91101809 CN 91101809 CN 91101809 A CN91101809 A CN 91101809A CN 1057971 A CN1057971 A CN 1057971A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Abstract
The present invention relates to alkyl ethoxylated alcohol and unsaturated fatty alcohol are total to the method that sulfation prepares the mix products system.This mix products system can be neutralized into mixed surfactant system.This method comprises with formula being the unsaturated alcohol of R-OH, and R is C
8-C
22Alkenyl and formula are R
1(OCH
2CH
2)
nThe alkyl ethoxylated alcohol of OH is sulfation together, R
1Be C
8-C
20Alkyl, n are 1～10 integers (comprising 1 and 10).Final product is the mix products system.This mix products system can be neutralized into the mixed surfactant system of the neutral salt that comprises described acidic sulfate.
Description
The invention relates to the common process of sulfating of alkyl ethoxylated alcohol and unsaturated fatty alcohol.Particularly, in method involved in the present invention, alkyl ethoxylated alcohol and unsaturated fatty alcohol sulfation together form the product of mixing system, and this product system contains the acidic sulfate and the unsaturated fatty acidic sulfate of alkyl ethoxylated.This product of mixing system can be neutralized, thereby forms the blended surfactant system.
Ethoxylated alcohol after the neutralization and unsaturated fatty acids alcohol sulfate are excellent surfactant, and are widely used in strong detergent, gentle washings, shampoo and other cleaning products.The unsaturated fatty acids vitriol of some kinds, as grease sodium sulfate, because its solvability, whipability, detergency and gentle performance, and become particularly preferred tensio-active agent.And the mixture of the vitriol of these ethoxylated alcohol and unsaturated fatty alcohol demonstrates the good washing performance.
But, use sulfur acidizing reagent, as SO
3, H
2SO
4And ClSO
3H, the reaction on the two keys of unsaturated alcohol reactant makes the sulphating complexity of unsaturated alcohol.So because the by product that side reaction produces, the sulfation reaction that adopts these common sulfur acidizing reagents to carry out unsaturated alcohol generally obtains low-quality product.And, even unsaturated alcohol fully sulfation obtain under the situation of pure products, this method also needs reagent expensive or that be difficult to operate usually, maybe needs to be not suitable for making this method to reach the reaction conditions of commercial production scale.Therefore, just need a kind of method for preparing unsaturated acid sulfuric ester of exploitation, traditional in the method commercial sulphuric acid reagent can use, and the sulphating product that obtains in the method is substantially free of the by product that side reaction causes.
Unsaturated fatty alcohol is carried out the existing in the literature report of Sulfated method.The United States Patent (USP) of authorizing Hailwood 2,079,347 that deliver May 4 nineteen thirty-seven discloses a kind of method for preparing unsaturated sulfuric ester, and wherein undersaturated long-chain alcohol or its mixture are handled with the adduct of sulphur trioxide and amine.In the method for the disclosure, unsaturated long-chain alcohol changes into their sulfuric ester or their salt, and not reaction generation on its unsaturated link(age).
The United States Patent (USP) of delivering November 16 nineteen thirty-seven of authorizing McAllister 2,099,214 discloses a kind of to the Sulfated method of unsaturated alcohol, wherein said alcohol and the reagent react of being made up of the affixture of sulphur trioxide and dioxane.When preparation affixture reactant, available chlorine sulfonic acid replaces sulphur trioxide.
The United States Patent (USP) of authorizing Siebenburger 2 that on November 10th, 1936 delivered, 060,254, disclose a kind ofly in the presence of excessive organic bases, make the addition compound reaction of unsaturated fatty alcohol and sulphur trioxide and liquid organic bases generate the method for the sulfuric ester of described alcohol.This sulfuric ester prepares under the condition that does not form other sulfonated products, and the example of these sulfonated products has the SO of passing through
3The H group replaces that hydrogen atom forms or by the sulfuric acid residue unsaturated link(age) is added and is shaped as.
The United States Patent (USP) 2 of authorizing people such as Snoddy that deliver April 6 nineteen thirty-seven, 075,914, disclose a kind of usefulness and reacted by (a) sulphur trioxide and metal chloride, or (b) reagent of chlorsulfonic acid and metal chloride or metal sulfate prepared in reaction to the Sulfated method of unsaturated alcohol.
To the Sulfated method of ethoxylated compound also is known in the literature.The United States Patent (USP) of authorizing Lengyel 4 that on August 7th, 1984 delivered, 464,292, a kind of method for preparing blended ethoxylated alcohol/ethoxy sulfate tensio-active agent is disclosed, wherein contain ethoxylated alcohol and or the starting mixt of alkyl alcohol or alkylaryl alcohol by sulfation partly, the conversion of preferably carrying out 50-80% generates the corresponding vitriol of initial reactant.
The United States Patent (USP) 3,687,999 of authorizing people such as Kapur that on August 29th, 1972 delivered, disclose a kind of in the presence of a small amount of or micro-borohydride, to the process of sulfating of ethoxylation long chain aliphatic or ethoxylated alkylphenol.
The United States Patent (USP) of authorizing Beiser 3,565,939 that on February 23rd, 1971 delivered discloses by using sulphating reagent such as H
2SO
4, SO
3Described ethoxylated alcohol sulphating is prepared the sulfuric ester of ethoxylated alcohol with chlorsulfonic acid.
The mixture of reaction products that sulphating method altogether of the present invention is produced contains the acidic sulfate of unsaturated fatty acidic sulfate and alkyl ethoxylated, this mixture can be neutralized and form the blended surfactant system, and this system contains the salt of described acidic sulfate.The composition that contains the composition of the ethoxylated sulfate that mixes with other compositions and contain the unsaturated fatty acids alcohol sulfate that mixes with other compositions also is known in the literature.The United States Patent (USP) 3,676,374 of authorizing people such as Zaki that on July 11st, 1972 delivered discloses a kind of liquid detergent composition, and said composition comprises alkylsulfonate, sulfonated or its mixture, ethoxylated alcohol or alkylphenol sulfate, and enzyme.
On June 9th, 1987 delivered authorizes people's such as Erilli United States Patent (USP) 4,671,895, discloses a kind ofly with paraffin sulfonate, and the higher alcohol sulfate of ethoxylation, nonionogenic tenside and a spot of alcohol sulfate are the liquid detergent composition on basis.
The United States Patent (USP) 3,979,340 that on September 7th, 1976 delivered authorizes people such as Klisch discloses a kind of liquid detergent composition, and said composition contains the mixture of the short infusion of alkene sulfonate, Alkylgruppe thoxamer vitriol and alkanolamide.
The United States Patent (USP) of authorizing Bentley 3 that on December 3rd, 1974 delivered, 852,221 disclose a kind of liquid detergent composition, and said composition contains fatty acid acyl amine component, sulfonated hydrotropic agent, the water-soluble alcohol and water of monohydroxy of alkene sulfonate, ether alcohol sulfate, replacement.
The United States Patent (USP) of authorizing Renaud 4,102,826 that on July 25th, 1978 delivered discloses a kind of liquid washing agent, and this washing composition contains C
14And/or C
15The paraffin monosulfonate most preferably is and complementary anionic detergent as the sulfation b-oxide of high fatty alcohol and the rudimentary strand alkylolamide of higher fatty acid, to coexist as in the water medium.
The United States Patent (USP) 4,052,342 of authorizing people such as Fernley that on October 4th, 1977 delivered discloses a kind of detergent composition, and said composition contains from C
10-C
18Low brilliant degree secondary alkyl sulfate and alcohol ethoxy vitriol and/or pure b-oxide that alkene is derived and.
The United States Patent (USP) 4 of authorizing people such as Takahashi that deliver November 1 nineteen eighty-three, 412,945 disclose a kind of highly enriched tensio-active agent paste, this paste contains the higher alcohols b-oxide vitriol of 50wt% at least and has molecular-weight average about 4,000-10,000 and the Voranol EP 2001 of the alkyl of 8-16 carbon atom.
But, the reaction of above-mentioned reference all openly is not total to the sulphating method, in its common sulphating method the pure and mild alkyl ethoxylated alcohol of unsaturated fatty acids together sulfation the product of mixing system is provided, this product system contains the acidic sulfate and the unsaturated fatty acidic sulfate of alkyl ethoxyquin.Therefore, one object of the present invention just provides a kind of like this method.
Another object of the present invention provides a kind of like this sulphating method altogether, and wherein traditional commercial sulphuric acid reagent can use, and reaction conditions can make it reach commercial production scale.
The present invention has realized these purposes.
The present invention relates to prepare the method for product of mixing system, this product system can be neutralized into the blended surfactant system.Described method comprises that (structural formula is R-OH, and wherein R is the C of straight or branched to make unsaturated fatty alcohol
8-C
22Alkenyl) and the alkyl ethoxylated alcohol (structural formula is R
1(OCH
2CH
2) nOH, wherein R
1Be C
8-C
20Alkyl, n is the integer of 1-10, comprises 1 and 10) mixture and sulfur acidizing reagent reaction, wherein unsaturated fatty alcohol add the alkyl ethoxylated alcohol to the molar ratio range of sulfur acidizing reagent from about 1: 1 to about 5: 1, generate the product of mixing system, this product system comprises that structural formula is R-OSO
3The unsaturated fatty acids acid sulfuric ester of H and structural formula are R
1(OCH
2CH
2) nOSO
3The alkyl ethoxyquin acidic sulfate of H.
According to the present invention, altogether sulphating method described herein comprises, makes the mixture sulfation of the pure and mild alkyl ethoxylated alcohol of unsaturated fatty acids with sulfur acidizing reagent, generates the mix products system that contains unsaturated fatty acids acid sulfuric ester and alkyl ethoxyquin acidic sulfate.This mix products system can be neutralized into mixed surfactant system, and mixed surfactant system contains the neutral salt of described acidic sulfate.
In sulphating method altogether of the present invention, structural formula is the unsaturated fatty acids alcohol reactant of R-OH, and wherein R is the C of straight or branched
8-C
22Thiazolinyl better is C
15-C
21Straight-chain alkenyl, preferably oil (oleyl) base, with structural formula be R
1(OCH
2CH
2) alkyl ethoxylated alcohol sulfation, the wherein R together of nOH
1Be C
8-C
20Alkyl better is C
10-C
16Alkyl, preferably C
10Alkyl, and n is the integer (comprising 1 and 10) of 1-10, better is the integer (comprising 3 and 8) of 3-8, preferably about 5.To point out that importantly the R group of unsaturated fatty acids alcohol reactant can not be an aromatic group, can not contain any aromaticity side group.
Unsaturated or the polyunsaturated fat of any list pure can be in sulphating method altogether of the present invention sulfation.The example that can be used as the unsaturated fatty acids alkylol cpd of reactant in the methods of the invention comprises (but being not limited to this) oleyl alcohol, suitable-11-cetene-1-alcohol, 3,7,11,15-tetramethyl--2-cetene-1-alcohol, the pure and mild anti-oleyl alcohol of suitable-7-tetradecene-1-, with oleyl alcohol for most preferably.
Though any alkyl ethoxylated alcohol can both be in altogether sulphating method of the present invention sulfation, to every molar sulphur acidifying reagent, must have an oxyethyl group in the molecule of alkyl ethoxylated alcohol at least.The example that can be used as the alkyl ethoxylated alcohol compound of reactant in the method for the invention comprises (but being not limited to this) CH
3(CH
2)
11(OCH
2CH
2)
3OH, CH
3(CH
2)
15(OCH
2CH
2)
4OH, CH
3(CH
2)
9(OCH
2CH
2)
5OH, CH
3(CH
2)
17(OCH
2CH
2)
2OH and CH
3(CH
2)
13(OCH
2CH
2)
7OH is CH with the structural formula
3(CH
2)
9(OCH
2CH
2)
5The alkyl ethoxylated alcohol compound of OH is for most preferably.
Many sulfur acidizing reagents well known by persons skilled in the art can be used to alkyl ethoxylated alcohol of the present invention and unsaturated fatty acids alcohol reactant sulfation.The example of be sure oing the concrete reagent that can use here comprises sulfuric acid, sulphur trioxide, chlorsulfonic acid, sulfuric acid methoxyl group ethyl ester sodium, sulfuric acid methoxy ethoxy ethyl ester sodium, oleum, pyridine SO
3And thionamic acid.Preferred sulfur acidizing reagent comprises sulfuric acid, chlorsulfonic acid and pyridine SO
3, again with sulfuric acid for most preferably.
The unsaturated fatty acids alcohol reactant adds that alkyl ethoxylated alcohol reactant is that preferably from about 1: 1 to about 3: 1, most preferred mol ratio was about 1: 1 from about 1: 1 to about 5: 1 to the molar ratio range of sulfur acidizing reagent.
The typical reaction mixture of the present invention comprises the about 35%wt of about 10%-, the about 25%wt of more typical about 15%-, the unsaturated fatty acids alcohol reactant of most typical about 22%wt; The about 50%wt of about 15%-, the about 35%wt of more typical about 25%-, the alkyl ethoxylated alcohol reactant of most typical about 31%wt; And the about 30%wt of about 10%-, more typical about 15%-is about 20%, the sulfur acidizing reagent of most typical about 17%wt.
Though be not to select for use, when the preparation reaction mixture, also can comprise solvent.When sulfation reaction carries out in the presence of solvent altogether, solvent generally will constitute the about 40%wt of about 10%-of reaction mixture, and more typical is the about 35%wt of about 25%-that constitutes reaction mixture, and most typical is the about 29%wt that constitutes reaction mixture.The solvent that can here use comprises ether and other organic compound.The example that is used as the ether compound of solvent in the present invention comprises dioxane, THF, Anaesthetie Ether and other ether.The example that is used as other organic compound of solvent in the present invention comprises methylene dichloride and hexane.Anaesthetie Ether most preferably in these solvents.To point out that importantly alcohol can not be used as solvent in the method for the invention.
Above-described altogether sulfation reaction carries out in about 0 ℃-Yue 80 ℃ temperature range typically, more typically is to carry out in about 20 ℃-Yue 60 ℃ temperature range.
The time cycle that sulfation reaction altogether of the present invention carries out is typically from about 2 hours to about 8 hours, more typically from about 3 hours to about 6 hours, the most typically from about 3.5 hours to about 4.5 hours.
Though not necessarily, sulfation reaction altogether of the present invention is typically carrying out in the vacuum range of the about 0.1mmHg of about 0.01-, is more typically carrying out in about 0.06mmHg scope from about 0.04-.The effect of vacuum is to remove relating to preferred H
2SO
4The water that generates in the sulfating reaction of sulfur acidizing reagent, and any solvent that uses in the reaction, this just makes the product productive rate reach maximum value.Off-gas pump also can be used for method of the present invention.Off-gas pump is used to remove altogether more issuable products of sulfation reaction of the present invention (as, the HCl that produces during as sulfur acidizing reagent when chlorsulfonic acid).Off-gas pump also can be used for removing any solvent that uses in the dereaction.
Mix products system from altogether sulphating method of the present invention obtains typically comprises the about 35%wt of about 20%-, the structural formula of the most about 35%wt is R-OSO
3The unsaturated fatty acids acid sulfuric ester of H, wherein R such as preamble define: typically comprise the about 45%wt of about 25%-, the structural formula of the most about 45%wt is R
1(OCH
2CH
2) nOSO
3The alkyl ethoxyquin acidic sulfate of H, wherein R
1Define with n such as preamble; Comprise the about 30%wt of 0%-, the typically about 10%wt of 0%-, the solvent of 0%wt the most typically; And comprise be less than 40%wt, typically be less than 30%wt, the most typically be less than initial reactant and the byproduct of reaction of about 20%wt.The mix products system that obtains from method of the present invention generally will not contain any solvent, because reaction generally carries out under vacuum, and the solvent that exists will be evacuated and extract.
Such just as recognized by those skilled in the art, the concrete reaction conditions of the inventive method will depend on the concrete reactant and the sulfur acidizing reagent of use, and they also mutual restriction.
In the method for the invention, the sulphating of unsaturated fatty acids alcohol reactant mainly occurs on the hydroxyl.Typically about 90%, more typically about 95%, the most typically surpass initial unsaturated alcohol reactant sulfation on its hydroxyl of 99%.If do not retrained by theory, the existence of believing alkyl ethoxylated alcohol co-reactant has been played mitigate effects to the sulfation reaction of unsaturated fatty alcohol, and this just helps suppressing sulfonation side reaction and the reaction on the two keys of unsaturated alcohol.The other benefit relevant with its bisulphate ester products with the ethoxylated alcohol reactant is that the isomerization of unsaturated fatty acids acid sulfuric ester product to anti-oil-based compounds do not take place basically.Another benefit of the present invention is, from this altogether the mix products system that obtains of sulphating method must further not handle, can help neutralization to satisfy the application of most of product by nationality.
In most preferably scheme of the present invention, the oleyl alcohol of equimolar amount and CH
3(CH
2)
9(OCH
2CH
2)
5The OH quilt is sulfation together.In the presence of ether solvents, the sulfur acidizing reagent sulfuric acid of equivalent is used for to these alcohol reactant sulfations, contains oil base acidic sulfate and CH so generated
3(CH
2)
9(OCH
2CH
2)
5OSO
3The mix products system of H.The present invention this most preferably the common sulfation reaction of scheme be under the vacuum of about 40 ℃-Yue 50 ℃ temperature range, about 4 hours time and about 0.05mmHg, to carry out.
These coreactions are undertaken by following formula:
The product of the common sulphating method of the present invention is unsettled often, therefore, should pass through the method known to those skilled in the art neutralized reaction product, generates the salt of prepared acidic sulfate.The example that is used to generate the neutralization reagent of these salt comprises the compound of those alkali metal containings or amido.These neutral salt are as tensio-active agent.
Just as described herein, the inventive method in and the mix products system can be used as the detergent composition of washing clothes.
Detergent composition
The laundry composition that can prepare the neutralized reaction product that contains the inventive method.These compositions are specially adapted to the washing operation of textiles.Use neutralization reaction product of the present invention can prepare solid and liquid detergent composition.Said composition generally contains the neutralized reaction product of the present invention of the about 40%wt of about 1%wt-.
Additional detergent components
Use the laundry composition of the neutralized reaction product preparation of the inventive method, also can contain the common detergent component and the ancillary component of this area convention amount.
Detergent surfactant
It is few to about 1% that surface active agent composition can constitute this paper laundry composition, but preferably said composition will contain the tensio-active agent of the 5%-that has an appointment about 40%, more preferably contains about 10%～30% tensio-active agent.
Concerning the softness of the washing of optimal combination and fabric, the composition of negatively charged ion (preferably linear alkylbenzene sulfonate) and nonionic (the preferably many ethoxylated alcohol of alkyl) tensio-active agent is preferred, but the tensio-active agent of other kinds also can use as semi-polarity, both sexes, zwitter-ion and cats product.These surfactant mixtures can also be:
A. nonionic detergent tensio-active agent
13 hurdles 14 that suitable nonionic detergent tensio-active agent briefly is disclosed in the people's such as Laughlin that delivered on December 30th, 1975 United States Patent (USP) 3,929,678 walk in 16 hurdles, 6 row, quote it as a reference at this.Useful nonionogenic tenside kind comprises:
1. the polyoxyethylene alkene condensate of alkylphenol.These compounds comprise the condenses of alkylphenol and ethylene oxide, and the alkyl of alkylphenol contains about 12 carbon atoms of about 6-, and can be linear configuration or chain configuration, and the amount that ethylene oxide exists is equivalent to every mole of alkylphenol about 25 moles ethylene oxide of 5-of will having an appointment.The example of this type compound comprises the condenses of condenses, diisooctyl phenol and about 15 mole ethylene oxides of every moles of phenol of condenses, binonylphenol and about 15 mole ethylene oxides of every moles of phenol of condenses, 4-dodecylphenol and about 12 mole ethylene oxides of every moles of phenol of nonyl phenol and about 9.5 mole ethylene oxides of every moles of phenol.Commercial available such ionic surfactant pack is drawn together Igepal
TMCO-630, GAF company sells; And Triton
TMX-45, X-114, X-100 and X-102 are Rohm ﹠amp; Haas company sells.
2. the condenses of fatty alcohol and about 25 mole ethylene oxides of about 1-.The alkyl chain of fatty alcohol can be straight or branched, primary alkyl or secondary alkyl, and contains about 22 carbon atoms of the 8-that has an appointment usually.Particularly preferably be and contain from the alcohol of about 20 carbon atom alkyls of about 10-and the condenses of about 10 mole ethylene oxides of the about 4-of every mol of alcohol.The example of this ethoxylated alcohol comprises the condenses of tetradecyl alcohol and about 10 mole ethylene oxides of every mol of alcohol, and the condenses of coconut alcohol (fatty alcohol mixture that alkyl chain length changes between the 10-14 carbon atom) and about 9 mole ethylene oxides.The example of commercial available this type nonionogenic tenside comprises Tergitol
TM15-S-9(C
11-C
15The condenses of straight chain alcohol and 9 mole ethylene oxides), Tergitol
TM24-L-6 NMW(C
12-C
14The condenses of primary alconol and 6 mole ethylene oxides has narrow molecular weight distribution), be Union Carbide Corporation and sell; Neodol
TM45-9(C
14-C
15The condenses of straight chain alcohol and 9 mole ethylene oxides), Neodol
TM23-6.5(C
12-C
13The condenses of straight chain alcohol and 6.5 mole ethylene oxides), Neodol
TM45-7(C
14-C
15The condenses of straight chain alcohol and 7 mole ethylene oxides), Neodol
TM45-4(C
14-C
15The condenses of straight chain alcohol and 4 mole ethylene oxides), being shell (Shell) chemical company sells; And Kyro
TMEOB(C
13-C
15The condenses of alcohol and 9 mole ethylene oxides), Procter ﹠amp; Gamble company sells.
3. the condenses of ethylene oxide and the hydrophobic group that forms by propylene oxide and propylene glycol condensation.The hydrophobic part of these compounds has the molecular weight of about 1500-about 1800, and presents water-insoluble.Polyoxyethylene partly is added to the trend that improves whole macromolecule water-solubility on the hydrophobic part, the liquid property that accounts for about 50% o'clock product of condenses gross weight up to the polyoxyethylene amount is recovered, and this is corresponding to the ethylene oxide condensation about 40 moles with as many as.The example of this type compound comprises some commercial available Pluronic
TMTensio-active agent, Wyandotte chemical company sells.
4. the condenses of ethylene oxide and propylene oxide and reacting ethylenediamine products therefrom.The hydrophobic part of these products is made of the reaction product of quadrol and excessive oxidation propylene, generally has the molecular weight of about 2500-about 3000.Hydrophobic part and ethylene oxide condensation contain the polyoxyethylene of the about 80%wt of about 40%-up to condenses, and have about 5, the molecular weight of 000-about 11,000.The example of this type nonionogenic tenside comprises some commercial available Tetronic
TMCompound, Wyandotte chemical company sells.
5. semi-polar nonionic surfactants comprises water-soluble amine oxides, and this amine oxide contains the alkyl of a part about 10-about 18 carbon atoms and two portions and is selected from the alkyl that contains about 3 carbon atoms of about 1-and the group of hydroxyalkyl; Alkyl and two portions that water miscible phosphine oxide, this phosphine oxide contain about 18 carbon atoms of the about 10-of a part are selected from the alkyl of about 3 carbon atoms of about 1-and the group of hydroxyalkyl; And water miscible sulfoxide, an alkyl and a part that this sulfoxide contains about 18 carbon atoms of the about 10-of a part are selected from the alkyl of about 3 carbon atoms of about 1-and the group of hydroxyalkyl.
Preferred semi-polarity nonionic detergent tensio-active agent is to have structural formula
Amine oxide surfactant, R wherein
2Be alkyl, hydroxyalkyl or alkyl phenyl or its mixture that contains about 22 carbon atoms of about 8-; R
3Be alkylidene group or hydroxy alkylidene or its mixture that contains about 3 carbon atoms of about 2-; X from 0 to about 3; And each R
4It is the polyoxyethylene thiazolinyl that contains the alkyl or the hydroxyalkyl of about 3 carbon atoms of about 1-or contain about 3 the ethylene oxide groups of about 1-.R
4Group can be connected with each other, and as by a Sauerstoffatom or nitrogen-atoms, forms a ring structure.
Preferred amine oxide surfactant is oxidation C
10-C
18Alkyl dimethyl amine and oxidation C
8-C
12The alkoxyl oxygen alkyl ethyl diethanolamine.
6. disclosed alkyl polysaccharide class thing in the United States Patent (USP) of delivering on January 21st, 1986 of authorizing Llenado 4,565,647, this alkyl polysaccharide class thing have a hydrophobic group and a polyose (as poly-glycosides) hydrophilic group.This hydrophobic group contains about 30 carbon atoms of the 6-that has an appointment, about 16 carbon atoms of preferably about 10-; This hydrophilic group contains about 10, about 3, about 2.7 sugar units of about 1.6-most preferably of about 1.5-preferably of the 1.5-that has an appointment.Any reductibility carbohydrate that contains 5 or 6 carbon atoms all can use, as the alternative glucosyl group part of glucose, semi-lactosi and galactosyl part.(hydrophobic group at random is attached at positions such as 2-, 3-, 4-, so make glucose or semi-lactosi and glucoside or galactoside position opposite.) between the carbohydrate keyed jointing can, as, add between the position and the unitary 2-of aforementioned sugars, 3-, 4-and/or 6-position of saccharide unit.
Optionally, and extremely do not need, the polyoxyalkylene chain can embed hydrophobic part and polyose part.Preferred alkylene oxide is an ethylene oxide.That typical hydrophobic group comprises is saturated or unsaturated, side chain or non-side chain, contain about 18, the alkyl of about 16 carbon atoms of about 10-preferably of about 8-.Preferred alkyl is the straight chain saturated alkyl.Alkyl can contain nearly 3 oh groups and/or polyalkyleneimine chain can contain up to about 10, preferably less than 5 alkylene oxide parts.Suitable alkyl polysaccharide class thing is octyl group, nonadecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl two, three, four, five and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises coconut alkyl two, three, four and five glucosides and fatty oil alkyl four, five and six glucosides.
Preferred alkyl polyglycoside thing has structural formula
R
5O(CnH
2nO) x t(glycosyl)
R wherein
5The group that is selected from has alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl or its mixture, and the alkyl group here contains about 18, about 14 carbon atoms of about 12-preferably of about 10-; N is 2 or 3, preferably 2; T is about 10 from 0-, and preferably 0; And x is about 10 from about 1.3-, and is preferably about 3 from 1.3-, most preferably is from about 1.3-about 2.7.Glycosyl is preferably from glucose.For preparing these compounds, at first the many ethoxy alcohols of synthol or alkyl make itself and glucose or source of glucose react again, generate glucoside (linking on the 1-position).The glycosyl units that adds then can they 1-position and 2-, 3-, 4-and/or the 6-position of front glycosyl units, preferably mainly be to link between the 2-position.
7. has structural formula
Fatty acid amide surfactant, R wherein
6Be to contain the preferably about 9-about 17 of the about 21(of about 7-) alkyl and each R of individual carbon atom
7The group that is selected from has hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl and-(C
2H
4O) xH, the x here change between about 1 to about 3.
Preferred acid amides is C
8-C
20Glutamine, single ethanol amide, diglycollic amide and isopropanol amide.
B. anionic detergent tensio-active agent
Be applicable to the anionic detergent tensio-active agent of the laundry composition that contains neutralized reaction product of the present invention, briefly be disclosed in United States Patent (USP) 3,929,678(1975 delivered December 30, authorize people such as Laughlin) 23 hurdles 58 walk to 29 hurdles 23 row and United States Patent (USP)s 4,294,710(1981 delivered October 13, authorized people such as Hardy) in.These two pieces of patents are incorporated herein by reference.Useful anion surfactant kind comprises:
1. common alkali metal soap, as contain about 24 carbon atoms of about 8-, preferably contain sodium salt, sylvite, ammonium salt and the pure ammonium salt of about 20 the carbon atom higher fatty acid of about 10-.Preferred alkali metal soap is sodium laurate, sodium stearate, sodium oleate and potassium palmitate.
2. the water-soluble salt of organosulfur acid-respons product, preferably an alkali metal salt, ammonium salt and pure amine salt.This product has alkyl group and acid sulphonate or the bisulphate ester group that contains about 20 carbon atoms of about 10-in its molecular structure.(moieties of fatty acyl group is included in the term " alkyl ".）
This group examples of anionic surfactants is sodium alkyl benzene sulfonate and alkyl benzene sulphonate (ABS) potassium, and wherein alkyl group contains about 15 carbon atoms of about 9-, can be the straight or branched configuration.For example, in the people's such as Guenther that deliver on November 5th, 1940 the United States Patent (USP) 2,220,099 and those types of describing in the United States Patent (USP) 2,477,383 of the Lewis that delivers December 26 nineteen forty-six.Useful especially is linear alkylbenzene sulfonate, and wherein the carbon atom average number of alkyl group is about 13 from about 11-, is abbreviated as C
11-C
13LAS.
Other anion surfactant comprises the alkyl glycerylether sodium sulfonate, and especially those are from the derive ether of the higher alcohols that comes of tallow and Oleum Cocois; Coco-nut oil fatty acid coconut monoglyceride and sodium sulfate; Alkylphenol inferior ethoxyl ether sodium sulfate or sylvite, wherein every mole contains about 10 ethylene oxide units of about 1-and alkyl group contains about 12 carbon atoms of about 8-.
The water-soluble salt that also comprises α-sulfonated fatty acid ester contains about 20 carbon atoms of about 6-in its fatty acid group, contain about 10 carbon atoms of about 1-in the ester group; The water-soluble salt of 2-fat acyloxy alkane-1-sulfonic acid contains about 9 carbon atoms of about 2-, alkane partly contains about 23 carbon atoms of about 9-in its fatty acyl group; The alkyl-sulphate (AS) that contains about 20 carbon atoms of about 10-in the alkyl group; Such as those structural formulas is R
8O(C
2H
4O) mSO
3The vitriol of M, wherein R
8Be C
10-C
16Alkyl (preferably) or hydroxyalkyl group, m is about 4 from about 0.5-, and M is the compatible positively charged ion that contains the sulfonation of olefin thing water-soluble salt of about 24 carbon atoms of about 12-; And contain about 3 carbon atoms of about 1-and contain the β-alkoxy alkane sulfonate of about 20 carbon atoms of about 8-at paraffin section at alkyl group.Useful sulfated alkyl ether is described in detail in United States Patent (USP) 4,807, and in 219, this patent was delivered on March 26th, 1985, authorized Hughes, was incorporated herein by reference.The about 18%wt(of about 8%-that above-mentioned tensio-active agent preferably occupies composition is basic calculation with acid), more preferably about 9%-about 14%.
The preferred alkyl ethoxylated sulphate surfactants of said structure formula is those wherein R
8Substituting group is C
12-C
15Alkyl group and m are from the material of about 1.5-about 3.These examples of substances are C
12-C
15The many oxyethyl groups of alkyl (2.25) vitriol (C
12-15E
2.25S); C
14-15E
2.25S; C
12-13E
1.5S; C
14-15E
3S; And composition thereof.
The particularly preferred tensio-active agent that is used for liquid detergent composition is a straight chain C
11-C
13Alkylbenzene sulfonate, alkyl-sulphate and alkyl ethoxylated sulfate (negatively charged ion), C
12-C
13Many ethoxy alcohols of alkyl (nonionic) and composition thereof.Contain alkyl and/or alkyl ethoxyquin vitriol and preferably include as the liquid detergent composition of detergent surfactant and be no more than this kind detergent surfactant of about 5%, and the ion-pair complex of anion mixture C preferably
11-C
13LAS or benzene sulfonate.The particularly preferred tensio-active agent that is used for granulated detergent is a straight chain C
11-C
13Alkylbenzene sulfonate and C
8-C
18Alkyl-sulphate and composition thereof.The mixture of these two kinds of anion surfactants most preferably, wherein linear alkylbenzene sulfonate to the weight ratio of alkyl-sulphate from about 0.5: about 3: 1 of 1-more preferably is from about 0.5: about 2: 1 of 1-.
3. anion phosphate tensio-active agent.
4.N-the succinamate that alkyl replaces.
C. amphoterics
Amphoterics can briefly be described as the aliphatic derivatives of secondary amine or tertiary amine, or the aliphatic derivatives of heterocyclic secondary and tertiary amine, wherein the fat base can be that straight or branched and one of them aliphatic substituting group contain about 18 carbon atoms of about 8-, and at least one aliphatic substituting group contains the anionic water-soluble group, as carboxyl, sulfonate, vitriol.As the example of useful here amphoterics, referring to United States Patent (USP) 3,929, people such as 678(Laughlin published on December 30th, 1975) 19 hurdles 38 walk to 22 hurdles, 48 row, and this patent is incorporated herein by reference.
D. zwitterionics
Zwitterionics can briefly be described as the derivative of secondary amine and tertiary amine, the derivative of heterocyclic secondary and tertiary amine, or the derivative of quaternary ammonium salt, quaternary phosphine or uncle's sulfonium compound.As the example of useful here zwitterionics, referring to United States Patent (USP) 3,929, people such as 678(Laughlin published on December 30th, 1975) 19 hurdles 38 walk to 22 hurdles, 48 row, and this patent is incorporated herein by reference.
E. cats product
Cats product also is used for containing the laundry composition of the neutralized reaction product of the inventive method.Cats product comprises a big compounds, it is characterized in that one or more organic hydrophobic grouping and the quaternary nitrogen that is usually to link to each other with acidic group in the positively charged ion.Azo-cycle compound is also thought the quaternary nitrogen compound.Suitable anionic compound is halogenide, Methylsulfate and oxyhydroxide.PH value less than about 8.5 washing soln in, tertiary amine has the character similar with cats product.
Suitable cationic surfactants comprises having structural formula:
〔R
9（OR
10）y〕〔R
11（OR
10）y〕
2R
12N
+X
-
Quaternary ammonium surfactant, R wherein
9Be alkyl or the alkyl phenyl group that contains about 18 carbon atoms of about 8-in the alkyl chain; Each R
10Be independently selected from group-CH
2CH
2-,-CH
2CH(CH
3)-,-CH
2CH(CH
2OH)-and-CH
2CH
2CH
2-; Each R
11Be independently selected from group C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl, two R
11Group connect together the ring structure that forms ,-CH
2CHOHCHOHCOR
13CHOHCH
2OH(is R wherein
13Be any hexose or molecular weight less than 1000 hexose polymkeric substance) and hydrogen (when y is not 0); R
12With R
11Identical, or such alkyl, wherein a R
9Add R
12 total carbon atom number is not more than about 18; Each y is 0-about 15 from the summation of 0-about 10 and y value; And X is any compatible negatively charged ion.
The preferred example of above-claimed cpd is the quaternary ammonium alkyl tensio-active agent, especially the single-long-chain alkyl tensio-active agent of describing in the said structure formula, R at this moment
12Be selected from and R
11Identical group.Most preferred quaternary ammonium surfactant is muriate, bromide and methylsulfuric acid C
8-C
16Alkyl trimethyl ammonium salt, C
8-C
16Alkyl two (hydroxyethyl) methyl ammonium salt, C
8-C
16Alkyl hydroxyethyl dimethyl ammonium salt and C
8-C
16Alkyl oxygen oxypropyl trimethyl ammonium salt.In the above-mentioned quaternary ammonium salt, methylsulfuric acid decyl trimethyl ammonium, Trimethyllaurylammonium chloride, bromination myristyl trimethyl ammonium and chlorination coco group trimethyl ammonium and methylsulfuric acid coco group trimethyl ammonium are preferred especially.
Announcement more comprehensively to these and other useful here cats products sees United States Patent (USP) 4,228,044(Cambre, on October 14th, 1980 published), this patent is incorporated herein by reference.
Detergent builders
The laundry composition that contains the neutralized reaction product of the inventive method also can contain inorganic and/or organic detergent washing assistant, to participate in the adjusting of hardness of minerals.These washing assistants constitute the about 80%wt of 0%-of composition.Liquid formulations preferably includes the about 50%wt of about 5%-, the detergent builders of the about 30%wt of about 5%-more preferably.Granular formula optimization ground comprises the about 80%wt of about 10%-, the detergent builders of the about 80%wt of about 24%-more preferably.
The polyacetic acid salt, carboxylate salt, multi-carboxylate and the polyhydroxy sulfonate that granular and the useful water-soluble organic washing-assisting detergent of liquid composition are comprised various basic metal, ammonium and replacement ammonium.Polyacetic acid salt and multi-carboxy acid salt washing agent's example is sodium salt, sylvite, lithium salts, ammonium salt and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), oxygen di-succsinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.The Citrate trianion form of basic metal or pure ammonium salt (preferably with) the normally form with citric acid is added in the composition, but also full the form of neutral salt add.
Particularly preferred multi-carboxy acid salt washing agent is at United States Patent (USP) 3,308, and 067(Diehl, on March 7th, 1967 published) in open, this patent is incorporated herein by reference.These materials comprise the homopolymer of aliphatic carboxylic acid and the water-soluble salt of multipolymer, and the example of these aliphatic carboxylic acids has toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid.
Other washing assistants are included in United States Patent (USP) 3,723, and 322(Diehl published on March 28th, 1973) in disclosed carboxylated carbohydrate.This patent is incorporated herein by reference.
Found that the ether multi-carboxylate is the useful free phosphate detergent washing assistant material of a class.Some ether multi-carboxylates are disclosed as detergent builders.Useful ether multi-carboxylate's example comprises oxygen di-succinate, has been disclosed in the United States Patent (USP) 3,128 of Berg, and 287(1964 delivered April 7) and people's such as Lamberti United States Patent (USP) 3,635,830(1972 delivered January 18) in.This two patent is incorporated herein by reference.
The ether multi-carboxylate who is used as a kind of particular type of washing assistant in the present invention is those materials with following general formula:
X is H or salt-forming cation.For example, if A in the top general formula and B are H, this compound is exactly oxygen di-succsinic acid and its water-soluble salt so.If A is OH and B is H, this compound is exactly tartrate monosuccinic acid (TMS) and water-soluble salt thereof so.If A is H and B
This compound is exactly tartrate disuccinic acid (TDS) and water-soluble salt thereof so.It particularly preferably is the mixture that uses these washing assistants here.TMS to the weight ratio of TDS from about 97: TMS that 3-is about 20: 80 and TDS mixture are especially preferred.Open in the people's such as Bush that these washing assistants were delivered on May 5th, 1987 the United States Patent (USP) 4,663,071.
Suitable ether multi-carboxylate also comprises ring compound, particularly alicyclic compound, such as those in United States Patent (USP) 3,923,679; 3,835,163; 4,158,635; The compound of describing in 4,120,874 and 4,102,903.All these patents are incorporated herein by reference.
Other useful cleaning washing assistants comprise the ether hydroxypolycarboxylic acid salt that following structural is represented:
Wherein M is hydrogen or positively charged ion, and the salt that obtains here is water miscible, preferably basic metal, ammonium or replacement ammonium cation; N be the about 15(of about 2-preferably n be that about 2-is about 10, more preferably n on average is about 2-about 4) and each R
14Can be identical or different and be selected from hydrogen, C
1-4Alkyl or C
1-4Substituted alkyl (preferred R
14Be hydrogen).
Disclosed 3 in the United States Patent (USP) 4,566,984 of the Bush that on January 28th, 1986 delivered, 3-dicarboxyl-4-oxa--1,6-adipate and related compound thereof, it also is suitable being used for this laundry composition.This patent is incorporated herein by reference.Other suitable washing assistants comprise C
5-C
20Alkyl succinic acid and salt thereof.Such particularly preferred compound is the dodecenyl succinic succsinic acid.
Useful washing assistant comprises that also carboxyl methoxy propyl diacid salt, carboxyl methoxy succinate, suitable hexanaphthene hexacarboxylic acid salt, suitable pentamethylene tetracarboxylic acid hydrochlorate, Phloroglucinol trisulfonate, the water-soluble polyacrylate of sodium and potassium (for example have about 2, the molecular weight of 000-about 200,000) and the multipolymer of maleic anhydride and vinyl methyl ether or ethene.
Other suitable multi-carboxylates are at United States Patent (USP) 4,144, and people such as 226(Crutchfield, on March 13rd, 1979 delivered) in disclosed polyacetal carboxylation, this patent is incorporated herein by reference.These polyacetal carboxylations can prepare by under polymerizing condition the ester of Glyoxylic acid hydrate and initiators for polymerization being put together.Then the polyacetal carboxylic acid ester who obtains is linked on the chemically stable end group,, prevent its depolymerization rapidly in alkaline solution to stablize the polyacetal carboxylic acid ester; The polyacetal carboxylic acid ester is converted into corresponding salt, and is added in the tensio-active agent.
Useful especially washing assistant comprises having general formula R
15-CH(COOH) CH
2(COOH) alkyl succinic acid, the i.e. derivative of succsinic acid, wherein R
15Be alkyl, as C
10-C
20Alkyl or alkenyl, C
12-C
16Preferably; Or R wherein
15Available hydroxyl, sulfo group, Sulfoxy or sulfone substituting group replace.All these all have description in above-mentioned patent.
The succinate washing assistant preferably uses with its water-soluble salt form, and its water-soluble salt comprises sodium salt, sylvite, ammonium salt and pure ammonium salt.
The object lesson of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.
Other useful clean washing assistants comprise C
10-C
18Alkyl list carboxylic (fat) acid and its salt.These lipid acid can get as deriving tallow, Oleum Cocois and the plam oil from the fat and the oil of animal and plant.Suitable saturated fatty acid also can carry out synthetic (for example, by the oil oxidation or by Fisher-Tropsch process to hydrogenation of carbon monoxide).Particularly preferred C
10-C
18The alkyl monocarboxylate is saturated coconut fatty acid, palm kernel fatty acid and composition thereof.
Sequestrant
The detergent composition here also can optionally contain the sequestrant of one or more iron and manganese.The material that these sequestrants can be selected from has fragrant chelating agent and its mixture of aminocarboxylate, amino phosphonates do, multifunctional replacement, and all these materials will offer some clarification on hereinafter.Do not retrain if do not accept opinion, believe that the benefit of these materials partly passes through to form the special ability that water soluble chelate compound removes de-iron and mn ion owing to them from washing soln.
That the aminocarboxylate that is used as optional sequestrant in the present composition has is one or more, at least two structural units preferably
Wherein M is hydrogen, basic metal, ammonium or replaces ammonium (as thanomin) and x is that 1-is about 3, preferably 1.Preferably, these aminocarboxylates do not contain alkyl or the alkylidene group more than about 6 carbon atoms.Practical amine carboxylate salt comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol diamino-acetic acid, its an alkali metal salt, ammonium salt and substituted ammonium salt and composition thereof.
At least when the phosphorus total amount of low levels allowed in detergent composition, amino phosphonates do also was applicable to the sequestrant as the present composition.That useful compound has is one or more, at least two structural units preferably
Wherein M be hydrogen, basic metal, ammonium or replace ammonium and x about 3 from 1-, preferably 1.This compounds comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), nitrilo three (methylene phosphonic acid salt) and diethylenetriamine five (methylene phosphonic acid salt).Preferably, these amino phosphonates do not carbon atom quantity more than 6 alkyl or alkylidene group.Alkylidene group can be shared by aggregated(particle) structure.
Also be useful in the fragrant chelating agent of multifunctional replacement the composition here.These materials comprise having general formula
Compound, at least one R wherein
16Be-SO
3H or-COOH or its water-soluble salt and composition thereof.The United States Patent (USP) 3,812 that is hereby incorporated by reference, 044(1974 delivered May 21, authorized people such as Connor) the fragrant chelating and the sequestering agent of multifunctional replacement disclosed.The preferred compound of this type that exists with sour form is dihydroxyl disulfobenzene and 1,2-dihydroxyl-3,5-disulfobenzene or especially other two sulfonation pyrocatechols.Alkaline detergent composition can contain an alkali metal salt, the ammonium salt of these materials or replace ammonium (as list or trolamine) salt form.
If use, these sequestrants constitute the about 10%wt of about 0.1%-of this paper detergent composition usually.More preferably, sequestrant constitutes the about 3.0%wt of about 0.1%-of said composition.
Stain remover
Useful in the present invention polymkeric substance stain remover comprises cellulose derivative, as the segmented copolymer of hydroxy ethers cellulose polymer compound, ethylene terephthalate and terephthalic acid polyethylene oxide base or poly(propylene oxide) base ester and positively charged ion guar gum or the like.
Derivatived cellulose as stain remover can buy commercial, comprises cellulosic hydroxy ethers such as Methocel
R(Dow) and cationic cellulose ether derivatives such as polymkeric substance JR-124
R, JR-400
RAnd JR-30M
R(Union Carbide Corp).Still referring to the United States Patent (USP) of delivering on December 23rd, 1,975 3,928,213 of authorizing people such as Temple, this patent is incorporated herein by reference.
Other effective stain removers are positively charged ion guar gums, as Jaguar Plau
R(Stein Hall) and Gendrive458
R(General Mills).
The material that used here preferred Mierocrystalline cellulose stain remover is selected from has methylcellulose gum, Vltra tears, hydroxy butyl methyl cellulose or its mixture, described cellulose polymer compound has 15-75 in 20 ℃ the aqueous solution, the viscosity of 000 centipoise.
Stain remover is the statistic copolymer with ethylene terephthalate and terephthalic acid polyethylene oxide ester (PEO) preferably.More particularly, these polymkeric substance comprise the repeating unit of terephthalic acid ethylene glycol and terephthalic acid polyethylene oxide, terephthalic acid ethylene glycol unit to the unitary mol ratio of terephthalic acid polyethylene oxide from about 25: about 35: 65 of 75-, described terephthalic acid polyethylene oxide unit contains the polyethylene oxide of about 2000 molecular weight of the 300-that has an appointment.The molecular weight of this polymkeric substance stain remover is about 25, about 55,000 scopes of 000-.Referring to the United States Patent (USP) of authorizing Hays 3,959,230 that on May 25th, 1976 delivered, this patent is incorporated herein by reference.Also will be referring to the United States Patent (USP) of delivering on July 8th, 1975 of authorizing Basadur 3,893,929(quotes as a reference), this patent disclosure similar multipolymer.Be surprisingly found out that these polymkeric substance stain removers can make the distribution of fabric cooking agent of the present invention and synthetic fabrics such as polyester, nylon, poly-cotton and the acrylic acid or the like of wide range balance each other.The distribution of this more homogeneous of fabric cooking agent causes the raising of fabric cooking quality.
Another preferred polymkeric substance stain remover is the crystallizable polyester that has the ethylene terephthalate repeating unit, this polyester contains the ethylene terephthalate unit of 10-15%wt and the terephthalic acid polyoxyethylene unit of 90-80%wt, the latter is derived from weight-average molecular weight 300-5,000 polyoxyethylene glycol, and in crystallizable polymers ethylene terephthalate unit and the unitary mol ratio of terephthalic acid polyoxyethylene between 2: 1 and 6: 1.The example of this polymkeric substance comprises commercial available material Zelcon
R5126(is from Dupont) and Milease
RT(is from ICI).
The preparation method of aforementioned polymer and they is at european patent application 185, and 417(Gosselink, on June 25th, 1986 published) in have more fully and describe.This patent is incorporated herein by reference.
If use, these stain removers constitute the about 5.0%wt of about 0.01%-of this paper detergent composition usually; Preferably, stain remover constitutes the about 3.0%wt of about 0.2%-of said composition.
Enzyme
Enzyme is preferred ancillary component, and the amount that accounts for whole composition is about 2% from about 0.025%-, preferably from about 0.05%-about 1.5%.The proteolytic activity that preferred proteolytic enzyme should provide is at least about every liter of 5Anson unit (about 1,000,000Delft unit), every liter of the about 70Anson unit of preferably about 15-, every liter of the about 40Anson unit of most preferably about 20-.The proteolytic activity of the about 0.05Anson unit of the about 0.01-of every gram product meets the requirements.Other enzymes comprise amylase, also need to be included in this composition.
Suitable proteolytic enzyme comprises numerous species, has known that these enzymes are applicable to detergent composition.The Savinase that commercial agent prepared from enzyme such as Novo Industries sell
TMAnd Alcalase
TMAnd the Delft of Holland, the Maxatase that Gist-Brocades sells
TMBe fit to.Other preferred enzyme composition comprise the Esperase that those commercial available trade names are SP-72
TM(Copenhagen of Denmark, A/S, Novo Industries production and selling) and AZ-Protease
TM(Delft of Holland, Gist-Brocades production and selling).
Suitable amylase comprises the Rapidase that Gist-Brocades sells
TMTermamyl with Novo Industries sale
TM
Can be at U.S. Patent number 4,101 to disclosing more completely of suitable enzyme, people such as 457(Place, on July 18th, 1978 publishes) and United States Patent (USP) 4,507,219(Hughes, publication on March 26th, 1985) in find.These two patents are incorporated herein by reference.
Other complementary detergent ingredients
When using with the habitual convention amount in this area (usually from 0-about 20%), other complementary compositions that can be included in the detergent composition that uses neutralized reaction product of the present invention comprise solvent, hydrotropic agent, solubilizing agent, suds suppressor, processing material, soil-suspending agent, corrosion inhibitor, dyestuff, filler, white dyes, sterilant, PH conditioning agent (monoethanolamine, yellow soda ash, sodium hydroxide etc.), enzyme stabilizers, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, shale fabric softener, spices etc.
Formula for a product
1. liquid composition
The liquid detergent composition that contains the neutralized reaction product of the inventive method can contain water and other solvents.A spot of low molecular weight primary or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol are suitable solvents.Liquid composition can comprise the neutralized reaction product of the inventive method as unique fabric cooking agent, and maybe this cooking agent also can combine with other fabric cooking agent.The active ingredient of liquid composition can mainly be a fabric conditioner, can comprise as those detergent ingredients disclosed herein, and can comprise that other are cleaned, other compositions that conditioning or this paper specifically do not list.
For liquid detergent composition, preferably include monohydroxy-alcohol so that surfactant dissolves, but the polyvalent alcohol that contains about 6 carbon atoms of about 2-and about 6 oh groups of about 2-can use the stability (if comprising enzyme in the composition) that also can improve enzyme.The example of polyvalent alcohol comprises propylene glycol, ethylene glycol, glycerol and 1,2-propylene glycol.Propylene glycol is particularly preferred alcohol.
The complementary component of other of such these liquid conditioner compositions is just all used always on its essence, and constitutes the about 20%wt of about 0.1%-of composition usually.The complementary composition of these of fabric conditioner comprises (but being not limited to this) tinting material, spices, bacterial inhibitor, white dyes, opalizer, viscosity modifier, fabric power of absorption toughener, emulsifying agent, stablizer, shrinkage control agent, spotting agent, sterilant, mycocide, corrosion inhibitor etc.
Water and the proportional part ground of other solvents in composition depend on the state of gained fabric cooking agent.At ambient temperature, fabric cooking agent must be to be insoluble to product substantially, and in the particle diameter specification of discussing before this.This will limit the quantity of solvent in choice of Solvent and the composition.
Liquid fabric condition composition of the present invention can be by conventional method preparation.
2. granular composition
Granular detergent composition can comprise the neutralized reaction product of the inventive method as unique fabric conditioner, or this amendment also can combine with other fabric conditioner.The active ingredient of granular combination can mainly be a fabric conditioner, can comprise as those detergent ingredients disclosed herein, and can comprise other compositions that clean, conditioning or this paper specifically do not list.
Embodying granular detergent composition of the present invention can form by routine techniques, for example can pass through single component (ion-pair complex exception) pulping in water, mixture to gained carries out spraying drying again, or by shuttle board or cylinder to the composition components granulation.
Aspect clothes washing method of the present invention, the aqueous solution of typically doing washing comprises the detergent composition of the present invention of the about 2%wt of about 0.1%-.Clothes to be washed stirs the effect that just can reach clean, decontamination and cooking fabric in this solution.
Amendment of the present invention is specially adapted to laundry, but also is suitable for as the hair conditioning composition in shampoo and the Wo 2008069000.
The description of front has illustrated essence of the present invention all sidedly.The purpose of embodiment given below is that the present invention will be described.Scope of the present invention is decided by embodiment following claim book.
Unless specify in addition, all parts of this paper, percentage ratio and ratio are all by weight.
The embodiment I
The mix products system that contains unsaturated fatty acids acid sulfate compound and alkyl ethoxyquin acidic sulfate is prepared as follows: the mixture of 2.05g96.4% sulfuric acid and 5ml diethyl ether is cooled to 0 ℃ with ice bath, meanwhile adds 3.78gCH
3(CH
2)
9(OCH
2CH
2)
5OH and 2.68g oleyl alcohol.Remove ice bath then, ether volatilizees under the aspirator pump vacuum.Then under the 0.05mmHg vacuum, reactant is heated to 40-50 ℃ of temperature, kept 4 hours.The product of mixing system contains oil base-OSO
3H, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3H and starting raw material, the pollution that causes by byproduct of reaction that does not have to aware.
The embodiment II
With the method for above-mentioned embodiment I, the bisulphate ester cpds that just will be contained in the mix products system is for further processing by being dissolved in 50ml ethanol, and neutralizes with 25ml 1N NaOH.This final neutralization composition of further handling is the blended surfactant system, and this system contains oil base-OSO
3Na, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3Na and starting raw material, the pollution that causes by byproduct of reaction that does not have to aware.
The embodiment III
The mix products system that contains unsaturated fatty acids acid sulfate compound and alkyl ethoxyquin acidic sulfate is prepared as follows: the mixture of 2.05g96.4% sulfuric acid and 5ml diethyl ether is cooled to 0 ℃ with ice bath, meanwhile adds 3.78gCH
3(CH
2)
9(OCH
2CH
2)
5OH and 2.40g be suitable-11-cetene-1-alcohol.Remove ice bath then, ether volatilizees under the aspirator pump vacuum.Then under the 0.05mmHg vacuum, reactant is heated to 50 ℃ of temperature, kept 4 hours.The mix products system contains CH
3(CH
2)
3CH=CH(CH
2)
10OSO
3H, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3H and starting raw material, the pollution that causes by byproduct of reaction that does not have to aware.
The embodiment IV
With the method for above-mentioned embodiment III, the bisulphate ester cpds that just will be contained in the mix products system is for further processing by being dissolved in 50ml ethanol, and neutralizes with 1N NaOH.This final neutralization composition of further handling is the blended surfactant system, and this system contains CH
3(CH
2)
3CH=CH(CH
2)
10OSO
3Na, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3Na and starting raw material, the pollution that causes by byproduct of reaction that does not have to aware.
The embodiment V
The mix products system that contains unsaturated fatty acids acid sulfate compound and alkyl ethoxyquin acidic sulfate is prepared as follows: 3.78g CH
3(CH
2)
9(OCH
2CH
2)
5OH and 2.96g3,7,11, the 15-tetramethyl--2-cetene-mixture of 1-alcohol in the 25ml diethyl ether is cooled to 0 ℃ with ice bath, meanwhile drips the 2.33g chlorsulfonic acid.Remove ice bath, reactant stirred 2 hours at ambient temperature.Ether volatilizees under the aspirator pump vacuum.The mix products system contains CH
3(CH(CH
3) (CH
2)
3)
3C(CH
3)=CHCH
2OSO
3H, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3H and starting raw material, do not have to aware by with 3,7,11, the pollution that the resulting product of side reaction of 15-tetramethyl--2-cetene-1-alcohol causes.It is to be noted that HCl is a product of sulfation reaction altogether between the special reaction thing of present embodiment.In fact all HCl have removed by the aspirator pump vacuum.
The embodiment VI
With the method for above-mentioned embodiment V, the bisulphate ester cpds that just is contained in the mix products system is for further processing to it by being dissolved in 50ml ethanol, and neutralizes with 1N NaOH.This final neutralization composition of further handling is a mixed surfactant system, and this system contains CH
3(CH(CH
3) (CH
2)
3)
3C(CH
3)=CHCH
2OSO
3Na, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3Na and starting raw material, the pollution that causes by byproduct of reaction that does not have to aware.This neutralization procedure may produce sodium-chlor.Sodium-chlor can be removed by method known to those skilled in the art.
The embodiment VII
The mix products system that contains unsaturated fatty acids acid sulfate compound and alkyl ethoxyquin acidic sulfate is prepared as follows: 3.78g CH
3(CH
2)
9(OCH
2CH
2)
5OH and 2.12g be suitable-and the 7-tetradecene-mixture of 1-alcohol in the 25ml diethyl ether stir down at 0 ℃, meanwhile adds 3.18g pyridine SO
3Reactant stirred 1 hour at ambient temperature, and ether then volatilizees under the aspirator pump vacuum.The mix products system contains CH
3(CH
2)
5CH=CH(CH
2)
6OSO
3H pyridine, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3H pyridine and starting raw material, the pollution that the resulting product of side reaction by with suitable-7-tetradecene-1-alcohol reactant that does not have to aware causes.
The embodiment VIII
With the method for above-mentioned embodiment VII, the bisulphate ester cpds that just is contained in the mix products system is for further processing by being dissolved in 50ml ethanol, and neutralizes with 1N NaOH.This final neutralization composition of further handling is a mixed surfactant system, and this system contains CH
3(CH
2)
5CH=CH(CH
2)
6OSO
3Na, CH
3(CH
2)
9(OCH
2CH
2)
5OSO
3Na, H
2O, pyridine and starting raw material, the pollution that causes by byproduct of reaction that does not have to aware.The vitriol that this neutralization procedure obtains can pass through method known to those skilled in the art (as crystallization from pyridine) from pyridine and H
2Separate among the O.
Claims (13)
1, a kind of method is characterized in that structural formula is the unsaturated fatty alcohol of R-OH, and wherein R is that oil base and structural formula are R
1(OCH
2CH
2)
nThe mixture of the alkyl ethoxylated alcohol of OH, wherein R
1Be straight or branched C
10Alkyl group and n are the integers (comprising 3 and 8) of 3-8, with sulfuric acid reaction, wherein unsaturated fatty alcohol add the alkyl ethoxylated alcohol to the vitriolic molar ratio range from about 1: about 3: 1 of 1-generates and to comprise that structural formula is R-OSO
3Unsaturated fatty acids acid sulfuric ester and the structural formula of H are
R
1(OCH
2CH
2)
nOSO
3The mix products system of the alkyl ethoxyquin acidic sulfate of H.
2, according to the process of claim 1 wherein that n is 5.
3, according to the method for claim 2, wherein the unsaturated fatty acids alcohol reactant adds that alkyl ethoxylated alcohol reactant is about 1: 1 to the mol ratio of sulfur acidizing reagent.
4, according to the method for claim 3, wherein reacting the time range of carrying out is about 2 hours-Yue 8 hours.
5, according to the method for claim 3, wherein reacting the time range of carrying out is about 3 hours-Yue 6 hours.
6, according to the method for claim 3, wherein the time range of reacting between the pure and mild ether sulfuric ester of unsaturated fatty acids is about 4.5 hours of about 3.5-.
7,, wherein be reflected in the about 0 ℃-Yue 80 ℃ temperature range and carry out according to the method for claim 4.
8,, wherein be reflected in the about 20 ℃-Yue 60 ℃ temperature range and carry out according to the method for claim 5.
9,, wherein be reflected in the about 40 ℃-Yue 50 ℃ temperature range and carry out according to the method for claim 6.
10,, wherein be reflected in the vacuum range of the about 0.1mmHg of about 0.01mmHg-and carry out according to the method for claim 7.
11, method according to Claim 8 wherein is reflected in the vacuum range of the about 0.06mmHg of about 0.04mmHg-and carries out.
12, according to the method for claim 3, wherein the mix products system comprises that the about 35%wt structural formula of about 20%-is R-OSO
3The unsaturated fatty acids acid sulfate compound of H and the about 45%wt structural formula of about 25%-are R
1(OCH
2CH
2) nOSO
3The alkyl ethoxyquin bisulphate ester cpds of H.
13, according to the method for claim 12, wherein the mix products system comprises the unsaturated fatty acids acid sulfate compound of about 35%wt and the alkyl ethoxyquin bisulphate ester cpds of about 45%wt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48746490A | 1990-03-01 | 1990-03-01 | |
| US487,464 | 1990-03-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1057971A true CN1057971A (en) | 1992-01-22 |
Family
ID=23935823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91101809 Pending CN1057971A (en) | 1990-03-01 | 1991-03-10 | The common sulphating method of ethoxylated alcohol and unsaturated fatty alcohol |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1057971A (en) |
| WO (1) | WO1991013057A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI713724B (en) * | 2016-03-31 | 2020-12-21 | 美商銀都拉瑪投資氧化物有限責任公司 | Enhanced solubilization using a combination of extended chain surfactants |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312934A (en) * | 1992-11-30 | 1994-05-17 | The Procter & Gamble Company | Synthesis of sulfated polyhydroxy fatty acid amide surfactants |
| GB9226003D0 (en) * | 1992-12-14 | 1993-02-10 | Unilever Plc | Detergent production |
| DE19542569A1 (en) * | 1995-11-15 | 1997-05-22 | Henkel Kgaa | Fatty alcohol (ether) sulfates with improved cold behavior |
| DE10237412A1 (en) * | 2002-08-16 | 2004-02-19 | Cognis Deutschland Gmbh & Co. Kg | Production of sulfated alcohols, useful as mild anionic surfactants in detergents or cosmetics, involves reaction of alcohols with acid sulfation products capable of transferring acid sulfate groups to the alcohol |
| MY174521A (en) * | 2012-04-24 | 2020-04-23 | Stepan Co | Unsaturated fatty alcohol derivatives from natural oil metathesis |
| ES2755108T3 (en) | 2013-03-13 | 2020-04-21 | Stepan Co | Surfactants based on monounsaturated fatty alcohol derivatives |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2044919A (en) * | 1931-05-02 | 1936-06-23 | Unichem Chemikalien Handels A | Lime, magnesia- and acid-resisting sulphonates produced from unsaturated fatty alcohols |
| US4464292A (en) * | 1981-01-02 | 1984-08-07 | Lengyel Stephen P | Mixed ethoxylated alcohol/ethoxy sulfate surfactants and synthetic detergents incorporating the same |
-
1991
- 1991-02-25 WO PCT/US1991/001111 patent/WO1991013057A1/en unknown
- 1991-03-10 CN CN 91101809 patent/CN1057971A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI713724B (en) * | 2016-03-31 | 2020-12-21 | 美商銀都拉瑪投資氧化物有限責任公司 | Enhanced solubilization using a combination of extended chain surfactants |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991013057A1 (en) | 1991-09-05 |
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