CN1182751A - Soil release oligoesters, their preparation and their use in detergents and cleaning compositions - Google Patents
Soil release oligoesters, their preparation and their use in detergents and cleaning compositions Download PDFInfo
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- CN1182751A CN1182751A CN 97121547 CN97121547A CN1182751A CN 1182751 A CN1182751 A CN 1182751A CN 97121547 CN97121547 CN 97121547 CN 97121547 A CN97121547 A CN 97121547A CN 1182751 A CN1182751 A CN 1182751A
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Abstract
The present invention provides oligoesters of formula 1, wherein R[1] and R[7] are linear chain or branching C[1]-C[18] alkyl, R[2] and R[6] are ethylidene, R[3] is 1, 4-phenylene, R[4] is ethylidene, R[5] is ethylidene, 1, 2-propylidene or statistical mixture composed of any two of them, n[1] and n[5] separately are number between 1 and 500, n[2] is a number between 10 and 140, n[3] is a number between 1 and 12, n[4] is a number between 7 and 40, n[3] added by n [4] is at least 11, the manufacturing method, their use in wash and cleaning composition, and wash containing new type oligoesters and the cleaning composition are provided.
Description
The present invention relates to the detergency oligomer ester, relate to their preparation method and relate to their purposes in washing composition and cleaning combination.
The detergency polymkeric substance is the theme of deep development always for many years.Initial exploitation is used as the textiles auxiliary agent of the arrangement usefulness of synthon (especially trevira), and they have been used as so-called washing auxiliary detergent in family expenses washing composition and cleaning combination so far.Except " detergency polymkeric substance ", another generic term that this class has the compound of detergency ability is " refusing dirty agent ", because they make surface treated have the dirt of refusing.
Main detergency polymkeric substance is based on the polyester of terephthalic acid, polyoxyalkylene glycol and monomeric diol.
These compounds owing to they structural similarities, easily absorb from the aqueous solution or washings by polyester textile or by polyester blend fabric, and form hydrophilic film on water-repellent fabrics.This film has the effect of minimizing fabric to the affinity of hydrophobicity oiliness and fatty dirt.Meanwhile, strengthened polyester textile by the wettability of aqueous cleaning solution.Two effects cause oiliness or the easier removal of fatty dirt, and these dirts generally are difficult to remove from polyester textile.
And, on the water vapour permeability (moisture absorption and adsorptivity) of the water-repellent fabrics of handling such as polyester or polyester/cotton BLENDED FABRIC, significant improvement being arranged, this has positive improvement effect to wear resistance.
Also have, the detergency polymkeric substance has also improved antistatic property and slip property.This helps handling fabric in the textile finishing process.
Many patents and patent application disclose the preparation of detergency polymkeric substance, the improvement of their effect and their application method.Use hereinafter and write a Chinese character in simplified form ET (ethylene glycol terephthalate), PET (polyethylene terephthalate) and POET (polyoxyethylene terephthalate).
US-3 557 039 discloses in the presence of the catalyzer that comprises lime acetate and ANTIMONY TRIOXIDE SB 203 99.8 PCT the method from dimethyl terephthalate (DMT) and ethylene glycol detergency polyester.
US-3 959 280 discloses with US-3 557 039 and has used the synthetic method of polyoxyethylene as reactant similarly, in addition.The feature that polyester showed that obtains is that the mol ratio of ET and POET is 25: 75-35: 65, and the molar weight of polyoxyethylene units is 300-700 in POET, and molar weight is 25, and 000-about 55,000 and fusing point are lower than 100 ℃.
Disclosing mean mol in US-4 125 370 is 5000-200,000 random PET-POET multipolymer.PET: the POET ratio is 20: 80-90: change in 10 scopes.It is 300-10 that polyoxyethylene units has molar weight, 000.The preparation of these polymkeric substance is described in US-3 959 280 and in US-3 479 212.
Known polyester not only comprises ethylene oxide group and terephthalic acid units from EP-A-0 241 985, and comprises propylene, 1, and 2-butylidene and/or 3-methoxyl group-propylene and glycerine unit, and by C
1-C
4Alkyl-blocked.
EP-B-0 185 427 discloses a kind of based on dimethyl terephthalate (DMT), ethylene glycol and/or propylene glycol and methyl-or the oligomer ester of ethyl polyoxyethylene glycol, and wherein each molecule on average contains 4-11 terephthalic acid units.
According to US-4 956 447,, can improve the detergency polymer properties by introducing in addition cationization of quaternary ammonium compound.
The sodium salt that US-4 427 557 and EP-A-0 066 944 disclose by using sulfoisophthalic acid carries out anion-modified polyester.Employed polyoxyethylene glycol has molar weight 200-1000g/mol.Obtaining molar weight with the polyreaction of ethylene glycol and terephthalic acid is 200010, the oligomer ester of 000g/mol.
EP-A-0 274 907 discloses the detergency polyester that the sulfo group ethylidene is end capped, contain terephthalate.
US-3 712 873 discloses the textile finishing preparaton that contains the 1-5% polyester, and this polyester is with terephthalic acid, polyoxyethylene glycol and C
2-C
4Aklylene glycol is basic and has molar weight is 30005000.This preparaton can or pad method by spraying and apply.
US-3 512 920 discloses by the low-molecular-weight polyester based on aklylene glycol, polyalkylene glycol and terephthalic acid and has handled cotton/polyester textile with starch derivative or derivatived cellulose, subsequently the method for thermal-setting in addition.
DE-A-22 53 063 discloses a kind of acid textile finishing composition, and it comprises the multipolymer of dicarboxylic acid and polyalkylene glycol or poly-cycloalkylidene glycol, if need also comprise aklylene glycol and cycloalkylidene glycol
WO-92/17523 discloses detergency polyester methyl blocking, that contain terephthalate in washing composition and the purposes in the fabric sofetening agent prescription especially.
The washing composition that comprises nonionogenic tenside and polyoxyethylene glycol and polyethylene terephthalate is disclosed among the DE-A-22 00 911.
EP-A-0 319 094 has described the ET/POET multipolymer is handled clothes in clothes-drying machine purposes.Except they can be used as the detergency polymkeric substance, it is emphasized that their antistatic effects especially to the clothes handled.
The formulation data of detergency polymkeric substance is disclosed in DE-A-33 24 258.By having PET: POET ratio=2-6: 1 PET/POET polyester is dissolved in or is scattered in being ejected on the washing assistant in the liquid nonionic surfactants and with mixture fills a prescription.
With the prior art is background, the present invention seeks to develop a kind of improved detergency oligomer ester.
Have now found that, with dimethyl terephthalate (DMT) and ethylene glycol and/or 1, the 2-propylene glycol is the oligomer ester on basis, the some of them glycol substituted by polyoxyethylene glycol and this oligomer ester by alkyl polyoxyethylene glycol end-blocking, the de-sludging performance that is had significantly is better than those polymkeric substance of prior art.
The invention provides the oligomer ester of general formula 1:
R wherein
1And R
7Be C straight chain or branching
1-C
18Alkyl, R
2And R
6Be ethylidene, R
3Be 1,4-phenylene, R
4Be ethylidene, R
5Be ethylidene, propylene or the statistics mixture that both form arbitrarily, n
1And n
5Be the number among the 1-500 independently of one another, n
2Be the number among the 10-140, n
5Be the number among the 1-12, n
4Be the number among the 7-40, n
3+ n
4Be at least 11.
Preferably, independently of one another, R
1And R
7Be the C of straight chain or branching
1-C
4Alkyl, n
1And n
5Be the number between 3 and 45, n
2Be the number among the 18-70, n
3Be the number among the 2-5, n
4Be the number among the 8-12, and n
3+ n
4It is the number between 12-18 or the 25-35.
Oligomer ester according to the present invention is from dimethyl terephthalate (DMT), ethylene glycol and/or propylene glycol, polyoxyethylene glycol and C
1-C
18Alkyl polyoxyethylene glycol synthetic, method is under the situation of adding catalyzer, under normal pressure, be heated to the about 220 ℃ temperature of 160-and carry out transesterification, the while distillation for removing methanol, under reduced pressure carry out condensation reaction then under the about 240 ℃ temperature of 160-, excessive glycol is removed in distillation simultaneously.Suitable transesterification and condensation catalyst be of the prior art those, example is a titanium tetraisopropylate, dibutyltin oxide and ANTIMONY TRIOXIDE SB 203 99.8 PCT/lime acetate.
The present invention also provides these application of detergency oligomer ester in washing composition and cleaning combination, especially improves the ability that they clean oiliness or fatty dirt, and these washing composition and cleaning combination are provided.
It is Powdered might using the washing composition and the wash products preparaton of oligomer ester of the present invention, granular, pasty state or gel form or liquid or solids wash piece.They contain at least 0.1%, the oligomer ester of the present invention of preferred 0.1-10% and preferred especially 0.2-3%.The desired use that depends on them, the character on the character of the textiles that the composition of preparaton should be adapted to be washed or the surface that is cleaned.They comprise common washing composition and cleaning-product component according to those prescriptions of prior art.The representative example of these washing composition and wash products composition is described below.
The total concn of tensio-active agent in finished product washing composition and wash products prescription is 1%-99% and preferred 5%-80% (all percentage ratio meter) by weight.Spendable tensio-active agent is an anionic, non-ionic type, both sexes or cationic.Also can use these surfactant mixtures.Preferred washing composition and wash products prescription comprise negatively charged ion and/or nonionogenic tenside and itself and other surfactant mixtures.
Suitable anion surfactant is a vitriol, sulfonate, carboxylate salt, phosphoric acid salt and their mixture.Suitable positively charged ion is a basic metal in context, for example sodium or potassium, or alkaline-earth metal, for example calcium or magnesium, and ammonium, substituted ammonium compound, comprise single-, two-or three-ethanol ammonium cation and their mixture.The anion surfactant of following type is special ideal:
Alkyl ester sulfonate, alkyl-sulphate, sulfated alkyl ether, alkylbenzene sulfonate, secondary alkane sulfonate or soap class, as described below.
Especially according to " The Journal of the American OilChemists Society " 52 (1975), the method for describing among the pp323-329 is by using gas SO for alkyl ester sulfonate
3Sulfonated C in addition
8-C
20The linear ester of carboxylic acid (being lipid acid).Suitable starting raw material is a natural fat, as butter, and Oleum Cocois and plam oil, or also can be natural synthetic.Preferred alkyl ester sulfonate is particularly useful for washing composition, is the compound of following formula:
R wherein
1Be C
8-C
20Alkyl, preferred alkyl and R are C
1-C
6Alkyl, preferred alkyl.M is the positively charged ion that forms water-soluble salt with the alkyl ester sulfonate radical.Suitable positively charged ion is a sodium, potassium, and lithium or ammonium cation, as Monoethanolamine MEA BASF, diethanolamine, trolamine.Preferably, R
1Be C
10-C
16Alkyl and R are methyl, ethyl or sec.-propyl.Especially preferred R wherein
1Be C
10-C
16The methyl ester sulfonate of alkyl.
The alkyl-sulphate here is general formula R OSO
3The water-soluble salt of M or acid, wherein R is C
10-C
24Alkyl preferably has C
10-C
20The alkyl of alkyl component or hydroxyalkyl and preferred especially C
12-C
18Alkyl or hydroxyalkyl.M is hydrogen or positively charged ion, alkali metal cation (sodium for example for example, potassium, lithium), or ammonium or replace ammonium, for example methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion and from alkylamine such as ethylamine, diethylamide, the quaternary ammonium cation that triethylamine and their mixture obtain.C
12-C
16Alkyl chain is preferred and C for low wash temperature (for example being lower than about 50 ℃)
16-C
18Alkyl chain is preferred for high wash temperature (for example being higher than about 50 ℃).
Sulfated alkyl ether is general formula R O (A)
mSO
3The water-soluble salt of M or acid, wherein R is unsaturated C
10-C
24Alkyl or hydroxyalkyl, preferred C
12-C
20Alkyl or hydroxyalkyl and preferred especially, C
12-C
18Alkyl or hydroxyalkyl.A is oxyethyl group or propoxy-unit, and m is the numeral greater than 0, preferably between about 0.5-about 6, and particularly preferably between about 0.5 and about 3 and M be hydrogen atom or positively charged ion such as sodium, potassium, lithium, calcium, magnesium, ammonium or replace ammonium cation.The object lesson of the ammonium cation that replaces be methyl-, dimethyl-, trimethyl ammonium and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, and from alkyl amine such as ethylamine, diethylamide, those that triethylamine or their mixture obtain.Example is C
12-C
18Fatty alcohol ether sulphate, wherein EO content is that every mole of fatty alcohol ether sulphate has 1,2,2.5,3 or 4 moles and wherein M be sodium or potassium.
In secondary alkane sulfonate, alkyl can be saturated or unsaturated, branching or straight chain with unsubstituted or replaced by hydroxyl.Sulfo group can wherein not have sulfonate radical at the beginning of chain and terminal uncle's methyl on any position of carbochain.Preferred secondary alkane sulfonate comprises having about 9-25 carbon atom, the linear alkyl chain of about 20 carbon atoms of preferably about 10-and especially preferably about 13-17 carbon atom.Positively charged ion for example is a sodium, potassium, ammonium, single-, two-or triethanol ammonium, calcium or magnesium, and their mixture.Sodium is preferred as positively charged ion.
Also suitable anion surfactant is alkenyl or alkylbenzene sulfonate.Alkenyl or alkyl can be branching or straight chain with unsubstituted or replaced by hydroxyl.Preferred alkylbenzene sulfonate comprises having about 9-25 carbon atom, and the linear alkyl chain and the positively charged ion of about 13 carbon atoms of preferably about 10-are sodium, potassium, ammonium, singly-, two-or triethanol ammonium, calcium or magnesium, and their mixture.For the surfactant system of gentleness, magnesium is preferred cation; On the other hand, use preferred sodium for the washing of standard.Be equally applicable to the alkenyl benzene sulfonate.
The term anion surfactant also comprises with sulphur trioxide makes C
12-C
24, preferred C
14-C
16The alpha-olefin sulfonation, the alkene sulfonate that obtains with post neutralization.Owing to the preparation method, these alkene sulfonates can contain the hydroxyl alkane sulfonate and the paraffinic hydrocarbons stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate of relatively small amount.The specific mixture of sulfonated is described among the US-3 332 880.
Further the preferred anionic surfactants tensio-active agent is a carboxylate salt, for example fatty acid soaps and similarly tensio-active agent.This soap can be saturated or undersaturated and can contain various substituting groups, as hydroxyl or α-sulfonate radical.As hydrophobic parts, it is about 30 preferably to have about 6-, straight chain, the saturated or unsaturated alkyl of about 18 carbon atoms of preferably about 10-.
What also be suitable as anion surfactant is the salt of acyl amino carboxylic acid, as react the acyl sarcosinate that forms in alkaline medium by fat acyl chloride and sodium sarcosinate; React the lipid acid-protein condenses that is obtained by fat acyl chloride and oligopeptide; The salt of alkyl sulfoamino-carboxylic acid; The salt of alkyl and alkyl aryl ether carboxylic acid; C
8-C
24Alkene sulfonate is by with the pyrolysis product of the alkaline earth metal citrate prepared sulfonation multi-carboxylate of sulfonation in addition, described in GB-1 082 179; Alkyl glycerol vitriol; oil base glycerine vitriol; the alkylphenol ether sulfate, uncle's alkane sulfonate, alkylphosphonic; alkyl ether phosphate; isethionate such as acyl isethinate, N-acyl amino esilate (N-acyltauride), alkyl succinate; sulfosuccinate, the monoesters of sulfosuccinate (especially saturated and undersaturated C
12-C
18Monoesters) and the diester of sulfo-succinic acid (especially saturated and undersaturated C
12-C
18Diester), acyl sarcosinate, the vitriol of alkyl polysaccharide, as the vitriol of alkyl poly-dextrose, the primary alkyl sulphates of branching and alkyl polyethoxye carboxylate salt are as general formula R O (CH
2CH
2)
kCH
2COO
-M
+Those, wherein R is C
8-C
22Alkyl, k are that number and the M among the 0-10 is positively charged ion, and resinous acid or hydrogenated resin acid are as rosin or staybelite or Yatall MA resin and Yatall MA resinous acid.Other example is described in " tensio-active agent and washing composition (Surface ActiveAgents and Detergent) " (I volume and II volume, Schwartz, Perry and Berch).
The example of suitable nonionogenic tenside is following compound:
The polyoxyethylene of alkylphenol, polyoxytrimethylene, polyoxybutylene condenses.
These compounds comprise having C
6-C
20The condensation product of alkylphenol of alkyl (it can be straight chain or branching) and alkylene oxide.
The compound that every mole of alkylphenol has about 5-25 mole alkylene oxide is preferred.The commodity list surface-active agent of this type is, for example, and Igepal CO-630, Triton X-45, X-114, X-100 and X102 and from the Arkopal N brand of Hoechst AG.These tensio-active agents are known as the alkyl phenolic alkoxy thing, for example, and alkylphenol ethoxylate.
The condensation product of the ethylene oxide that fatty alcohol and about 1-are about 25 moles.
The alkyl chain of fatty alcohol can be straight chain or branching, can be primary alkyl or secondary alkyl, and generally contain about 22 carbon atoms of the 8-that has an appointment.Particularly preferably be the C that every mol of alcohol has about 18 mole ethylene oxides of about 2-
10-C
20The condensation product of alcohol.This alkyl chain can be saturated or unsaturated.Narrow (close limit ethoxylate) or wide (wide region ethoxylate) homology that alcohol ethoxylate can have ethylene oxide distributes.The example of the commodity nonionogenic tenside of this type is Teritol 15-S-9 (linear secondary C
11-C
15The condensation product of alcohol and 9 mole ethylene oxides), Tergitol 24-L-NMW (linear primary C
12-C
14The condensation product of alcohol and 6 mole ethylene oxides, narrow molar weight distributes).The part of this class product is the Genapol brand from Hoechst AG.
The condensation product of ethylene oxide and hydrophobic matrices, this matrix is formed by the condensation reaction of propylene oxide and propylene glycol.
The hydrophobic parts of these compounds preferably has molecular weight between about 1500 and about 1800.Ethylene oxide adds to the solvability that causes on the hydrophobic parts having improved in water.Polyoxyethylene content reach the condensation product gross weight about 50% before product be liquid, this corresponding to condensation up to about 40 moles ethylene oxide.The examples of commercial of this class product is from the Pluronic brand of BASF AG with from the Genapol PF brand of Hoechst AG company.
The condensation product of the reaction product of ethylene oxide and propylene oxide and quadrol.
The hydrophobic unit of these compounds is made up of the reaction product of quadrol and excessive oxidation propylene and is generally had an about 2500-3000 of molecular weight.Ethylene oxide is added on this hydrophobic unit, is about 5000-11 until the polyoxyethylene content of the about 80 weight % of about 40-with until molecular weight, and 000.The examples of commercial of this compounds is from the Tetronic brand of BASF AG with from the Genapol PN brand of Hoechst AG company.
Semi-polar nonionic surfactants
It is oxide-based that this class ionic surfactant pack is drawn together water-soluble amine, and water soluble oxidized phosphine and water-soluble sulfoxide respectively have the alkyl of about 18 carbon atoms of about 10-.Semi-polar nonionic surfactants comprises the amine oxide of following formula
Wherein R has the alkyl that chain is about about 22 carbon atoms of 8-, hydroxyalkyl or alkylphenol group, R
2Be alkylidene group or hydroxy alkylidene with about 2-3 carbon atom, or their mixture, each radicals R
1Be to have the alkyl or the hydroxyalkyl of about 3 carbon atoms of about 1-or have the polyoxyethylene group of about 1-3 ethylene oxide unit and x is a number among about 0-about 10.Radicals R
1Can interconnect and form ring by oxygen or nitrogen-atoms.This class amine oxide is C especially
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
The fatty acid acyl amine
Fatty acid amide has following formula
Wherein R has about 21 carbon atoms of about 7-, alkyl and each R of about 17 carbon atoms of preferably about 9-
1Be hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl or (C
2H
4O)
xH, wherein x from about 1 to about 3 changes.Preferred C
8-C
20Amides, a glycollic amide, diglycollic amide and isopropanol amide.
Other suitable nonionogenic tenside is alkyl and alkenyl oligoglycosides, with the fatty acid polyglycol diol ester or the aliphatic amide polyglycol ester that under each situation, in fatty alkyl, have 8-20, preferred 12-18 carbon atom, alkoxylate triglycine acid amides (triglycamide), mixed ether or mixing formal, alkyl oligoglycosides, alkenyl oligoglycosides, lipid acid N-alkyl glucose amide, phosphinoxides, dialkyl sulphoxide and protein hydrolystate.
The representative instance of both sexes and zwitterionics is an alkyl betaine, alkyl amido betaine, and aminopropionate, amino glycinate or have the amphoteric imidazoline compound of following formula:
R wherein
1Be C
8-C
22Alkyl or alkenyl, R
2Be hydrogen or CH
2CO
2M, R
3Be CH
2CH
2OH or CH
2CH
2OCH
2CH
2CO
2M, R
4Be hydrogen, CH
2CH
2OH or CH
2CH
2COOM, Z are CO
2M or CH
2CO
2M, n are 2 or 3, preferred 2 and M be hydrogen or positively charged ion such as basic metal, alkaline-earth metal, ammonium or alkanol ammonium.
The preferred amphoterics of this chemical formula is monocarboxylic acid salt and dicarboxylate.Their example is an Oleum Cocois both sexes carboxyl propionic salt, Oleum Cocois amido carboxyl propionic acid, Oleum Cocois both sexes carboxyl glycinate (being also referred to as Oleum Cocois both sexes diacetin in addition) and Oleum Cocois both sexes acetate.
Other preferred amphoterics is alkyl dimethyl trimethyl-glycine and alkyl two polyethoxye trimethyl-glycines, wherein alkyl has about 22 carbon atoms of about 8-, it can be straight chain or branching, preferably have 8-18 carbon atom and especially preferably have about 18 carbon atoms of about 12-.These compounds are for example sold with trade(brand)name Genagen LAB by Hoechst AG.
Suitable cationic surfactants is to belong to R
1N (CH
3)
3 +X
-, R
1R
2N (CH
3)
2 +X, R
1R
2R
3N (CH
3)
+X
-, or R
1R
2R
3R
4N
+X
-The quaternary ammonium salt of the replacement of type or unsubstituted straight chain or branching.Radicals R
1, R
2, R
3And R
4Preferably and independently of one another be to have chain length between 8-24 carbon atom, the not substituted alkyl between 10 and 18 carbon atoms especially has the hydroxyalkyl of about 4 carbon atoms of about 1-, phenyl, C
2-C
18Alkenyl, C
7-C
24Aralkyl, (C
2H
4O)
xH, wherein x is that about 1-is about 3, alkyl contains one or more ester groups, or the ring-type quaternary ammonium salt.X is suitable negatively charged ion.
Can comprise that in the present invention other washing composition and wash products composition comprise inorganic and/or organic washing-assisting detergent, to reduce water hardness.
These washing assistants can exist in washing composition and wash products composition with the ratio of the about 80 weight % of about 5%-.Inorganic builders for example comprises an alkali metal salt of polyphosphoric acid, ammonium salt and alkanol ammonium salts, for example tri-polyphosphate, pyrophosphate salt and glassy polymer metaphosphate, phosphonate, silicate, carbonate comprises supercarbonate and sesquicarbonate, vitriol and silico-aluminate.
The example of silicate-like builder is an alkalimetal silicate, especially SiO
2: Na
2O compares those between 1.6: 1 and 3.2: 1, and the leaf silicates, and for example the leaf water glass described in US-4 664 839, can obtain with trade mark SKS from Hoechst AG.SKS-6 is particularly preferred leaf silicate-like builder.
The silico-aluminate washing assistant is particularly preferred for the present invention.These especially have general formula Na
z[(AlO
2)
z(SiO
2)
y] xH
2The zeolite of O, wherein z and y are at least 6 integers, and the ratio of z and y is between 1.0 and about 0.5, and x is the integer between about 15-about 264.
The suitable ion-exchanger based on silico-aluminate can obtain by commercial.These silico-aluminates structurally can crystalline or unbodied, and is natural or synthetic making.Preparing these methods based on the ion-exchanger of silico-aluminate is described among US-3 985 669 and the US-4 605 509.Preferably the ion-exchanger based on the synthetic crystallization silico-aluminate is can be with model zeolite A, and zeolite P (B) (being included in those disclosed among the EP-A-0 384 070) and X zeolite obtain.Preferably have the silico-aluminate of particle diameter between 0.1 and 10 μ m.
Suitable organic washing-assisting detergent comprises the multi-carboxy compound class, and for example ether multi-carboxylate and oxygen base disuccinate are described in US-3 128 287 and US-3 635 830." TMS/TDS " washing assistant that relates to US-4 663 071 equally.
Other suitable washing assistant comprises ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxyl methyl oxygen base succsinic acid, an alkali metal salt, ammonium salt and the substituted ammonium salt of polyacetic acid (for example, ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA)), and the multi-carboxylic acid, as mellitic acid, succsinic acid, oxygen base disuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxyl methyl oxygen base succsinic acid and their solubility salt.
Based on the washing assistant of Citrate trianion, for example citric acid and its solubility salt, especially sodium salt is preferred poly carboxylic acid washing assistant, it can particularly be used from the granular preparation with zeolite and/or leaf silicate one individually.Other suitable washing assistant is disclosed 3 in US-4 566 984,3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.
If can use based on the washing assistant of phosphorus and especially want to prepare the hand washing usefulness soap blank, might use various alkali metal phosphates, for example tripoly phosphate sodium STPP, trisodium phosphate and former sodium phosphate.Might use the phosphonate washing assistant equally, as ethane-1-hydroxyl-1,1-diphosphonate and at for example US-3 159581, US-3 213 030, and US-3 422 021, disclosed other known phosphonate among US-3 400 148 and the US-3 422 137.
In a preferred embodiment of the invention, conventional wash products composition can be selected from those components commonly used in the cleaning combination, as surfactant and washing assistant.If need, the wash products composition also can comprise can strengthen cleaning performance, is used for handling or nurses being cleaned object, or change one or more cleaning additives or other material of the function of wash products composition.Suitable cleaning additive is included in the material of regulation among the US-3 936 537 in the wash products composition.The cleaning additive that can use in wash products composition of the present invention comprises, for example, and enzyme, especially proteolytic enzyme, lipase and cellulase, profoamer, foam restriction agent, anti-tarnishing agent and/or sanitas, suspension agent, colorant, filler, white dyes, sterilizing agent, alkali, hydrotropic agent, antioxidant, enzyme stabilizers, essence, solvent, solubilizing agent, anti redeposition agent, dispersion agent, color transfer inhibitor, polyamine N-oxide class for example, as poly-(4-vinylpridine N-oxide compound), Polyvinylpyrolidone (PVP), poly-N-vinyl-N-methylacetamide and N-vinyl imidazole and N-vinylpyrrolidone copolymers, processing aid, softening agent and antistatic auxiliary agent.
If desired, washing composition of the present invention and wash products composition can comprise the SYNTHETIC OPTICAL WHITNER that one or more are common, and activator or stablizer, peroxy acid especially, it with detergency oligomer ester reaction of the present invention.In general, must guarantee that employed SYNTHETIC OPTICAL WHITNER is compatible with the wash products composition.Can use common test method, as the bleaching activity of the cleaning combination of easy preparation measuring method as the function of period of storage for this reason.
Peroxy acid can be the mixture of free peracid or inorganic persalt (for example Sodium peroxoborate or SPC-D) and organic peracid precursor (it changes into peroxy acid when the mixture of persalt and this peroxyacid precursor is dissolved in the water).The organic peroxy acid precursor is known as bleach-activating agent usually in the prior art.
The example of suitable organic peroxide acid is disclosed in US-4 374 035, and US-4 681 592, and US-4634 551, and US-4 686 063, US-4 606 838 and US-4 671 891.Be suitable for bleaching clothes and contain perborate bleach and the example of the composition of activator is disclosed in US-4 412934, US-4 536 314, US-4 681 695 and US-4 539 130.
The example that is preferred for peroxy acid of the present invention comprises peroxide dodecanedioic acid (DPDA), crosses the nonyl acid amides (NAPSA) of oxydisuccinic acid, the nonyl acid amides (NAPAA) of peroxide hexanodioic acid and decyl diperoxy succsinic acid (DDPSA).According to the method for US-4 374 035, in soluble granula, preferably contain peroxy acid.Preferred granular bleaching preparaton comprises, percentage ratio by weight, the compound of the heat release solubility of 1%-50%, for example boric acid; The surface active ingredient compatible of 1%-25%, for example C13LAS with peroxy acid; One or more sequestrant stablizer, for example trisodium phosphates of 0.1%-10%; With the water-soluble salt of 10%-70%, for example sodium sulfate.
The SYNTHETIC OPTICAL WHITNER that contains peroxy acid is used with a kind of like this amount, so that obtainable available oxygen content is between about 0.1% and about 10%, preferably between about 0.5% and about 5%, especially between about 1% and 4%.Percentage ratio is based on the gross weight of wash products composition.
The SYNTHETIC OPTICAL WHITNER that contains peroxy acid of appropriate amount, wash products composition of the present invention based on a unitary dose, when under 15-60 ℃, being used to comprise the typical washings of about 65 premium on currency, produce the available oxygen of about 1ppm to about 150ppm, preferably about 2ppm is to the available oxygen of about 20ppm.Washings should have pH value between 7 and 11, preferably between 7.5 and 10.5, in order that enough bleaching effects are provided.6 hurdle 1-10 with reference to US-4 374 035 are capable.
Perhaps, bleaching composition can comprise suitable organic peroxy acid precursor, when it produces a kind of in the above-mentioned peroxy acid during with hydroperoxidation in alkaline aqueous solution.Hydrogen peroxide cource can be any inorganic peroxide that discharges hydrogen peroxide in the aqueous solution, as Sodium peroxoborate (monohydrate and tetrahydrate) and SPC-D.
The ratio of SYNTHETIC OPTICAL WHITNER in this novel wash products composition that contains superoxide is between 0.1wt% and about 95wt%, preferably between about 1wt% and about 60wt%.If bleaching composition also is the wash products composition for preparing fully, the content of SYNTHETIC OPTICAL WHITNER that contains superoxide is preferably between about 1wt% and about 20wt%.
The amount of the activator of bleaching agent that can use with detergency oligomer ester of the present invention generally is at 0.1-60wt%, preferably between 0.5-40wt%.If employed bleaching composition is the detergent composition for preparing fully simultaneously, then wherein the amount of existing bleach-activating agent preferably between about 0.5-20wt%.
The oxygen that the content of peroxy acid and detergency oligomer ester of the present invention preferably obtains from peroxy acid and the weight ratio of detergency oligomer ester of the present invention are about 4: about 1: 30 of 1-, especially about 2: about 1: 15 of 1-and especially about 1: about 1: 7.5 of 1-.This mixture can use as the product for preparing fully or as the additive of washing composition.
Wash products composition of the present invention can comprise the enzyme that one or more are conventional, and it does not react with novel detergency oligomer ester of the present invention.Particularly preferred enzyme is a cellulase.The cellulase of Shi Yonging can be to be characterized as optimum PH value range between 5 and 9.5 from also should embodying of bacterium or fungi acquisition in this case.Suitable cellulase is disclosed among the US-4 435 307.Described cellulase is the bacterial strain of being planted Pseudomonas (Humicola insolens) by corruption, especially plant from corruption that bacterium DSM1800 bacterial strain produces, or belong to generation cellulase-212 mycetogenetic of Aeromonas (genus Aeromonas) from another kind, and from the extractive cellulase of hepatopancreas of some shipworm (marine mollusks).Suitable cellulase is disclosed in GB-A-2 075 028 equally, GB-A-2 085 275 and DE-A-2 247 832.
Preferred cellulase is described in WO-91/17243.Contain about at the most 50mg in the wash products composition of the present invention, the enzyme of the about 10mg of preferably about 0.01mg-/every g wash products composition.Based on the washing composition that comprises detergency oligomer ester of the present invention and the weight of wash products composition, the ratio of enzyme is 0.001wt% at least, preferably between the about 5wt% of about 0.001wt%-, especially between about 0.001wt% and the about 1wt% and particularly between the about 1wt% of about 0.01wt%-.
Detergency oligomer ester of the present invention preferably is used for textile washing liquid with the concentration between the about 60ppm of about 30-with the concentration between the about 120ppm of about 1-, is polyester, and polyester/cotton blending thing and other synthetic textiles provide effective cleaning and scale removal to handle.Textile washing liquid preferably alkalescence, especially between about 7.5 and about 10.5, wherein there is typical detergent ingredients in the PH scope between about 7 and about 11.
Surprisingly, as long as consider pH value and anionic surfactant compound, the washing system that exists in washing composition and cleaning combination also can be to be used for cleaning combination of the present invention corresponding to amount of the prior art usually.In these compositions, they fulfil their general application target, i.e. the cleaning of fabric or bleaching, and the scale removal performance of detergency oligomer ester of the present invention is not had any detrimental effect.
In order to obtain soil-releasing finiss, detergency oligomer ester of the present invention also can be used in the commercially available domestic fabric softening agent.These softening agents mainly comprise softening component, help tenderizer, emulsifying agent, and spices, colorant and ionogen, and be formulated into that PH is lower than 7, the preferred acidity between 3 and 5.
Employed softening component is the quaternary ammonium salt of following type
R wherein
1=C
8-C
24Just or iso-alkyl, preferred C
10-C
18Positive alkyl,
R
2=C
1-C
4Alkyl, preferable methyl,
R
3=R
1Or R
2
R
4=R
2Or hydroxyethyl or hydroxypropyl or its oligopolymer,
The X-=bromine, chlorine, iodine, methylsulfate, acetate moiety, propionate, lactate.
The example is a Varisoft TA 100, chlorination two tallow alkyl Dimethyl Ammonium, and chlorination two tallow alkyl methyl hydroxypropyl ammoniums, chlorination hexadecyl trimethyl ammonium or corresponding benzyl derivative are as dodecyl dimethyl benzyl ammonium chloride.The ring-type quaternary ammonium salt also can use as the alkyl morpholine derivative.
Except quaternary ammonium compound, also might use imidazolinium compounds (1) and imidazolidine derivatives (2)
R=C wherein
8-C
24Positive alkyl or iso-alkyl, preferred C
10-C
18Positive alkyl,
The X=bromine, chlorine, iodine, methylsulfate,
A＝-NH-CO-，-CO-NH-，-O-CO-，-CO-O-。
A particularly preferred compounds is so-called ester quat.They are reaction product of alkanolamine and lipid acid and use common alkylation or hydroxyalkylation reagent in addition quaternized subsequently.
Preferred alkanolamine is the compound of following formula
R wherein
1=C
1-C
3Hydroxyalkyl, preferred hydroxyethyl and
R
2, R
3=R
1Or C
1-C
3Alkyl, preferable methyl.
Trolamine and methyldiethanolamine are particularly preferred.
The particularly preferred initial product of other of ester quat is amino glycerol derivative, as the dimethylamino propylene glycol.
Alkylation or hydroxyalkylation reagent are alkyl halides, preferable methyl chlorine.Methyl-sulfate, oxyethane and propylene oxide.
The example of ester quat is the compound of following formula
Wherein R-C-O is from saturated or undersaturated C
8-C
24Lipid acid obtains.The example is a caproic acid, and is sad, hydrogenation, non-hydrogenation or partially hydrogenated beef fat acid, stearic acid, oleic acid, linolic acid, mountain Yu acid, palm stearin acid, tetradecanoic acid and elaidic acid.N is in the 0-10 scope, in the preferred 0-3 scope, and preferred especially 0-1.
With other clothes softening agent raw material of detergency oligomer ester blended of the present invention be for example based on the amidoamines of dialkyl group triamine and longer chain fatty acid,, and their ethoxylate and/or quaternized variant.These compounds have following structure:
R wherein
1And R
2Be C independently
8-C
24Just or iso-alkyl, preferred C
10-C
18Positive alkyl,
A is-CO-NH-or-NH-CO-,
N is 1-3, preferred 2 and
M is 1-5, preferred 2-4.
In the quaternized process of uncle's amino, might introduce radicals R in addition
3, it can be C
1-C
4Alkyl, preferable methyl and counter ion X, it can be chlorine, bromine, iodine or methylsulfate.Amido amino ethoxy thing and their quaternary ammonium derivative are with trade(brand)name Varisoft510, Varisoft512, and Rewopal V3340 and Rewoquat W222 LM obtain.
The preferred concentration of oligomer ester of the present invention in the fabric softener preparaton is corresponding to being those of detergent mixture defined.
Except above-mentioned purposes in washing composition and fabric softener/laundry post-treatment composition, oligomer ester of the present invention can be used in all family expenses cleaning combinations and neutralizes in all industrial cleaning combinations, to obtain the good de-sludging effect with regard to hydrophobic soil.Family expenses or industrial cleaning combination can comprise tensio-active agent, washing assistant, white dyes, the above-mentioned representative example of SYNTHETIC OPTICAL WHITNER and enzyme.
The example of family expenses cleaning combination is the clean-out system of all purposes, cleaning composition, carpet cleaner and dip composition.
The example of industry cleaning combination is clean-out system and the rumbling compound that is used for plastics such as cylinder and auto parts machinery, and the clean-out system of coated surface such as body of a motor car and rumbling compound (Pflegemittel).
The cleaning combination that is formulated into liquid form and contains oligomer ester of the present invention generally has neutrality-acid PH.
Embodiment
Embodiment 1
With the 194.2g dimethyl terephthalate (DMT), 39.8g ethylene glycol, 90.6g 1, the 2-propylene glycol, 0.37g anhydrous sodium acetate and 0.19g titanium tetraisopropylate join the KPG agitator is housed, 20cmVigreux post (having the gloomy bridge tube of gram dish) is in interior 1 liter of four neck flask with thermometer and gas introduction tube.To make the atmosphere of mixture be inertia and be heated to 165-167 ℃ through half an hour with nitrogen.Through 2.5 hours temperature is increased to 215-220 ℃ again.Under about 165 ℃ of internal temperature, begin to carry out transesterification and therefore begin distillating carbinol.After about 5 hours, distilled out the methyl alcohol more than 98% with respect to desired amount.This mixture is cooled to about 80 ℃ and add the methyl polyoxyethylene glycol 750 of 72.0g then, the methyl polyoxyethylene glycol 1820 of 91.2g and the polyethylene glycol 1500 of 387.5g.Atmosphere in the flask is become inertia once more and is heated to 200-220 ℃, through about 1 hour pressure is reduced to 5 millibars (mbar) then and at 220-240 ℃ of following condensation 2-5 hour, ethylene glycol and 1 in this process, the mixture of 2-propylene glycol is steamed to be removed.After condensation finished, mixture covered and cooling with nitrogen.Behind cool to room temperature, product is cured into solid matter.Productive rate 730g.
With similar among the embodiment 1, oligomer ester of the present invention also can prepare by enough following starting raw materials:
Embodiment 2213.5g dimethyl terephthalate (DMT) 43.7g ethylene glycol 106.2g 1,2-propylene glycol 0.41g sodium acetate, anhydrous 0.21g titanium tetraisopropylate 39.6g methyl polyoxyethylene glycol 75050.2g methyl polyoxyethylene glycol 1820426.3g polyethylene glycol 1500 productive rate 720g embodiment 3145.6g dimethyl terephthalate (DMT) 109.0g 1,2-propylene glycol 0.28g sodium acetate, anhydrous 0.14g titanium tetraisopropylate 82.2g methyl polyoxyethylene glycol 750581.3g Macrogol 3000 productive rate 800g embodiment 4194.2g dimethyl terephthalate (DMT) 39.8g ethylene glycol 96.6g 1,2-propylene glycol 0.37g acid sodium, anhydrous 0.19g titanium isopropylate 54.0g methyl polyoxyethylene glycol 75068.4g methyl polyoxyethylene glycol 182068.9g polyethylene glycol 1500 129.2g polyoxyethylene glycol 800258.3g Macrogol 3000 productive rate 760g embodiment 5223.3g dimethyl terephthalate (DMT) 45.7g ethylene glycol 111.1g 1,2-propylene glycol 0.42g acid sodium, anhydrous 0.22g titanium tetraisopropylate 28.2g methyl polyoxyethylene glycol 75035.7g methyl polyoxyethylene glycol 1820445.6g polyethylene glycol 1500 productive rate 720g embodiment 6174.7g dimethyl terephthalate (DMT) 19.0g ethylene glycol 107.5g 1,2-propylene glycol 0.33g sodium acetate, anhydrous 0.17g titanium isopropylate 83.8g methyl polyoxyethylene glycol 750174.4g polyethylene glycol 1500 348.8g Macrogol 3000 productive rate 765g embodiment 748.5g dimethyl terephthalate (DMT) 10.0g ethylene glycol 24.2g 1,2-propylene glycol 0.10g sodium acetate, anhydrous
0.05g titanium tetraisopropylate
730g methyl polyoxyethylene glycol 20,000
97.0g polyethylene glycol 1500
Productive rate 880g
Embodiment 8
2 33.0g dimethyl terephthalate (DMT)
47.7g ethylene glycol
115.9g 1, the 2-propylene glycol
0.44g sour sodium is anhydrous
0.2 3g titanium isopropylate
22.8g normal-butyl Macrogol 200
465.0g polyethylene glycol 1500
Productive rate 700g
Embodiment 9
194.2g dimethyl terephthalate (DMT)
39.8g ethylene glycol
96.6g 1, the 2-propylene glycol
0.37g sour sodium is anhydrous
0.19g titanium isopropylate
226.5g????GenapolT800
387.5g polyethylene glycol 1500
Productive rate 800g
With detergency oligomer ester of the present invention with regard to its de-sludging effect with the detergency polymer phase ratio of prior art.
For this reason, this material joins in the detergent mixture with the concentration of 1%-2%, and this preparaton has been used for washing in advance polyester test fabric WFK30A (WFK=washs room research institute [Laundry ResearchInstitute] Krefeld).Pretreated by this way fabric is dried and makes dirty with exhausted machine oil.Placement allows oil effect after 1 hour, not adding detergency oligomer ester of the present invention or not adding under the situation of detergency polymkeric substance of prior art, washs the cloth specimen of this test usefulness.The reflectivity of experiment with measuring fabric then.The detergency polymkeric substance of employed prior art is following compound:
The comparative example 1
According to EP-B-0 185 427,23 pages, Table IV, the compound of 4 row uses with specified amount in the table under each situation.
The comparative example 2
According to EP-B-0 185 427,23 pages, Table IV, the compound of 5 row uses with specified amount in the table under each situation.
The comparative example 3
Repel-O-Tex SRP4, Rhone-Poulenc uses with specified amount in the table under each situation.
The comparative example 4
Sokalan9976, BASF AG uses with specified amount in the table under each situation.
Table 1: wash conditions
| Washing machine | ????Linitest |
| The water hardness | ????20°dH |
| Liquor ratio | ????1∶40 |
| Wash temperature | ????40℃ |
| Washing time | 30 minutes |
| Detergent concentration | ????6g/l |
Table 2: the composition of liquid washing agent
| Liquid washing agent I | Form (wt%) |
| GenapolOA?080 | ????12.0 |
| HostapurSAS60 | ????17.0 |
| Fatty acid mixt cocinic acid/oleic acid | ????14.0 |
| KOH 85% intensity | ????2.6 |
| Trolamine | ????2.0 |
| Citrate trisodium dihydrate | ????5.0 |
| Dequest?2066 | ????4.0 |
| 1, the 2-propylene glycol | ????5.0 |
| Ethanol | ????3.0 |
| Detergency oligomer ester or polyester | 1 or 2 |
| Water | 100 surplus |
Table 3: the washing effect of oligomer ester of the present invention in liquid washing agent I
| Detergent mixture I | Reflectivity (%) |
| I does not have additive | ????21.5 |
| The following oligomer ester of I+1% | |
| ????Ex.1 | ????34.0 |
| ????Ex.2 | ????39.2 |
| ????Ex.3 | ????38.9 |
| ????Ex.4 | ????39.8 |
| ????Ex.5 | ????40 |
| ????Ex.6 | ????38.9 |
| ????Ex.7 | ????31.8 |
| ????Ex.8 | ????39.1 |
| ????Ex.9 | ????35.1 |
Table 4: the detergency polyester of oligomer ester of the present invention and prior art is washing effect relatively, uses in liquid washing agent I
| Detergent mixture I | Reflectivity (%) |
| I does not have additive | ????21.9 |
| The following oligomer ester of I+1% | |
| The comparative example 1 | ????24.8 |
| The comparative example 2 | ????22.6 |
| The comparative example 3 | ????32.0 |
| The comparative example 4 | ????26.3 |
| ????????Ex.1 | ????34.0 |
| ????????Ex.5 | ????40 |
| ????????Ex.6 | ????38.9 |
Table 5: as the washing effect of the function of working concentration.Contrast with prior art detergency polyester.
| Detergent mixture I | Reflectivity (%) |
| I does not have additive | ????21.5 |
| I+1% comparative example 3 | ????30.5 |
| The oligomer ester of I+1% embodiment 1 | ????34.0 |
| I+2% comparative example 3 | ????36.0 |
| The oligomer ester of I+2% embodiment 1 | ????39.5 |
Detergency oligomer ester of the present invention is tested just washing enhancement from test fabric WFK, that made dirty equally.
For this reason, according to table 2 they are introduced in the liquid washing agent.The detergency polymkeric substance of prior art is as comparison.Subsequently, black test fabric WFK30C and WFK30D are washed and measurement of reflectivity.Under each situation, carry out 4 wash(ing)cycles.Wash conditions corresponding in the table 1 those.Obtain following result:
Table 6: above-mentioned oligomer ester is to the washing enhancement of WFK30C
| Detergent mixture I | Reflectivity (%) as the function of wash(ing)cycle |
| ?????1x | ?????2x | ?????3x | ?????4x | |
| I does not have additive | ????35.0 | ????36.4 | ????37.7 | ????38.5 |
| I+1% comparative example 3 | ????35.6 | ????38.5 | ????40.7 | ????42.6 |
| I+1％Ex.1 | ????35.9 | ????43.8 | ????55.0 | ????62.8 |
Table 7: above-mentioned oligomer ester is to the washing enhancement of WFK30D
| Detergent mixture I | Reflectivity (%) as the function of wash(ing)cycle | |||
| ?????1x | ?????2x | ?????3x | ?????4x | |
| I does not have additive | ????41.8 | ????44.7 | ????46.6 | ????47.9 |
| I+1% comparative example 3 | ????44.0 | ????51.1 | ????56.3 | ????60.2 |
| I+1％Ex.1 | ????47.0 | ????59.7 | ????64.7 | ????66.9 |
The note Genapol OA 080/ pure C of employed trade(brand)name
14/ C
15Fatty alcohol ethoxylate (having 8 EO) Hoechst AG Hostapur SAS 60/ secondary C
13-C
17The n-paraffin sulfonate sodium, 60% intensity Hoechst AG Repel-O-Tex/ ethylene glycol-polyoxyethylene glycol-terephthalic acid copolymer comprised Rhone-Poulenc 70%, residue is sodium sulfate and sodium silicoaluminate Sokalan 9976/ 50%Na
2SO
4On the Monsanto 25% intensity aqueous solution of seven sodium salts of 50% nonionic polycondensate BASF Dequest 2066/ diethylenetriamine-five (methylene phosphonic acid)
Claims (14)
1, the oligomer ester of Chemical formula 1
R wherein
1And R
7Be C straight chain or branching
1-C
18Alkyl, R
2And R
6Be ethylidene, R
3Be 1,4-phenylene, R
4Be ethylidene, R
5Be ethylidene, propylene or the statistics mixture that both form arbitrarily, n
1And n
5Be the number among the 1-500 independently of one another, n
2Be the number among the 10-140, n
3Be the number among the 1-12, n
4Be the number among the 7-40, n
3+ n
4Be at least 11.
2, according to the desired oligomer ester of claim 1, wherein R
1And R
7Be the C of straight chain or branching
1-C
4Alkyl.
3, according to claim 1 or 2 desired oligomer ester, wherein n
1And n
5Be the number between the 3-45 independently of each other.
4, according to any one desired oligomer ester, wherein n among the claim 1-3
2It is the number between the 18-70.
5, according to one or multinomial desired oligomer ester, wherein n among the claim 1-4
3It is the number between 2 and 5.
6, according to one or multinomial desired oligomer ester, wherein n among the claim 1-5
4It is the number between 8 and 12.
7, according to one or multinomial desired oligomer ester, wherein n among the claim 1-6
3+ n
4Be number among the 12-18 or the number between the 25-35.
8, according to washing composition and the cleaning combination of or multinomial desired oligomer ester among the claim 1-7, detergent builder, the purposes in the cleaning combination of laundry post-treatment composition and crust at textiles.
9, according to one or multinomial desired oligomer ester among the claim 1-7 at powdery, granular, pasty state, the potent type washing composition of gel or liquid form, the light duty washing composition, the color washing composition, Wool detergent, the curtain washing composition, assembling box washing composition (Baukastenwaschmittel), at soap blank, detergent, clothes spreading mass (W schest rke) and clothes stiffening agent, the flatiron auxiliary agent, fabric softener, general purpose clean-out system, hand washing composition, the clean-out system on plastics and coated surface and rumbling compound, and the purposes in carpet cleaning and the dip composition.
10, be used on textiles, obtaining the aqueous solution of decontamination arrangement property or the purposes of preparation according to one or multinomial desired oligomer ester among the claim 1-7.
11, use with liquid, paste, gel or particle form according to one or multinomial desired oligomer ester among the claim 1-7.
12, according to the preparation method of or multinomial desired oligomer ester among the claim 1-7, it is included in and is with or without polyoxyethylene glycol and C
1-C
18Under the situation of alkyl polyoxyethylene glycol and interpolation catalyzer, allow dimethyl terephthalate (DMT), ethylene glycol and/or propylene glycol at first under normal pressure, be heated to the about 220 ℃ temperature of 160-and carry out transesterification, the while distillation for removing methanol, under reduced pressure carry out condensation reaction then under the about 240 ℃ temperature of 160-, excessive glycol is removed in distillation simultaneously.
13, according to the method for preparing oligomer ester of claim 12, wherein employed catalyzer is a titanium tetraisopropylate, dibutyltin oxide or ANTIMONY TRIOXIDE SB 203 99.8 PCT/lime acetate.
14, a kind of composition, it is selected from by powdery, granular, pasty state, the washing composition of the textiles of gel or liquid form and cleaning combination, detergent builder, the cleaning combination of laundry post-treatment composition and crust, potent type washing composition, the light duty washing composition, the color washing composition, Wool detergent, curtain washing composition, the assembling box washing composition, soap blank, detergent, clothes spreading mass and clothes stiffening agent, the flatiron auxiliary agent, fabric softener, general purpose clean-out system, hand washing composition, the clean-out system on plastics and coated surface and rumbling compound, and in this group that carpet cleans and dip composition is formed, said composition can comprise tensio-active agent, washing assistant, other composition that SYNTHETIC OPTICAL WHITNER and/or this based composition are commonly used, it comprises the desired oligomer ester according to claim 1-7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19644034.3 | 1996-10-31 | ||
| DE19644034 | 1996-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1182751A true CN1182751A (en) | 1998-05-27 |
Family
ID=7809751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97121547 Pending CN1182751A (en) | 1996-10-31 | 1997-10-29 | Soil release oligoesters, their preparation and their use in detergents and cleaning compositions |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN1182751A (en) |
| AU (1) | AU4287497A (en) |
| BR (1) | BR9705182A (en) |
| CZ (1) | CZ343397A3 (en) |
| HU (1) | HU9701769D0 (en) |
| ID (1) | ID18634A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104684961A (en) * | 2012-07-31 | 2015-06-03 | 科莱恩金融(Bvi)有限公司 | Polyesters |
| CN104704103A (en) * | 2012-08-18 | 2015-06-10 | 科莱恩金融(Bvi)有限公司 | Use of polyesters in washing and cleaning agents |
| CN115551984A (en) * | 2020-05-20 | 2022-12-30 | 科莱恩国际有限公司 | Soil release polyesters for use in detergent compositions |
| US11884775B2 (en) | 2017-11-28 | 2024-01-30 | Clariant International Ltd. | Renewably sourced soil release polyesters |
-
1997
- 1997-10-09 ID IDP973401A patent/ID18634A/en unknown
- 1997-10-24 AU AU42874/97A patent/AU4287497A/en not_active Abandoned
- 1997-10-29 CN CN 97121547 patent/CN1182751A/en active Pending
- 1997-10-29 HU HU9701769A patent/HU9701769D0/en unknown
- 1997-10-29 CZ CZ973433A patent/CZ343397A3/en unknown
- 1997-10-30 BR BR9705182A patent/BR9705182A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104684961A (en) * | 2012-07-31 | 2015-06-03 | 科莱恩金融(Bvi)有限公司 | Polyesters |
| CN104704103A (en) * | 2012-08-18 | 2015-06-10 | 科莱恩金融(Bvi)有限公司 | Use of polyesters in washing and cleaning agents |
| US11884775B2 (en) | 2017-11-28 | 2024-01-30 | Clariant International Ltd. | Renewably sourced soil release polyesters |
| CN115551984A (en) * | 2020-05-20 | 2022-12-30 | 科莱恩国际有限公司 | Soil release polyesters for use in detergent compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| HU9701769D0 (en) | 1997-12-29 |
| ID18634A (en) | 1998-04-30 |
| AU4287497A (en) | 1998-05-07 |
| BR9705182A (en) | 1999-06-29 |
| CZ343397A3 (en) | 1998-05-13 |
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