EP0185522B1 - Gemischte Phenylendiester als Persäurevorläufer - Google Patents

Gemischte Phenylendiester als Persäurevorläufer Download PDF

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Publication number
EP0185522B1
EP0185522B1 EP85309075A EP85309075A EP0185522B1 EP 0185522 B1 EP0185522 B1 EP 0185522B1 EP 85309075 A EP85309075 A EP 85309075A EP 85309075 A EP85309075 A EP 85309075A EP 0185522 B1 EP0185522 B1 EP 0185522B1
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Prior art keywords
hydrogen peroxide
compound
composition
alkyl
phenylene
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French (fr)
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EP0185522A2 (de
EP0185522A3 (en
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Ronald Augustus Fong
Stephen Bradford Kong
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Clorox Co
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Clorox Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • This relates to novel peracid precursors and the in situ generation of peracid in aqueous solution by combining a source of hydrogen peroxide, and the novel peracid precursor which are phenylene mixed diesters, in water.
  • Peroxygen bleaching compounds such as hydrogen peroxide, sodium percarbonate, sodium perborate monohydrate or tetrahydrate, are useful for bleaching fabrics, textiles and other materials. Unfortunately these sorts of peroxygen bleaches appear less effective when bleaching temperatures of less than 70°C are utilized. Thus, the low wash temperature found in American washing machines make the use of these bleaches less effective than in European-type washing machines, which typically use water temperatures above 70°C. Therefore, attempts have been made to use activators in combination with these peroxygen bleaches.
  • NABS sodium acetyloxy benzene sulfonate
  • the invention provides a compound of the general structure:
  • the invention also provides a solid or liquid bleaching composition comprising:
  • Selected adjuncts can be added to these bleaching compositions, such as surfactants, stabilizers, buffers and builders.
  • the invention also includes a method for synthesizing the above noted precursor compounds and a method of bleaching.
  • washing temperatures of up to 100°C are common in Europe. However, there remains a need to provide peracid precursors which are effective to promote good bleaching in wash temperatures below 70°C, more preferably below 60°C, and most preferably below 50°C.
  • any combination of these substituents may be present in the precursors of this invention.
  • R 5 of NR 5+ 4 is selected from H, alkyl of 1-24 carbon atoms, and mixtures thereof and R 6 is alkyl of 1 to 20 carbon atoms
  • any combination of these substituents may be present in the precursors of this invention.
  • the substituents are charged moieties, e.g. S0 3
  • appropriate counterpart ions may be present.
  • appropriate counterions may be chosen from H + , alkali metal salts (Na + , Li + , K + ), although alkaline earth salts (calcium, magnesium, barium) or even ammonium salts may be possible.
  • alkali metal salts Na + , Li + , K +
  • alkaline earth salts calcium, magnesium, barium
  • ammonium salts may be possible.
  • appropriate counterions can include halides, (CI-, Br-, I - ), methosulfates, sulfates and nitrates. These aforementioned counterions may also be present with respect to the substituted R 1 , R 4 and R 6 groups, as appropriate.
  • the compounds according to the invention include, ortho, meta and para-substituted phenylene mixed diesters, (i.e. wherein R 1 ⁇ R 4 ) of resorcinol, hydroquinone and catechol, which are exemplified below:
  • Hydroquinone (1,4-benzenediol; 1,4-dihydroxybenzene; p-dihydroxybenzene) is a white crystalline compound which can be obtained by dry distillation of quinic acid or by reduction of quinone.
  • Resorcinol (1,3-benzenediol; 1,3-dihydroxybenzene; m-dihydroxybenzene) is a crystalline compound with a faint aromatic odor, and a sweet/bitter taste. It may be produced by the alkali fusion of galbanum and asafetida resins.
  • Catechol (1,2-benzenediol; 1,2-dihydroxybenzene; o-dihydroxybenzene) is a crystalline compound with a phenolic odor and a sweet and bitter taste. It may be obtained by dried distillation of catechin which is found in the aqueous extract of catechu, which is an extract of an East Asian acacia plant.
  • the dihydroxybenzenes are weak acids with two dissociation constants. They are generally classified as antioxidant agents and are useful analytical reagents. Their structures, uses and chemistries are more thoroughly explored in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., vol. 13, pages 39-69 (1981), which pages are incorporated herein by reference.
  • the mixed diesterified derivatives of these dihydroxybenzene compounds according to the invention are generally produced by reacting a monoesterified dihydroxybenzene having a group O-C(O)-R 1 or O ⁇ C(O) ⁇ R 4 with an appropriate acid anhydride providing the other group O ⁇ C(O) ⁇ R 1 or O ⁇ C(O) ⁇ R 4 in the presence of a strong acid.
  • a monoesterified dihydroxybenzene having a group O-C(O)-R 1 or O ⁇ C(O) ⁇ R 4 with an appropriate acid anhydride providing the other group O ⁇ C(O) ⁇ R 1 or O ⁇ C(O) ⁇ R 4 in the presence of a strong acid.
  • solubility/dispersibility and hence performance can be improved by the addition of solubilizing groups such as SOg, CO 2 , NRQ+. Placement of these solubilizing groups may have different effects on the precursor compositions. For example, if the solubilizing groups are placed on the aromatic ring or at or near the end of the alkyl groups of the esters, increased solubility may be observed. Placing the solubilizing groups next to the carbonyl carbon on the ester group or electron withdrawing substituents on the aromatic leaving group may increase the perhydrolysis rate.
  • halogen groups may be added by typical halogenation reactions, in which a typical source of halogen is combined with the selected dihydroxybenzene starting material in the presence of a Lewis Acid. Nitration, on the other hand, occurs when the dihydroxybenzene is reacted with nitric acid in the presence of sulfuric acid. Sulfonation occurs when the dihydroxybenzene is reacted with concentrated sulfuric acid. On the other hand, amination will generally be produced by reacting a source of amino with the dihydroxybenzene in the presence of liquid ammonia. Further, as with typical benzene- derived compounds, acylation and alkylation can occur via Friedel-Crafts reactions.
  • solubilizing groups such as sulfonate (-SO ) or carboxylate ( ⁇ CO ) groups. These appear to impart good solubilityldispersibility properties to the peracid precursors of this invention. Additionally, it is preferred that a counterpart ion (counterion) to the sulfonate or carbonate group be chosen from H + or an alkali metal ion selected from sodium, potassium or lithium, although alkaline earth counterions and even ammonium counterions may be appropriate.
  • the precursors can be incorporated into a liquid or solid matrix for use in liquid or solid detergent bleaches by dissolving into an appropriate solvent or surfactant or by dispersing onto a substrate material.
  • appropriate solvents include acetone, non-nucleophilic alcohols, ethers or hydrocarbons. Other more water-dispersible or -miscible solvents may be considered.
  • the precursors of the present invention could be incorporated onto a non-particulate substrate such as disclosed in published European Patent Application EP 98 129, whose disclosure is incorporated herein by reference.
  • the phenylene diesters of this invention which contain mixed chain lengths, i.e., a shorter carbon chain length of at least one ester functionality, and a longer carbon length at the second ester functionality, provides extremely proficient bleaching.
  • one of the ester functionalities has an alkyl straight chain length of less than 5, e.g., wherein R 1 or R 4 is CH 3 , and the other alkyl group's chain length is greater than 5 carbon atoms, peroxyacids which are, respectively, hydrophilic and hydrophobic are generated.
  • the believed advantage thereof is that particulate .soils, e.g., clay soil, and hydrophilic stains, e.g., tea and wine, can be attacked with a hydrophilic peroxyacid bleach while oily soils, e.g., sebum, can be attacked with a hydrophobic peroxyacid bleach.
  • a hydrophilic peroxyacid bleach e.g., tea and wine
  • oily soils e.g., sebum
  • Pre-formed peracids appear, however, to have storage stability problems and may lose significant amounts of active oxygen (A.O) upon prolonged storage.
  • EP 98 129 discloses in one embodiment, separate peracid precursors which are impregnated on a fabric substrate. Problematic to this approach are the added manufacturing steps to producing different peracid precursors and using slurrying, emulsifying or other techniques to bind the different precursors to the substrate.
  • a particularly preferred combination of the present invention is when one ester is an acetate (e.g., R 1 is CH 3 ) and the other is an hexanoate, heptanoate, octanoate or nonanoate (e.g., R 4 is -(CH 2 ) 4 CH 3 to -(CH Z ),CH 3 ).
  • the total number of backbone carbons of R 1 plus R 4 should be in the range of 2-20, more preferably 5-20, most preferably 7-14.
  • any dihydroxybenzene whether catechol, hydroquinone or resorcinol, can be used as perhydrolysis leaving groups, and that the resulting antioxidant does not appreciably or rapidly consume the oxidant formed, i.e., the peroxyacid(s).
  • Resorcinol and catechol may be the preferred leaving groups because, of the byproducts of perhydrolysis of ortho, meta and para phenylene diesters, hydroquinone may be the most readily oxidizable.
  • an alternate mode and preferred embodiment is to combine the precursors with a surfactant.
  • Particularly effective surfactants appear to be nonionic surfactants.
  • Preferred surfactants of use include linear ethoxylated alcohols, such as those sold by Shell Chemical Company under the brand name Neodol.
  • Suitable nonionic surfactants can include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oxide and about 1 to 10 moles of propylene oxide per mole of alcohol; linear and branched alkyl- phenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.
  • nonionic surfactants may include polyoxyethylene carboxylic acid esters, fatty acid glycerol esters, fatty acid and ethoxylated fatty acid alkanolamides, certain block copolymers of propylene oxide and ethylene oxide, and block polymers of propylene oxide and ethylene oxide with propoxylated ethylene diamine. Also included are such semi-polar nonionic surfactants like amine oxides, phosphine oxides, sulfoxides, and their ethoxylated derivatives.
  • Anionic surfactants may also be suitable.
  • anionic surfactants may include the ammonium, substituted ammonium (e.g., mono-, di-, and triethanolammonium), alkali metal and alkaline earth metal salts of C 6 -C 20 fatty acids and rosin acids, linear and branched alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates, alkane sulfonates, olefin sulfonates, hydroxyalkane sulfonates, fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates and acyl N-methyltaurides.
  • substituted ammonium e.g., mono-, di-, and triethanolammonium
  • Suitable cationic surfactants may include the quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom is a C12-C18 alkyl group and the other three groups are short chained alkyl groups which may bear inert substituents such as phenyl groups.
  • suitable amphoteric and zwitterionic surfactants which contain an anionic water-solubilizing group, a cationic group and a hydrophobic organic group may include amino carboxylic acids and their salts, amino dicarboxylic acids and their salts, alkylbetaines, alkyl aminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain tertiary sulfonium compounds.
  • Other examples of potentially suitable zwitterionic surfactants can be found described in Jones, U.S. 4,005,029, at columns 11-15, which are incorporated herein by reference.
  • anionic, nonionic, cationic and amphoteric surfactants which may be suitable for use in this invention are depicted in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 22, pages 347-387, and McCutcheon's Detergents and Emulsifiers, North American Edition, 1983, which are incorporated herein by reference.
  • the hydrogen peroxide source may be selected from the alkali metal salts of percarbonate, perborate, persilicate and hydrogen peroxide adducts and hydrogen peroxide. Most preferred are sodium percarbonate, sodium perborate mono- and tetrahydrate, and hydrogen peroxide. Other peroxygen sources may be possible, such as monopersulfates and monoperphosphates. In liquid applications, liquid hydrogen peroxide solutions are preferred, but the precursor may need to be kept separate therefrom prior to combination in aqueous solution to prevent premature decomposition.
  • the buffer may be selected from sodium carbonate, sodium bicarbonate, sodium borate, sodium silicate, phosphoric acid salts, and other alkali metal/alkaline earth metal salts known to those skilled in the art.
  • Organic buffers such as succinates, maleates and acetates may also be suitable for use. It appears preferable to have sufficient buffer to attain an alkaline pH, i.e., above at least about 7.0.
  • the filler material which, in a detergent bleach application, may actually constitute the major constituent, by weight, of the detergent bleach, is usually sodium sulfate.
  • Sodium chloride is another potential filler.
  • Dyes include anthraquinone and similar blue dyes. Pigments, such as ultramarine blue (UMB), may also be used, and can have a bluing effect by depositing on fabrics washed with a detergent bleach containing UMB. Monastral colorants are also possible for inclusion.
  • Brighteners such as stilbene, styrene and styrylnapthalene brighteners (fluorescent whitening agents), may be included. Fragrances used for esthetic purposes are commercially available from Norda, International Flavors and Fragrances and Givaudon.
  • Stabilizers include hydrated salts, such as magnesium sulfate, and boric acid.
  • a preferred bleach composition in which a mixed diester compound as in (III) above is the precursor, has the following ingredients:
  • the above composition is formulated to deliver, desirably, about 14 ppm A.O. at a pH of about 10.5.
  • Other peroxygen sources such as sodium perborate monohydrate or sodium percarbonate are suitable. If a more detergent-type product is desired, the amount of filler can be increased and the precursor halved or further decreased.
  • novel precursors of this invention are synthesized by the methods which are disclosed below. Additionally, performance results are shown below in the EXPERIMENTAL section.
  • acetoxylated resorcinol is obtained through commercial sources (from American Hoechst). It is placed in a reaction vessel with an equimolar amount of dioctanoic acid anhydride (from Aldrich Chemicals), in the presence of methanesulfonic acid to promote acid catalysis, and reacted at room temperature (21°C) for one hour. A 95% yield of the 1 octanoyloxy-3-acetoxy benzene (resorcinol acetate octanoate) and octanoic acid as a by-product results.
  • any of the dihydroxybenzenes are suitable for use as starting materials. If non-nucleophilic solvents are required, as in base catalysis, acetone (dimethyl ketone), ethyl or methyl acetate, tetrachloromethane, dichloromethane, ethylene chloride, chloroform, and others appear appropriate to the synthesis.
  • the catalyst 4-dimethylaminopyridine, appears to promote transesterification by acting to form a reactive intermediate.
  • Other suitable catalysts may include pyridine and other tertiary aliphatic and aromatic amines.
  • the base which may act to tie up any carboxylic acid moieties formed in the reaction, may include triethylamine, tetramethyl piperidine, NaHC0 3 , Na 2 CO 3 , and suitable tertiary amines. In the selection of suitable bases, care must be taken to insure solubility of the ingredients in the reaction. Similarly, if acid catalysis is the chosen route of synthesis, concentrated sulfuric acid, hydrochloric acid, and methanesulfonic acid are among the catalysts of choice known to those skilled in the art.
  • the compound synthesized in I (resorcinol acetate octanoate) was combined in aqueous solution with sufficient hydrogen peroxide to yield a hydrogen peroxide:precursor ratio (based on ester equivalents) of about 1.4:1.
  • the reaction conditions were pH 10.5 (based on 0.02M NaHC0 3 ), temperature 25°C, and 1 g/1 liter of a nonionic surfactant, Neodol 25-12 (which is a linear ethoxylated alcohol with predominant chain length of 12-15 carbon atoms, averaging about 12 moles of ethylene oxide per mole of alcohol).
  • the concentration of II (resorcinol acetate octanoate) was 4.375 x 10- 4 M, H 2 0 2 was about 1.225 x 10 -3 M, to result in an H 2 0 2 :precursor (based on ester equivalents) ratio of about 1.4:1. Yields of about 75% peracid were obtained. Low levels of diacyl peroxide were detected consistent with the high peracid yield.
  • any acetyl octanoyl diacyl peroxide formed may be rapidly re-perhydrolyzed, i.e., converted back into peracid, without the need for a large excess of hydrogen peroxide. Further experiments appear to bear out the low diacyl peroxide formation in the inventive compositions.

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  • Chemical Kinetics & Catalysis (AREA)
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Claims (19)

1. Verbindung der allgemeinen Struktur:
Figure imgb0025
worin R1 Alkyl mit weniger als 5 Kohlenstoffatomen bedeutet und X1, X2, Y und Z individuell ausgewählt werden unter H, SO
Figure imgb0026
, CO
Figure imgb0027
, NO2, NR
Figure imgb0028
-Halogen, R6 und ihren Gemischen,
worin R4 von
Figure imgb0029
Alkyl mit 5 bis 11 Kohlenstoffatomen bedeutet, R5 von NR
Figure imgb0030
ausgewählt wird unter H, Alkyl mit 1 mit 24 Kohlenstoffatomen und ihren Gemischen, und R6 Alkyl mit 1 bis 20 Kohlenstoffatomen bedeutet.
2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß mindestens einer der Substituenten X1, X2, Y und Z Halogen, ausgewählt aus der Gruppe CI-, F-, Br- und J-, bedeutet.
3. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß mindestens einer der Substituenten X1, X2, Y und Z SO- 3 mit einem Gegenion bedeutet, welches H+ oder ein Alkalimetallkation, ausgewählt unter Natrium, Kalium oder Lithium, ist.
4. Verbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß O.CO.R1 und O.CO.R4 in para-Beziehung zueinander stehen.
5. Verbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß O.CO.R1 und O.CO.R4 in ortho-Beziehung zueinander stehen.
6. Verbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß O.CO.R1 und O.CO.R4 in meta-Beziehung zueinander stehen.
7. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß R1 CH3 und R4 C5-11-Alkyl bedeuten.
8. Verbindung nach Anspruch 7, dadurch gekennzeichnet, daß R4 C5-8-Alkyl bedeutet.
9. Bleichzusammensetzung, dadurch gekennzeichnet, daß sie enthält:
(a) eine Quelle für Wasserstoffperoxid, und
(b) eine wirksame Menge für das Bleichen aus einer Persäurevorstufe, die eine Verbindung nach einem der Ansprüche 1 bis 8 ist.
10. Zusammensetzung nach Anspruch 9, dadurch gekennzeichnet, daß sie zusätzlich (c) ausreichende Mengen eines Puffers enthält, so daß ein alkalischer pH-Wert erhalten wird, wenn die Zusammensetzung in wäßrige Lösung gegeben wird.
11. Zusammensetzung nach Anspruch 9 oder 10, dadurch gekennzeichnet, daß sie zusätzlich (d) ein oberflächenaktives Mittel enthält, welches mit der Vorstufe nicht reagiert.
12. Zusammensetzung nach Anspruch 11, dadurch gekennzeichnet, daß das oberflächenaktive Mittel ausgewählt wird unter anionischen, nichtionischen, zwitterionischen, kationischen, amphotären oberflächenaktiven Mitteln und ihren Gemischen und bevorzugt ein anionisches oberflächenaktives Mittel ist.
13. Zusammensetzung nach Anspruch 9 bis 12, dadurch gekennzeichnet, daß die Quelle für Wasserstoffperoxid ausgewählt wird aus Alkalimetallsalzen von Percarbonat, Perborat, Persilicat, Wasserstoffperoxidaddukten und Wasserstoffperoxid.
14. Zusammensetzung nach Anspruch 13, dadurch gekennzeichnet, daß die Wasserstoffperoxidquelle ausgewählt wird unter Natriumperboratmonohydrat oder -tetrahydrat, Natriumpercarbonat und Wasserstoffperoxid.
15. Zusammensetzung nach Anspruch 13 oder 14, dadurch gekennzeichnet, daß das Verhältnis von Wasserstoffperoxid, das durch die Wasserstoffperoxidquelle geliefert wird, zu der Vorstufe größer ist als 1:1 Wasserstoffperoxid zu Esteräquivalent.
16. Zusammensetzung nach einem der Ansprüche 9 bis 15, dadurch gekennzeichnet, daß die Vorstufe ausgewählt wird aus Phenylenmonoacetatmonohexanoat, Phenylenmonoacetatmonoheptanoat, Phenylenmonoacetatmonooctanoat und Phenylenmonoacetatmonononanoat.
17. Verfahren zur Entfernung von Verunreinigungen aus Textilmaterialien bzw. Flächengebilden, dadurch gekennzeichnet, daß das Textilmaterial bzw. Flächengebilde mit einer Bleichzusammensetzung nach einem der Ansprüche 9 bis 16 behandelt wird.
18. Verfahren zur Herstellung einer Bleichzusammensetzung, dadurch gekennzeichnet, daß
(a) eine Quelle für Wasserstoffperoxid, und
(b) eine Menge, die zum Bleichen wirksam ist, einer Persäurevorstufe nach einem der Ansprüche 1 bis 8 vermischt werden.
19. Verfahren zur Synthese einer Verbindung der Formel nach Anspruch 1, dadurch gekennzeichnet, daß ein geeignetes Dihydroxybenzol, ausgewählt aus der Gruppe, die im wesentlichen besteht aus Hydrochinon, Resorcin und Catechol, wobei das Dihydroxybenzol unter Bildung der Gruppe O―C(O)―R1 oder O―C(O)―R4, worin R1 und R4 die in Anspruch 1 gegebenen Bedeutungen besitzen, monoverestert ist mit der ungefähr äquimolaren Menge eines Carbonsäureanhydrids unter Bildung der anderen Gruppe O―C(O)―R1 oder O-C(O)-R4, umgesetzt wird.
EP85309075A 1984-12-14 1985-12-12 Gemischte Phenylendiester als Persäurevorläufer Expired - Lifetime EP0185522B1 (de)

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US681983 1976-04-30
US68198384A 1984-12-14 1984-12-14

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EP0185522A3 EP0185522A3 (en) 1987-07-01
EP0185522B1 true EP0185522B1 (de) 1990-11-07

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CA (1) CA1270717A (de)
DE (1) DE3580460D1 (de)
ES (2) ES8801893A1 (de)
TR (1) TR22733A (de)

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Also Published As

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ES8802581A1 (es) 1988-09-01
TR22733A (tr) 1988-05-24
EP0185522A2 (de) 1986-06-25
DE3580460D1 (de) 1990-12-13
ES550880A0 (es) 1988-03-01
ES8801893A1 (es) 1988-03-01
CA1270717A (en) 1990-06-26
EP0185522A3 (en) 1987-07-01
ES557775A0 (es) 1988-09-01

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