Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—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, exemplary of which are phenylene mono - and diesters, in water, said precursors being of the general structure: wherein R 1 , R 2 , X 1 , x 2 , Y and Z are defined within the specification.
• Peroxygen bleaching compounds such as hydrogen peroxide, sodium percarbonate, sodium perborate monohydrate or tetrahydrate, are useful for bleaching fabrics, textiles and other materials.
• these sorts of peroxygen bleaches appear less effective when bleaching temperatures of less than 70 0 C are utilized.
• the low wash temperatures 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
• Preferred embodiments include phenylene monoesters wherein R 2 is O H and R 1 is straight chain alkyl of 1 to 11 carbon atoms; and phenylene diesters wherein R 2 is - both R 2 and R 4 straight chain comprising alkyls of 1 to 11 carbon atoms.
• 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.
• the invention generally relates to novel peracid precursors Typical precursors are esters, imide or enol ester compounds which are combined with a source of peroxygen, such as hydrogen peroxide, sodium percarbonate or sodium perborate. These particular types of precursors are commonly used in Europe where washing temperatures are generally higher than is prevalent in the United States. Washing temperatures of up to 100°C are common in Europe.
• the substituents R 1 , R 4 and R 6 may additionally be either straight chain, branched chain, have some unsaturation (for example, if R 1 , R4 or R 6 is derived from natural oils or fatty acids, e.g., oleic acid), and may be substituted at various positions on the carbon chain.
• any combination of these substituents may be present in the precursors of this invention.
• substituents are charged moieties, e.g. SO - 3 , appropriate counterpart ions (counterions) may be present.
• R comprise alkyl of 1 to 20, more preferably 1 to 15, and most preferably 1 to 11 carbon atoms. particularly preferred are phenylene monoesters of about 6-11 carbon atoms in length, which appear to provide surface active peracids when combined with a hydrogen peroxide source in aqueous solution.
• phenylene monoesters of about 6-11 carbon atoms in length, which appear to provide surface active peracids when combined with a hydrogen peroxide source in aqueous solution.
• EXPERIMENTAL Example I I , these particular compounds were found to be excellent in perhydrolysis, giving good yields of the desired peracid, with surprisingly low levels of diacyl peroxide, which, as described in Chung it al, U.S. 4,412,934, may be problematic.
• R may be straight chain, branched, unsaturated or substituted.
• a source of hydrogen peroxide e.g., sodium perborate monohydrate
• two different oxidizing species appear to be present which can attach to different types of soils, i.e., hydrophilic soils such as tea and wine, and oily soils, such as sebum.
• the phenylene diesters of (III) include ortho, meta and para-substituted phenylene diesters, such as diacetate, dihexanoate, dioctanoate and mixed (i.e., wherein R 1 ⁇ R 4 ) ester derivatives 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.
• the diesterified derivatives of these dihydroxybenzene compounds are generally produced by reacting them with an appropriate acid anhydride in the presence of a strong acid.
• the general procedures for making these precursors are set forth below in EXPERIMENTAL. Additionally, the preferred phenylene monoesters are depicted below in EXPERIMENTAL.
• solubility/dispersibility and hence performance can be improved by the addition of solubilizing groups such as SO - 3 , CO - 2 , NR 3+ 4 .
• solubilizing groups such as SO - 3 , CO - 2 , NR 3+ 4 . 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 - 3 ) or carboxylate (-CO2) groups. These appear to impart good solubility/dispersibility 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 once 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.
• precursors containing 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 C H 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.
• E P 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 is -(CH2)4CH3 to -(CH 2 ) 7 CH 3 ).
• the total number of backbone carbons of R plus R 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.
• the ester equivalents of the phenylene diester precursors Based on two reactive sites, i.e., the ester equivalents of the phenylene diester precursors, a ratio of 1:1 hydrogen peroxide: ester is possible, although ratios greater than this are also within the invention. It is preferred that the molar ratio of hydrogen peroxide: ester be from about 1:20 to 20:1, more preferably about 1:10 to 10:1, most preferably about 1:1 to 5:1.
• 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 alkylphenoxy (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 C 12 -C 18 alkyl group and the other three groups are short chained alkyl groups which may bear inert substituents such as phenyl groups.
• 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 p H , 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 U MB . 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 N orda, International Flavors and Fragrances and Givaudon.
• Stabilizers include hydrated salts, such as magnesium sulfate, and boric acid.
• the above composition is formulated to deliver, desirably, 14 parts per million total available oxygen (ppm A.O.), at a pH of about 10.5
• 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.
• resorcinol may be combined with about an equimolar amount of dioctanoic acid anhydride, and ethyl acetate solvent, a non-nucleophilic solvent, in the presence of 4-dimethylaminopyridine, a catalyst, and a base, such as triethylamine, at room temperature, to produce the desired 1 octanoyloxy-3-hydroxy benzene (resorcinol monooctanoate).
• 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.
• resorcinol In a reaction vessel, resorcinol is placed with an equimolar amount of hexanoic acid anhydride (from Aldrich Chemicals). Concentrated sulfuric acid (98%) is added to the solution and heated at 100°C for 3 hours. A crude reaction product was obtained from this acid catalysis containing the 1,3 dihexanoyloxybenzene (resorcinol dihexanoate) and hexanoic acid.
• reaction mixture is diluted with diethyl ether and the hexanoic acid removed by extraction with 5% NaHC0 3 .
• the ether phase is dried under Na 2 S0 4 and rotary evaporated to remove the solvent.
• hydroquinone dihexanoate the resulting solid is recrystallized with EtOH/H 2 0 to give a pure solid (m.pt. 56-57°C).
• resorcinol dihexanoate the liquid is distilled and the product fraction collected at 175-180/0.5mm Hg. Isolated yields are generally 90% for either synthesis.
• 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 A ldrich 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.
• the concentration of II (resorcinol acetate octanoate) was 4.375 X 10 4 M, H 2 O 2 was about 1.225 X 10 -3 M, to result in an H 2 O 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.
• Standard bleaching and detergent adjuncts may be added to the compositions disclosed.
• exemplary of such adjuncts are builders (sodium carbonate, sodium tripolyphosphate, etc.), fillers (e.g., sodium sulfate), brighteners, enzymes (e.g., alkaline proteases), defoaming agents, and the like known to those skilled in the art.
• further esterification of the phenylene diesters may be possible, for example, resulting in tri- and quaternary-, substituted phenylene precursors.
• the claims hereto further llustrate the invention.

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Citations (12)

• 1985
  • 1985-12-10 TR TR49502/85A patent/TR22733A/xx unknown
  • 1985-12-11 CA CA000497390A patent/CA1270717A/en not_active Expired
  • 1985-12-12 DE DE8585309075T patent/DE3580460D1/de not_active Expired - Lifetime
  • 1985-12-12 EP EP85309075A patent/EP0185522B1/de not_active Expired - Lifetime
  • 1985-12-13 ES ES550880A patent/ES8801893A1/es not_active Expired
• 1987
  • 1987-10-16 ES ES557775A patent/ES8802581A1/es not_active Expired

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