AU613900B2

AU613900B2 – Quaternary ammonium or phosphonium peroxycarbonic acid precursors and their use in detergent bleach compositions
– Google Patents

AU613900B2 – Quaternary ammonium or phosphonium peroxycarbonic acid precursors and their use in detergent bleach compositions
– Google Patents
Quaternary ammonium or phosphonium peroxycarbonic acid precursors and their use in detergent bleach compositions

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Publication number
AU613900B2

AU613900B2
AU13125/88A
AU1312588A
AU613900B2
AU 613900 B2
AU613900 B2
AU 613900B2
AU 13125/88 A
AU13125/88 A
AU 13125/88A
AU 1312588 A
AU1312588 A
AU 1312588A
AU 613900 B2
AU613900 B2
AU 613900B2
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AU
Australia
Prior art keywords
precursor
alkyl
sodium
composition
group
Prior art date
1987-03-17
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AU1312588A
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Inventor
Robert William Riley Humphreys
Stephen Alan Madison
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Unilever PLC

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Unilever PLC
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1987-03-17
Filing date
1988-03-15
Publication date
1991-08-15

1988-03-15
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Unilever PLC

1988-09-15
Publication of AU1312588A
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Critical
patent/AU1312588A/en

1991-08-15
Application granted
granted
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1991-08-15
Publication of AU613900B2
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Critical
patent/AU613900B2/en

2008-03-15
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Ceased
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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton

C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton

C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton

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

C11D3/393—Phosphorus, boron- or silicium-containing compounds

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

C11D3/3917—Nitrogen-containing compounds

C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames

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

C11D3/3917—Nitrogen-containing compounds

C11D3/3927—Quarternary ammonium compounds

Description

AUSTRALIA
PATENTS ACT 1952 COMPLETE SPECIFICATION Form
(ORIGINAL)
FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: S Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: UNILEVER PLC UNILEVER HOUSE
BLACKFRIARS
LONDON EC4
ENGLAND
Actual Inventor: Address for Service: CLEMENT HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.
Complete Specification for the invention entitled- QUATERNARY AMMONIUM OR PHOSPHONIUM PEROXYCARBONIC ACID PRECURSORS AND THEIR USE IN DETERGENT BLEACH COMPOSITIONS The following statement is a full description of this invention including the best method of performing it known to me:-
J
1A C 6034 (R) UATERNARY AMMONIUM OR PHOSPHONIUM PEROXY CARBONIC ACID PRECURSORS AND THEIR USE IN DETERGENT BLEACH
COMPOSITIONS
BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to novel bleach precursors, peracids generated therefrom and use of these materials in detergent compositions.
2. The Prior Art It is well known that active oxygen-releasing compounds are effective bleaching agents. These compounds are frequently incorporated in detergent compositions for stain and soil removal. Unlike the traditional sodium hypochlorite bleaches, oxygen-releasing compounds are less aggressive and thus more compatible with detergent compositions. They have, however, an important limitation: the activity of these compounds is extremely temperature-dependent. Thus, oxyqen-releasing bleaches are essentially only practical when the bleaching solution is heated above 60°C. At a temperature of just 0 C, extremely high amounts of the active oxygenreleasing compounds must be added to the system to achieve any bleach effect. Although this would indicate the desirability of high temperature operation,, high temperatures are both economically and practically disadvantageous.
At bleach solution temperatures below 60°C, the active oxygen-releasing compounds are rendered much less effective regardless of their level in the system. With respect to bleaching of laundry in automatic household washing machines, it must be noted that these machines are normally operated at wash-water temperatures below
-I
2 C 6034 (R) Consequently, there has developed a need for substances which promote release of active oxygen at temperatures below 60″C. These substances are generally referred to in the art as bleach precursors, although they have also been called promoters and activators.
Normally, bleach precursors are used in conjunction with persalts capable of releasing hydrogen peroxide in aqueous solution, perborate being the most widely used persalt.
Typically, the precursor is a reactive compound such as a carboxylic acid ester that in alkaline solution containing a source of hydrogen peroxide, e.g. a persalt, will generate the corresponding peroxy acid.
000 The reaction involves nucleophilic substitution on to S the precursor by hydroperoxy anions (HOO-) and is facilitated by precursors having good leaving groups.
Often the reaction is referred to as perhydrolysis.
Early patents in the area of precursor chemistry include US Patent 3,256,198 and US Patent 3,272,750, each of S which suggests the use of organic carbonate esters as bleach aids. British Patent 836,988 and British Patent 864,798 were forerunners disclosing the use of aliphatic carboxylic acid esters as adjuncts for accelerating the S bleaching of persalts such as sodium perborate or .000* percarbonate.
US Patent 4,283,301 discloses a peroxygen bleach and a precursor of the general formula: 0 0 O II II l R-C-Z or Z-C-R 2
-C-Z
wherein R is an alkyl chain containing from 5 to 13 carbon atoms, R 2 is an alkyl chain containing from 4 to 24 carbon atoms and each Z is a leaving group as defined therein.
3 C 6034 (R) US Patent 4,412,934 reports compositions incorporating bleach precursors of the general formula: 0
R-C-L
wherein R is an alkyl group containing from 5 to 18 carbon atoms and L is a leaving group.
Similar disclosures are found in US Patent 4,486,327, EP 0 098 129, EP 0 106 584, EP 0 106 634, EP 0 120 591, EP 0 163 331, EP 0 166 571, EP 0 185 522, EP 0 170 386, EP 0 153 222, EP 0 150 223 and EP 0 202 698. Among the preferred leaving groups are those having solubilizing functionality including sulphonic, sulphuric, carboxylate and quaternary ammonium salt groups.
A typical precursor within the concept of the aforedescribed patents is sodium n-nonanoyloxybenzene sulphonate presently commercialized as a component of a branded detergent. This sulphonate, in combination with sodium perborate, effectively releases peroxygen S fragments upon perhydrolysis, as well as sodium 4sulphophenol. Once released, the p-sulphophenol fragment Sunfortunately provides no additional fabric washing benefit.
Esters such as sodium n-nonanoyloxybenzene sulphonate are reported to require greater than stoichiometric amounts of alkaline hydrogen peroxide. For example, US Patent 4,536,314 discloses hydrogen peroxide/activator ratios ranging from greater than 1.5:1 to 10:1. High peroxide ratios are necessary with these activators to ensure high rates of peracid formation and to account for the unavoidable depletion of peroxide by natural soils. These high ratios are econom.i4ally wasteful.
US Patent 3,686,127 recognizes the shortcomings of precursors, the leaving groups of which provide no J1 4 C 6034 (R) additional fabric washing benefit. Therefore, the patent suggests use of alkylated sulphophenol carboxylic esters which release leaving groups that provide detergent and emulsifying properties. However, with this modification to the leaving group structure, the yield of peracid falls to essentially non-useful levels. For instance, sodium 2-acetoxy-5-hexylbenzene-sulphonate yields 43% peracid after 5 minutes but the unsubstituted derivative yields 80% peracid. Presumably, unfavourable steric or electrostatic interactions arising from the alkyl substituents retard the rate of perhydrolysis.
US Patent 4,397,757 reports that having quaternary ammonium groups on the precursor is advantageous because it allows precursor and intermediate species to substantively attach on to surfaces undergoing bleaching, e.g. fabric surfaces. Substantivity was said to lead to enhanced stain removal, particularly at low temperature. A drawback of this technology is the expense in preparing the precursors; the synthesis involves several steps and requires excess reagent.
Starting materials are also not readily available.
While the aforementioned precursors have all been reported effective at stain removal, there is still need of more efficient systems. Stain removal efficiency may be improved either by a precursor that generates equivalent bleach at a lower precursor molar level or operates at lower levels of hydrogen peroxide source, Not only do lower levels of peroxide source or precursor provide better economics, they also permit increased flexibility in detergent formulation.
Consequently, it is an object of the present invention to provide a detergent bleach composition with a precursor that permits bleaching over a wide temperature range including that of under ~J L C 6034 (R) It is another object of the present invention to provide certain novel bleach precursors which have hitherto not been described in the art.
A further object of the present invention is to provide a precursor having a group capable of imparting additional benefits to treated substances including that of detergency and/or fabric softening while still achieving high peracid-generating levels.
Another object of the present invention is to provide a precursor that can be economically synthesized from readily available starting materials and in a minimum number of synthetic steps, A final object of the present invention is to provide novel peroxy acids generated from the bleach precursors by perhydrolysis with hydrogen peroxide or persalts.
SUMMARY OF THE INVENTION A bleach precursor compound is provided having the formula:
R
1 0 Z~ R 2 +Q R 4 OCL (I) d3 wherein:
R
1
R
2 and R 3 are each a radical selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aryl, phenyl, hydroxyalkyl, polyoxyalkylene and R 4 0COL; or two or more of R 1
R
2 and R 3 together form an alkyl-substituted or unsubstituted, nitrogen-containing heterocyclic ring system; or at least one of R 1
R
2 and R 3 is attached to R 4 to form an alkyl-substituted or unsubstituted, nitrogencontaining heterocyclic ring system;
R
4 is selected from a bridging group consisting of L 6 C 6034 (R) alkylene, cycloalky)ene, alkylenephenylene, phenylene, arylene, and polyalkoxylene and wherein the bridging group can be unsubstituted or substituted with CI-C 2 0 alkyl, alkenyl, benzyl, phenyl and aryl radicals; Z- is a monovalent or multivalent anion leading to charge neutrality when combined with Q+ in the appropriate ratio and wherein Z- is sufficiently oxidatively stable not to interfere significantly with bleaching by a peroxy carbonic acid; Q is nitrogen e-r-phesphru-; and L is a leaving group selected from the group consisting of:
_R
5
Y
0 SO0
CH
2
-C
N C R 6 0 C R 6 -N NH,
C
Y 0
R
5 0 CH C CR CH 2 and 0 C CHR 7 wherein
R
5 and R 6 are a CI-C 12 alkyl group, R 7 is H or Rr, and Y is H or a water-solubilizing group, selected from
-SO-
3 -COO-M+, -SO- 4 M -N+(RS) 3 X’ NO 2 OH, and 0-N(R 5 2 and mixtures thereof; wherein M is a hydrogen, alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium cation. X» is a halide, hyd )xide, phosphate, sulph4te, methyl sulphate or acetate anion.
i 1 .1 7 C 6034 (R) A peroxygen acid is also provided having the formula: R1 0 J1 Z- R 2 Q R 4 OCOOH (II)
R
3 Furthermore, a detergent bleaching composition is provided comprising i) from 1 to 60% of a peroxygen compound capable of yielding hydrogen peroxide in an aqueous solution; ii) from 0.1 to 40% of the bleach precursor of formula I described hereinabove; iii) from 0 to 50% of a surfactant; and iv) from 0 to 70% of a detergent builder.
DETAILED DESCRIPTION OF THE INVENTION There have now been discovered a novel group of compounds having the formula: RI 0
I’
Z- Rg +Q R 4 OCL
R
3 which meet many of the ojectives outlined. Peroxy carbonic acid precursors of the formula I have been found to generate peroxy carbonic acids that are superior bleaching agents, giving substantially higher levels of stain removal for a given level of persalt than observed with known precursors.
A most important component of precursor compound is the leaving group Leaving groups of the appropriate structure facilitate reaction of the bleach precursor with hydrogen peroxide in basic aqueous solution to generate a peroxy carbonic acid bleach as follows: R1 0 HOO R 1 0 I I+ I It Z» R 2
+Q-R
4 -0OL Z» R2- Q-R 4 -0COOH L- (eq. 1) 3 R3
R
3
R
3 C 6034 (R) Leaving groups effective for the present invention will induce rapid formation of the peroxy carbonic acid in the presence of a peroxygen source under practical conditions, e.g. in detergent solution during laundering of clothes. Generally, L must be of an electronattracting structure which promotes successful nucleophilic attack by the perhydroxide anion. Leaving groups which exhibit such properties are those in which the conjugate acid has a pKa in the range of from about 6 to about 13, preferably from about 7 to about 11, most preferably from about 8 to about 11.
Many and diverse leaving group structures have been described in the patent literature and are useful for this invention. For example, US Patent 4,412,934, US Patent 4,483,778, European Patent Application 170,386 and European Patent Application 166,571 provide examples of desirable leaving groups and are herein incorporated by way of reference.
The compounds of the invention have leaving structures L selected from the group consisting of: -o0 -o0K 0y 00 0 0 0 SC R
NH,
R
5
C
I It Y 0 0 -CH H CH 2 and 0 C CHR 7 9 C 6034 (R)
R
5 and R 6 are a C 1
-C
1 2 al~kyl group, R 7 is H or R 5 and Y is H or a water-solubilizing group, selected from
-SO-
3 -COO-M+, -SO- 4
-N+(R
5 3
NO
2 OH, and
O*-N(R
5 2 and mixtures thereof; wherein M+ is a hydrogen, a:Lkali metal, ammonium or alkyl or hydroxya2,kyl -substituted ammonium cation. X- is a halide, hydroxide, phosphate, sulphate, methyl sulphate or acetate anion.
Most preferred of the leaving groups is thle phenol sulphonate type. Especially preferred is the 4sulphophenol group. Sodium, potassium and ammonium cations are the preferred counter-ions to the suiphopheno], structures Although phosphonium groups Where Q is phosphorus are within the scope of this inVention, for economic reasons it is most preferred that Q be nitrogen. Furthermore, the precursor and respective peracid derivative compounds should preferably contain a~ quaternary ammonium cation surrounded by R 1 1 n 3 ,ec h same or different and having C 1
-C
2 0 atom radicals selected from the group consisting of alicyll alYylaryl, benzyl, hydroxyalkyl, heterocyclic rings containing the quatex-nary nitrogen groups Where RI and R 4 or RI and R2 are Joined together, and mixtures of groups thereof, In particular, it is desirable that RIl be a short-chain
C-
1
-C
4 alkyl radical, preferably methyl, While R 2 and R 3 be a longer chain C 7 -02 0 alkyl or alkylaryl, such as a stearyl, lauryl, or benzyl group. With regard to the R 4 bridge between the quaternary nitrogen and carbonate groups, it is desirable that R 4 be a bridging group selected from C 2
-C
2 0 a1llne, C6-0~ 1 2 phonylcrne, CS-C2 0 cycloalkyJleneo and C 8
‘-C
20 41ky3,one phenylene groups.
Preferably, the alkylene groups should have 2 carbon atoms. Further, the bridging group can be Unsubstitubed C 6034 (R) or substituted with C 1
-C
2 0 alkyl, alkenyl, benzyl, phenyl and aryl radicals.
The preferred precursors and peroxygen acid derivative compounds are exemplified by structures III and IV.
Within the context of this invention, there may be compounds having the general structure where R 1 and
R
4 together or RI and R 2 together form an arylsubstituted or unsubstituted, nitrogen-containing heterocylic ring system. Representative of these systems are rings defining pyridine, morpholine, pyrrolidine, piperidine and piperazine.
R
1 0 Y Z- R 2 +N R 4 OC O (III)
R
3 r II Z- R 2 N R 4 OCOOH (IV)
A
3 The following compounds are illustrative of precursors within the present invention. It is also to be understood that upon perhydrolysis elimination of the leaving group, as defined above, there remains an organic peroxygen acid derivative of the structures outlined below, 2-(N-benzyl-NN-dimethylammonium)ethyl sodium 4sulopophenyl carbonate chloride 2-(N,N,N-trimethylammonium)ethyl sodium 4sulphophenyl carbonate chloride 2-(N,N-ditallow-N-methylammonium)ethyl sodium 4sulphophenyl carbonate chloride 3-(N-nonyl-N,N-dimethylammonium)propyl sodium 2sulphophonyl carbonate chloride 11 C 6034 (R) 2- (N-benzyl–N,N-diethylamnonium) ethyl sodium 2suiphophenyl carbonate methosuiphate 2- (N-benzyl-N,N-dimethylammoniui) ethyl disodium 2, 4-disuiphophenyl carbonate metho-,ulphate 2- (N-butyl-N,N-dimethylammonium) ethyl sodium 4carboxyphenyl carbonate bromide 2- (N-stearyl-N,N-diethylammonium) ethyl 2triethanolammoniumphenyl carbonate dichloride 2- (N-diethylhexyl-N-N-dimethylammoriium) ethyl 2- (dimethyl amine oxide)pheny. carbonate chloride 2-(N,N,N-triethylammoniun) ethyl disodium 2,4disuiphophenyl carbonate methosuiphate 4- (N,N,N-trimethylamnmonium) butyl sodium 4-suiphophenyl carbonate bromide 2-(N,N,N-tributylammonium) ethyl sodium 4triethanolammoniumphenyl carbonate dichloride 2-(N,N,N-trimethylammonium)ethyl socdium 4- (diethylamine oxide) phenyl carbonate chloride 2-(N,N,N-t±-ibenzylammonium) ethyl 4-carboxyphenyl carbonate methosulphate 1- N-dihexyl-N-methylmmoniui) -3-pheny’l-2-propyl disodium 2,4-disulphophenyl carbonate chloride 2-(N,N,N-tributylamnmonium) (4-hexyiphenyl) -1-propyl sodium 4-suiphophenyl carbonate chloride 6-f (N,NN-triethylammonium)methyl) -6–codecyl sodium carboxyphenyl carbonate chloride 2- (N,N-didodecyl-N-ethylammonium) prory sodium 4sulphophenyl carbonate chloride 2-f N-benzyl-N-(2-hydroxyethyl) -N~-dodecylaminonium] ethyl sodium 4-sulphophenyl carbonate chloride 2- (N-decyI,-N,N-diethyl.ammoniun) ethyI 4-sulphophenyl sodium carbonate chloride 4- (N-phenyl-N, N-dicdodecylammoniium) bUtyl sodium 4sulphophenyl carbonate chloride -6-dodecyl sodium 4sulphophenyi. carbonate chloride 2-f 2-dodecyl-4- (NN,N-triethylammonium) phenyl] ethyl 12 C 6034 (R) sodium 4-sulphophenyl carbonate chloride Sodium (4-sulphophenoxycarbonyloxy) ethyl] -4de–cylpyridinium chloride Sodium N- 12- (4-sulphophenoxycarbonyloxy) ethyl] imidazolium chloride Disodium bis( (4-sulphophenoxycarbonyloxy) ethyl] inethyldodecyl ammonium chloride Trisodium trisl (4-sulphophenoxycarbonyloxy) ethyl]dodecyl ammonium chloride 2- (N,N,N-trimethylammonium) tetradecyl sodium 4suiphophenyl carbonate chloride 2- (N-octyl-N,N-dimethylaumonium) ethyl sodium 4suiphophenyl carbonate chloride 2- (N,N-didecyl-N-methylammonium) ethyl sodium 4suiphophenyl carbonate chloride 2-(N-benzyl-N-dodecyl-N-methylammonium) ethyl sodium 4suiphophenyl carbonate chloride 2- (NIN,N-trioctylammonium) ethyl rdit,.m 4-sulphophenyl carbonate chloride 1- (N,N,N-trimethylammonium) -2–dodecy. sodium 4sulphophenyJ. carbonate chloride (N-benzyl-N, N-diethylammonium) -3-dodecyl sodium 4suiphophenyl carbonate chloride 1- (N-benzyl-N,N-dibutylammonurt) -2–octyl sodium 4carboxyphenyl carbonate chloride 2 N,t’-trihex41ylammonium) -1-phenyl ethyl 4- (dimethylanine oxide) phenyl carbonate chloride 122- N, N-tri ethyl ammonium) dodecyl 4triethanolamraoniumphenyl carbonate dichloride 2 (N-hexyl N-dimethyl ammonium) ethyl sodilmr 4suiphophenyl carbonate methosuiphate sulphophenyl carbonate chloride 2 (trimethylphospho–nium) ethyl sodium 4 -suiphophenyl, carbonate chlorid~e 2- (cital2.owmethylphosphonium) ethyl sodium 4- 13 Precursors of the present invention represent a new class of quaternary ammonium- substituted peroxy carbonic acid bleaches. The precursors described by structure generate the corresponding percarbonic acids rapidly in the presence of hydrogen peroxide or hydrogen peroxide generating 14- C 6034 (R) persalts such as sodium perborate. Outstanding bleaching is achieved on hydrophilic stains such as tea and red wine. Effective bleaching of tea and red wine stains may occur as low as 20 0 C and even be perceptible at G od bleaching is obtained even at a low molar ratio of hydrogen peroxide to precursor (as low as 1:1) or at a low theoretical percarbonic acid level (5 ppm active oxygen). Typically, the ratio of hydrogen peroxide (or a peroxygen compound generating the equivalent amount of
H
2 0 2 to precursor will range from 0.5:1 to 10:1, preferably 1:1 to 4:1, most preferably 1:1 to less than 1.5:1. Hydrophobic type stains such as that imparted by spaghetti sauce may even successfully be attacked by appropriate members of the herein disclosed peroxy carbonic acid class. Thus, the precursors of the invention provide effective colour safe, cold water bleaching systems.
Although not to be bound by any theory, it is believed that the quaternary ammonium or phosphonium group enhances the interaction between bleach and the negatively charged fabric surface in detergent solution.
Moreover, it is believed that the higher electrophilicity of the peroxy carbonic relative to the peroxy carboxylic type acid functions to increase oxidative power against stains. Thus, peroxy carbonic acid and ester precursors are performance distinguished from known systems such as described in US Patent 4,397,757 and US Patent 4,412,934.
The foregoing precursors may be incorporated in detergent bleach compositions which require as an essential component a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution.
C 6034 (R) Hydrogen peroxide sources are well known in the art.
They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates and persulphates. Mixtures of two or more such compounds may also be suitable. Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because it has excellent storage stability while also dissolving very quickly in aqueous bleaching solutions.
Rapid dissolution is believed to permit formation of higher levels of percarboxylic acid which would enhance surface bleaching performance.
A detergent formulation containing a bleach system consisting of an active oxygen-releasing material and a novel compound of the invention will usually also contain surface-active materials, detergency builders and other known ingredients of such formulations.
The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in literature, for example in «Surface Active Agents and Detergents», Volumes I and II, by Schwartz, Perry and Berch. The total level of the surface-active material may range up to 50% by weight, preferably being from about 1% to 40% by weight of the composition, most preferably 4 to Synthetic anionic surface-actives are usually watersoluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about QJ8 to about 22 carbon atoms, the term alkyl being used to V.r W naj 16 C 6034 (R) include the alkyl portion of higher aryl radicals.
Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C 8
-C
1 8 alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C 9
-C
2 0 benzene sulphonates, particularly sodium linear secondary alkyl
(C
10
-C
15 benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C 9
-C
18 fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alphaolefins (C 8
-C
2 0 with sodium bisulphite and those derived by reacting paraffins with SO 2 and Cl 2 and then hydrolyzing with a base to produce a random sulphonate; sodium and ammonium c 7
-C
12 dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly CI0-C20 alpha-olefins, with 503 and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergent compounds are sodium (C 11
-C
1 5 alkylbenzene sulphonates, sodium (C 1 6
-C
1 8 alkyl sulphates and sodium
(C
16
-C
1 8 alkyl ether sulphates, Examples of suitable nonionic surface-active compounds which may be used, preferably together with the anionic -iqurface-active compounds, include in particular the />i r ction products of alkylene oxides, usually ethylene 11 C 6034 (R) oxide, with alkyl (C 6
-C
22 phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (C 8
-C
18 primary or secondary linear or branched alcohols with ethylene oxide, generally 6-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine. Other so-called nonionic surface-actives include alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
Amounts of amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic, anionic and nonionic actives.
As stated above, soaps may also be incorporated in the compositions of the invention, preferably at a level of less than 30% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic compounds. Soaps which are used are preferably the sodium, or less desirably potassium, salts of saturated or unsaturated C 10
-C
24 fatty acids or mixtures thereof. The amount of such soaps can be varied between about 0.5% and about 25% by weight, with lower amounts of about 0.5% to about 5 being generally sufficient for lather control. Amounts of soap between about 2% and about 20%, especially between about 5% and about are used to give a beneficial effect on detergency. This is particularly valuable in compositions used in hard water when the soap acts as a supplementary builder.
«T 0′ 18 C 6034 (R) The detergent compositions of the invention will normally also contain a detergency builder. Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ionexchange materials and 4) mixtures thereof.
Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its watersoluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetalcarboxylates as disclosed in US Patents 4,144,226 and 4,146,495.
Examples of precipitating builder materials include sodium orthophosphate, sodium carbonate and long-chained fatty acid soaps.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives.
In particular, the compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxysuccinate and the waterinsoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
These builder materials may be present at a level of, /or example, from 5 to 80% by weight, preferably from IT q~lr J 1q C 6034 (R) to 60% by weight.
When the peroxygen compound and bleach precursor are dispersed in water, a peroxy acid (IV) is generated which should deliver about 0.1 to about 50 ppm active oxygen per liter of water; preferably oxygen delivery should range from 2 to 30 ppm. Surfactant should be present in the wash water from about 0.05 to 2.0 grams per liter, preferably from 0.15 to 0.50 grams per liter.
When present, the builder amount will preferably range from about 0.1 to 6.0 grams per liter.
Apart from the components already mentioned, the detergent ompositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphates and silicones, anti-redeposition agents such as sodium carboxymethyl cellulose and alkyl or substituted alkylcellulose ethers, other stabilizers such as ethylene diamine tetraacetic acid, fabric softening agents, inorganic salts such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes such as proteases, cellulases, lipases and amylases, germicides and colourants.
The bleach precursors and their peroxycarbonic acid derivatives described herein are useful in a variety of cleaning products. These include laundry detergents, laundry bleaches, hard surface cleaners, toilet bowl cleaners, automatic dishwashing compositions and even denture cleaners. Precursors of the present invention can b introduced in a variety of product forms if -4 C 6034 (R) including powders, on sheets or other substrates, in pouches, in tablets or in non-aqueous liquids such as liquid nonionic detergents.
The following Examples will more fully illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise illustrated, EXAMPLE 1 Preparation of Choline Chloroformate Chloride
[(CH
3 1 3
NCH
2 CHCOCOClC- Phosgene (113 g, 1.15 moles) was condensed in a 500 ml three-neck flask equipped with an inlet gas dispersion tube, dropping funnel, magnetic stirring bar, and dry ice/acetone condenser topped with a drying tube. The phosgene was contained in a small cylinder and was introduced via the gas dispersion tube. A dry ice/acetone bath was used to keep the phosgene at -30 0
C.
Thereinto was added 250 ml dry chloroform (dried over anhydrous calcium chloride for 48 hours) by means of a dropping funnel. Dry, pulverized choline chloride (40 g, 0.29 mole; dried in a vacuum oven at 250 0 C for 24 hours) was added thereto. The mixture was stirred rapidly at 0 for 1 hour and then allowed to warm to room temperature. Eventually, the reaction mixture separated into two layers. Stirring was continued overnight; hydrogen chloride and any phosgene that escaped during this process was directed to two traps containing 1 N sodium hydroxide.
Workup of the reaction mixture was accomplished by removing the dispersion tube and dropping funnel and attaching a single piece distillation unit to the reaction flask. The receiver flask was covered with a blanket of dry ice. All volatiles were removed from the A L L I 23. C 6034 (R) reaction solution by aid of a water aspirator, leaving white, crystalline choline chloroformate chloride. This product was used without further purification.
Attempts were made to obtain the NMR spectrum of choline chloroformate chloride in a variety of solvents.
Unfortunately, this compound is soluble only in water, in which decomposition and accompanying decarboxylation interferes severely with spectral quality. As a result, NMR analysis of choline chloroformate could not be reported. However, the infrared spectrum in Nugol showed a representative carbonyl peak at 1765 cm 1 Preparation of 2-(NN,N-Trimethylammonium)ethyl Sodium 4-sulphophenyl Carbonate Chloride (SPCC) 0 Cl- (CH 3 3
N+CH
2
CH
2 0C -S03Na Sodium 4-phenolsulphonate dihydrate (6,4 g, 0.028 mol) and sodium hydroxide (1.1 g, 0.028 mol) were dissolved in 60 ml distilled water. Chlolina chloroformate chloride (5.6 g, 0,028 mol) was added while stirring the reaction mixture with a high speed stirrer. After all of the choline chloroformate chloride had dissolved (1-2 minutes), the reaction mixture was frozen in dry ice and freeze-dried. The resulting white solid was analyzed by NMR to be >60 mole of the desired product (SPCC), the major impurities being choline chloride and unreacted sodium 4-phenolsulphonate.
Alternatively, the reaction mixture can be treated with an equal volume of acetone. Thereby the desired product precipitates from solution.
Unreacted p-phenolsulphonate was removed by boiling the crude SPCC in methanol, followed by filtration and ATdprying. Typically, 50 g SPCC was added to 500 ml dry ‘NT C 6034 (R) ethanol. The mixture was boiled and solid SPCC was collected by filtration and dried to give SPCC essentially free of unreacted sodium p-phenolsulphonate (by 60 MHz NMR).
NMR MD 2 0, trimethylsilylacetic acid standard) :3.03 9H); 3.5″3,8 4H); 7.23 2H); 7.77 2H).
EXAMPLE 2 Preparation of e.-(N-benzyl-N.N-dimethvlammonium).
ethyl Chloroformate Chloride Phosgene (35 ml1, 48.5 g, 0,49 mol) was oondensed in apparatus identical with that aforesaido Dry chloroform ml, dried over anhydrous calcium chloride) was added to the phosgene and the solution held at -30′ with a dry ioe/acetone bath. Benzyldimethyl-2-hydroxyethyl ammonium chloride (24.6 g, 0,144 mol) in 100 ml dry chloroform was slowly added through the dropping funnel* The reaction mixture vas held at -300 until the addition was complete. Thereaftee the reaction mixture was allowed to warm to room toraperature and stir overnight, Wor}kup was carried out as described previously. The yrield of crystalline product was 24.6 g This material Was used without further purification.
ir (neat, solid, cm- 2 1784, 1488, 1460o 1414, 1376, 1254, 1219, 1163t 875, 773.
Preparation ,of 2- (N4-benzvl- -dimethyl) ethyl sodium 4-sultpjhonhenyjl -carbonate Chloride (SPBMC), 0 Cl- (CH 3 2
N’ICH
2 Cfl 2 0» _O–Q.S0 3 Na CH2C 6
H
Sodiutt phenolsOuiphonate dihydrate (3.94 gt 0,017 mol)
M
23 C V «4 08; and sodium hydroxide (0.68 g, 0.017 mol) were d lved in distilled water (11 ml) and 2-(N-benzyliNwiaxhz1 ammonium)-ethyl chloroformate chloride (3.20 O017 mol) was added while stirring the reaction miT4ytu-. with a high speed stirrer. After dissolution of the chloroformate, the reaction mixture was quickly dLluted to 300 ml with water and freeze-dried. Spectral analysis of the resulting white solid indicated an SPBDMC yield of 47% with unreacted sodium phenolsulphonate and 2-(Nbenzyl-N,N-dimethyl-ammonium) ethano chloride being the principal impurities. The carbonate was used without further purification.
NMR (DMSO/D 2 0, trimethylsilylacetic acid standard) 7.30 2H); 7.60 51); 7.80 2H); 3.07 6H), ir (neat, solid, om- 1 1766, 1489, 1250, 1212, 1122, 1032, 1010, 704, 616, 567.
EXAMPLE 3 Prparation of 2- N-butyl-NN-dimethyvlammonium)ethyl Chloroformate Bromide This rompound was prepared by the procedure described for 2-(N-benyl-NN-dimethylanmonium)ethyl chloroformate chloride. For this experiment, the reagents were as follows: 2-(N-butyi-N4,N-dimethylammonium) ethanol bromide (10.0 g, X 10-2 mol), phosgene (17.5 g, 0.177 mol) and dry chloroform (75 ml). After workup, 2-(N-butyl-N,Ndimethylammonium) ethyl chloroformate chloride was used without further purification. An infrared spectrum of the product (neat) revealed a carbany’ peak at 1770 cm si;ALi 24 C 6034 (R) Preparation of 2- (N-butyl-NN-dimethvlammonium~ ethyl Sodium 4–Sulphophenyl Carbonate Bromidee (SPBuDMC) 0 Br- (CH 3 2
N+CH
2 CH OC ONa (C1 2 3 This compound was prepared by the procedure described for 2- (l-benzyl) -N,N4-dimethylammonium) ethyl sedium 4suiphophenyl carbonate bromide. Typical reagent levels were as follows: 2- (N-butyl-N,N-dimethylammonium) ethyl chloroformate ,bromide (4.03 go 17.2 x 10-2 mol), sodium 4-phenol sulphonate dihydrate (4.00 g, 1.72 x 10-2 mol), sodium hydroxide (0.70 g, 1.75 x 10-2 inol), and water (8.0 ml).
spectral 4nalysis of the white, solid product indicated the SPBuDMC yield was 66% with unreacted sodium phenol sulphonate and 2- (N-butyl-IN,N-dimethylammonium) ethyl bromtide being the prinicipal impurities. These impurities made assignment of aliphatic peaks in the NI4R spectrum difficult and, as a result, only the aromatic proton peak positions of the phenolsuiphonate group and nitrogen bouind methyl group in the product are herein reported.
NNIII (020, trimethylsilylacetic acid standard) :7.7 (do 2H1); 7.2 (do 211); 2.9 6H-).
EXAMPLE 4 Preag~tion of 2-r4-NN,NN-trimetbvlammonium)thenyl,1- E~thanol chloride Methylene chloride (50 ml) and 2-[4-(N1,W-dimethylamino)poheny’ljethanol (5.00 g, 3.03 x 10-2 mol) were placed in a 100 rl round-bottom flask equipped with a dropping funnel, condensor, and magnet-ic stirring bar, Methyl ‘iVAt \iodide (4.29 go 2.03 x 10-2 Mol) was added dropwise C 6034 (R) through the dropping funnel. Precipitate began to form immediately. After addition of all of the methyl iodide, the reaction mixture was stirred for an additional minutes. Tha product was collected by vacuum filtration, washed with methylene chloride, and dried in a vacuum oven. Spectral analysis confirmed the structure of the product as 2-[N,N,N-trimethylammonium)phenyl]ethanol iodide. The iodide salt was converted to the hydroxide salt by passing through a Bio Rad AG21K resin exchanged with sodium hydroxide. Neutralization of the hydroxide salt with dilute hydrochloric acid, followed by frezedrying, gave the desired chloride salts.
Preparation of 2-,’4-(N,NN-trimethylammonium)phenyll ethyl Chloroformate Chloride This compound was prepared by the procedure described for 2-(N-benzyl-N,N-dimethylammonium)ethyl chloroformate chloride. Typ.cal reagent levels were as follows: 2-[4-(N,N,N-ft imethylammonium)phenyl]ethanol chloride (4,56 g, 2.12 x 10- 2 mol), phosgene (8.40 g, 8.48 x 10 2 mol), and dry chloroform (30 ml).
After workup, 2-[4-(N,N,N-trimethylammonium)phenyl] ethyl chloroformate chloride was used without further purification.
Preparation of 2-[4-(N,N,N-trimethylammonium)rhenVll ethyl Sodium 4-Sulphophenyl Carbonate Chloride (SPTPEC) 0 Cl-(CH3)3N+- -CH 2
CH
2 0C SO 3 Na This compound was prepared by the procedure described for 2-(N-benzyl-N,N-dimethylammonium)ethyl sodium 4sulphophenyl carbonate chloride. Typical reagent levels were as follows: 2-(4-(N,N,N-trimethylammonium)phenyl]ethyl chloroformate 21b C 6034 (R) chloride 10 g, 1. 50 X 10-2 mci) sodium 4j,,henolsulphonate dihydrate (2.42 g, 1.50 x 10-2 Mol), sodium hydroxide (0.59 g, 1.50 x 10-2 mol) and water (6.4 ml).
The product c-ystallized from the reaction mixture.
After drying, spectral analysis confirmed the product structure as 2- (N,N,N-trimethylammonium) phenyl]ethyl sodium 4-sulphophenyl carbonate chloride. Purity was approximately 65% (by NMR).- The product was purified by boiling in methanol, followed by filtration and drying. The NMR spectrum of the purified product showed complete absence of unreacted sodium phenol sulphonate.
NM4R (D 2 0, trimethylsilylacetic acid standard): 7.55 2H); 7.45 2H); 7,20 2H); 7.00 2H); 4.30 2H1); 3.35 9H); 2.85 2H1).
ir (solid, photoacoustic cm- 1 3023, 1755, 12519, 1462, 1151, 1123, 957, 852, 836, 818 EXAMPLE Pre’Paration of 1. l-Dimethyl-3-hvdroxcvpiDeridinium Chloride This compound was prepared by the procedure described for (N,N,N-trimethylamrnonium)phenyllethanoi chloride. Typical reagent levels were as foillows: 3-hydroxy-l-methylpiperidine (21.7 g, 0.188 mol), iodomethane (40.0 g, 0.280 mol) and methylene chlor4ide ml).
NMR (D 2 01 TMS external standard): vN 4.10 (in, 111); 3.30 (in, 2H1); 27 C 6034 (R) 3.16 3H); 3.03 311); 2. 13 16 (in, 4H) Preparation of 1. l-Dimethvlpiperidium-3-chloroformate Chloride This compound was prepared by the procedure described for 2-(N-benzyl-N,N-dimethylammonium) ethyl chiorofornate chloride. Typical reagent levels were as follows: 1, l-dimethyl-3-hydroxypiperidinium chloride (24.0 g, 0.124 mol), phosgene (41.6 ml, 0.583 mol) and dry chloroform (100 ml).
After workup, 1, l-dimethylpiperidinium–3-chloroformate chloride was used without further purification.
Preparation of Sodium 3-(l,1-Dimethylpiperidinium) 4-Sulphophenyl Carbonate-Chloride (SPDPC) 0 C1 -OC 0 S03Na
CH
3 CH 3 This compound was prepared by the procedure described for 2- (N-benzyl-N,N-dimethylammonium) ethyl sodium 4sulphophenyl carbonate chloride. Typical reagent levels were as follows: 1, l-dimethylpiperidinium-3-chloroformate chloride (4.65 g, 2.19 x 10-2 mol), sodium 4-sulphophenol dihydrate (5.10 g, 2.19 x 10-2 mol), sodium hydroxide (0.88 g, 2.20 x 10-2 mol), and water (10 ml).
Spectral analysis of the white, solid product indicated the SPDPC yield was approximatively 70%, with major impurities being unreacted sodium 4-sulphophenol and S1,l-dimethyl-3-hydroxypiperidinium chloride.
28 C 6034 (R) NMR (D 2 0, TMS external standard): 7.56 211); 7.08 2H); 9.92 (in, 1H1); 3.52-2.96 (mn, 4H) 2.136 3H); 2.83 311); 1.72 (in, 4H).
EXAMPLE 6 Preparation of 1. l-Dimethyl-4-hvdroxvpiperidinium Chloride This compound was prepared by the procedure described for 2-[4-N,N,N-trinethylammronium) phenyl]ethanol chloride. Typical reagent levels were as follows: 4hydroxy-l-methyl-piperidine (21.7 g, 0.188 inol), iodoinethane (40.0 g, 0.280 inol), and methtylene chloride Ml) NMR (D 2 0, TMS external standard) 3.96 (mn, 1H1); 3.40 (mn, 411); 3.12 611); 2.00 (mn, 411).
Preparation of 1. l-Diinethylpiperidiniumn-4chloroforinate Chloride This compound was prepared by the procedure described for 2- (N-benzyl-N,N-dimethylamnonium) ethyl chlorofornate chloride, Typical reagent levels were as follows: 1, l-dimethyl-4-hydroxypiperidinium chloride (24.0 g, 0.145 mol), phosgene (41.6 ml, 0.583 mol), and dry chloroformn (100 ml).
After workup, the product was used without further purification.
Preparation of Sodium 4-(1.1-dimethvlpiperidinium) 4-sulphophenvl Carbonate Chloride (SPDMPC 24 c 6034 (R) H3c 01 H +N OC -S0 3 Na
H
3
C
This compound was prepared by the procedure described for 2-(N-benzyl-N,N-dimethylammonium)ethyl sodium 4sulphophenyl carbonate chloride. Typical reagent levels were as follows: 1,1-dimethylpiperidinium-4-chloroformate chloride (4.65 g, 2.19 x 10- 2 mol), sodium 4-sulphophenol dihydrate (5.10 g, 2.19 x 10 2 mol), sodium hydroxide (0.88 g, 2.20 x 10- 2 mol), and water (10 ml).
The white, solid product was purified by boiling in ethanol, followed by filtration and drying to give a solid containing no unreacted sodium 4-sulphophenol nor 1,l-dimethyl-4-hydroxypiperidinium chloride by NMR analysis.
NMP (D 2 0, trimethylsilylacetic acid standard): 7.75 2H); 7.22 2H); 5.10 1H); 3.44 4H); 3.14 3H); 3.10 3H); 2.24 4H).
EXAMPLE 7 Preparation of 2-(N,NN-trimethylammonium)ethyl 4-Nitrophenyl Carbonate Chloride (STNC) o0
[(CH
3 3
+NCH
2
CH
2 0CO- -NO 2 Cl- This compound was preparedy the procedure described for 2-(N-benzyl-N,N-dimethylammonium)ethyl sodium 4sulphophenyl carbonate bromide. Typical reagent levels were as follows: 2-(N,NN-trimethylammonium)ethyl chloroformate chloride g, 3.5 x 10 2 mol), 4-nitroph’nol (4.8 g, 3.5 x 2 mol), 4-nitrophenol (4.8g, 3.5 X 10- 2 mol), sodium hydroxide (1.4 g, 3.5 x 10 2 mol), and water (15 ml).
C 6034 (R) Spectral analysis of the white solid indicated the product yield was greater than 90% with 4-nitrophenol and choline chloride being the principal impurities. The product was used without further purification.
NMR (D 2 0, TMS external standard): 3.5-3.8 4H); 3.05 9H); 7.23 2H); 8.18 2H).
EXAMPLE 8 Peracid Generation From Precursors Peroxycarbonic acid precursors described herein can be used to generate peroxycarbonic acid bleaches in basic aqueous solution containing a source of hydrogen peroxide and, optimally, may contain typical detergent ingredients. Peroxycarbonic acid generation was demonstrated by adding a premeasured sample of precursor to 500 ml aqueous buffer solution at the desired pH, heated to 40° in a thermojacketed beaker, and containing the approximate level of hydrogen peroxide (added as either 30% hydrogen peroxide or sodium perborate monohydrate). The hydrogen peroxide source was added just prior to addition of the precursor. The milliliter aliquots of solution were withdrawn from the beaker at regular intervals and were added to a 250 ml titration flask containing crushed ice (150 glacial acetic acid (30 ml) and 40% aqueous potassium iodide (5 ml).
After development for ten minutes with occasional agitation, the iodine produced was titrated with standard sodium thiosulphate solution. Time zero was taken as the point of introduction of precursor into the peroxide solution. Precursor perhydrolysis experiments were generally carried out for a maximum of 15 minutes.
Since hydrogen peroxide itself contributes to the total active oxygen in these titrations, controls or «blanks» were obtained by carrying out a perhydrolysis experiment C 6034 (R) in the absence of precursor. These hydrogen peroxide blanks were subtracted from the total active oxygen titration in the presence of bleach precursor to give the level of active oxygen produced by precursor perhydrolysis.
Peroxycarbonic acid generation was determined at pH 8, 9, and 10. Borax buffer was used for experiments at pH 9 and 10 while phosphate buffer was employed for experments carried out at pH 8. Adjustment of the buffer systems at 40°C to the exact pH was carried out with 1 M hydrochloric acid or sodium hydroxide solution.
Tables I and II list the peroxycarbonic acid yields as a percent of theoretical from SPCC and SPBCMC, respectively.
TABLE I. Perhydrolysis Yields From SPCC pH 1 Minute 3 Minutes 5 Minutes 10 Minutes 15 Minutes 29% 29% 17% 28% 38% 16% 9% 29% 24% 6% 25% 13% 0% 13% Conditions: 3
M.
40°C, [SPCC] 9.4 x 10- 4 M, [H 2 0 2 9.4 x TABLE II. Perhydrolysis Yields From SPBDMC rr4 1 Mi nli+o 3 Minutes 5 Minutes 1 Mi niii~R 1 5 Mi ri+ YnH 1 II- n»4- 3 iues 5Mnte 0Miue 5 iue 21% 49% 34% 32% 2.4% 0% Conditions: 3
M.
40″C, [SPBDMC] 9.4 x 10- 4 M, 1[202] 9.4 x From the data in Tables I and II, it can be seen that precursors SPCC and SPBDMC generate peroxycarbonic acid rapidly. Peracid is generated quickly, even at pH 8.
32 C 6034 (R) Peroxycarbonic acid decomposition during the perhydrolysis results in less than quantitative yields based on precursor level.
EXAMPLE 9 Bleaching From Peroxycarbonic Acid Precursor/Peroxide Systems The stain bleaching ability of peroxycarbonic acids generated from the synthesized precursors was demonstrated on common stains such as tea, red wine, and blackberry juice. Typically, cotton test pieces (10 cm x cm) stained with the appropriate stain were washed in a Terg-O-Tometer in 1 1 of aqueous solution containing a given level of bleach precursor, hydrogen peroxide, buffer, and surfactant (generally sodium dodecylbenzene sulphonate).
Washes were carried out at 40°C for 15 minutes. Stain bleaching was measured reflectometrically using a Colorgard System/05 Reflectometer, Bleaching is indicated by an increase in reflectance, reported as AR.
In general, adR of one unit is perceivable in a paired comparison while AR of two units is perceivable monadically. In reporting the reflectance change, the change in reflectance caused by general detergency and bleaching by the excess hydrogen peroxide has been accounted for. Thus R can acutally be expressed as: AR (Reflectance of stained fabric washed with precursor/H 2 0 2 and detergent Reflectance of stained fabric before washing) (Reflectance of stained fabric washed with H 2 0 2 and detergent alone Reflectance of stained fabric before washing).
In the case of spaghetti stain, bleaching is measured as «Ab» where the quantity «Ab» is the change in the b-axis 33 C 6034 (R) of the Hunter colour scale. The spaghetti stain is initially yellow and loses colour with bleaching and thus bleaching produces a n-egative change in b. Since peroxide-only controls were also carried out with the spaghetti sauce stains, percarbonic acid bleaching is actually reported as «Ab».
TABLE III Bleach Perforance rSPccI M 9.4 X 10-4 6.3 x 10-4 3.2. x 10-4 9.4 X 10-4 9.4 x 10-4 9.4 x 10-4 9.4 x 1O»4 9.4 x 10-4 9.4 X 1- 9.4 x l0M 9.4 X 10-3 9.4 X 10-3 4.7 x 10-3 1.9 x 10-3 9.4 x 1- 1.9 x 10-3 1.9 x 1- 1.9 x 10-3 40 O 40 20 15 10 Tea 19. 5 15. 4 9.5 21.0 19. 0 13 .0 9.7 7.1 4.3 4R Red Wine Blackberry 25.1 15.3 18.5 13.9 10.9 13.0 23.3 23.9 17.8 10.7 8.6 8.4 Structure
SPBDMC
SPBuDI4C
SPTPEC
SPDPC
Precursor M .W2!Q2Th 7. 5XI0 4 9 4×10- 4 9. 4xI0 4 9. 4×10-4 3 xIO’ 4 9.4×10- 4 9. 4X10- 3 1. 9X10- 3 9. 4x 1 3 d R T. Tea Red OC Wine 40 13.5 15.7 40 9.7 12.9 40 18.9 21.9 40 16.4 18.4 8.0 8.i7 4.8 5.2 7.3 40 13.4 13.3 6.0 5.7 3.0 4.4 2.8 3.3 40 15.9 9.3 12,1 9.4 _6b Spagrhetti 0 SPDMPC 9.4X10- 4 STNC 9. 4XI0 4 C 6034 (R) It can be seen that bleaching from these peroxycarbonic acid bleaches is excellent, giving substantial stain removal on a variety of stains. As evidenced from Table, the SPCC system has been studied most extensively. A number of observations may be gleaned from the Table with respect to SPCC. At a theoretical percarbonic acid yield of 15 ppm active oxygen (9.4 x 10 4
M),
outstanding bleaching is obtained at 40 0 C in 15 minutes on hydrophilic stains such as tea, red wine and blackberry. Bleaching remains outstanding at hydrogen peroxide/precursor ratios as low as 2:1. Even at 1:1, bleaching is very good compared to state-of-the-art systems such as sodium nonanoyloxybenzene sulphonate with perborate. At a theoretical percarbonic acid yield of 5 ppm active oxygen (3.1 x 10 4 bleaching of hydrophlic stains is comparable to that obtained with sodium nonanoyloxybenzene sulphonate with perborate at ppm active oxygen theoretical peracid. Levels of ppm active oxygen give very good bleaching at 20°C and perceivable bleaching even as low as Precursors other than SPCC all gave very good to outstanding bleaching on tea and red wine stains at and 15 ppm active oxygen theoretical percarbonic acid yield. Most interestingly, SPTPEC gave a modest but perceptible bleaching on spaghetti sauce stain. The observation is unusual in that this stain is hydrophobic whereas the class is most effective against hydrophilic stains. Equally interesting is the observation that SPDPC and SPDMPC are effective in cold water. These results indicate that low terperature bleaching is a general property of percarbonic acid substituted with quaternary ammonium functionality.
The foregoing description and examples illustrate selected embodiments of the present invention. In the 4ight thereof, various modifications will be suggested v, C 6034 (R) to one skilled in the art, all of which are within the spirit and purview of this iryt mtion.

Claims (22)

1. A bleach precursor compound having the formula; R 1 O II Z R 2 +Q R 4 OCL 2 wherein: R 3 Rl, R 2 and R 3 are each a radical of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aryl, phenyl, hydroxyalkyl, polyoxyalkylene or R 4 000L; or two or more of RP, R 2 and R 3 together form an alkyl-substituted or unisubstituted, ntrogen-containing heterocyclic ring system; S.or at least one of Ri, R 2 and R 3 Is attached to R 4 to form an alkyl-substituted or unsubstituted, nitrogen- containing heterocyclic ring system; R4 is a bridging group of alkylene, cycloalkylene, alkylenephenylene, phenylene, arylene, or polyalkoxylene and wherein the bridging group can be unsubstituted or substituted with C 1 -C 20 alkyl, alkenyl, benzyl, phenyl or aryl radicals; Z. is a monovalent or multivalent anion leading to charge neutrality when combined with Q+ in the appropriate ratio and wherein Z is8 sufficiently oxidatively stable not to interfee significantly with bleaching by a peroxy carbonic acid; Q is nitrogen e Q-pe and L is a leaving group of which the conjugate acid has a pka in the range from 6 to 13, and is H H 82 r cS H Y 0 U 0 /CU 2 C C R61-NNi :I -g~F -C,0 CH C% CHI CH2, (i I 0 C C HR7~ L_ I: 37 wherein: R 5 and Rg are a C -CI 2 alkyl group, R 7 is H or and Y is H or a solubilizing group, selected from -SO-3M -COO -SO 4 M -N (R 5 3 X NO 2 OH, and 0 N(R 5 2 and mixtures thereof; M+ is a hydrogen, alkali metal, ammonium or alkyl or hydroxyalkyl-suhstituted ammonium cation, X is a halide, hydroxide, phosphate, sulphate, methyl sulphate or acetate anion.

2. The precursor of Claim 1 wherein L has the formula: 0 lo O i–SO 3 M wherein M+ is a sodium, potassium or ammonium cation

3. The precursor of Claim 1 or 2 wherein Q ts ntvce. ad RI, R 2 and R 3 are each the same or different CI-C 2 0 atom radicals of alkyl, alkylaryl, benzyl, hydroxyalkyl, or 1S heterocyclic rings containing the quaternary nitrogen where R 1 and RP 4 or R 1 and R2 are joined together, or mixtures of groups thereof.

4. The precursor of Claim 3 wherein R 1 is selected from short-chain c 1 -C 4 alkyl radicals,

5. The precursor of Claim 3 or 4 wherein R 2 and RP 3 are each a longer chain C7-C20 alkyl or alkylaryl radical,

6. The precursor tf Claim 5 wherein baid longer chain racdual is a benzyl, lauryl or stearyl group.

7. The precursor of any one of Claiws 1-4 wherein R 4 is a bridging group of C 2 -C 0 alkylene, C6-Q 12 phenylene, C 5 -C 20 cycloalkylene or C 8 -C 20 alkylphenyline groups,

8. The precursr of Claim 7 wherein the R 4 bridging group is a C2CG alkylene or C 6 -C 12 phenylene group. 9, The pr curser of any one of Claims 3 to 8 wherein aid heterocycli. ring is selecte from pyridino, morpholine, L 1 pyrrolidone, piperidine or piperazine. The precursor of any one of Claims 1 to 9 where-n Y is a suiphonic acid salt. 11, The precursor of Claim 1 wherein the compound is 2-(N,N,N–trimethylaminonium)ethyl 4-suiphophenyl carbonate salt.

12. The precursor of Claim 1 wherein the compound is 2-(N–benzyl-N,N-dimethylammionium)ethyl 4-suiphophenyl carbonate salt. lu The precursor of Claim 1 wherein the compound is 2-(N–butyl-N,N-dimethylarmmonium)ethyl 4-suiphophenyl carbonate salt. 14, The precursor of Claim 1 wherein the compound is 2- E4-(N,N,N-trimethylammonium)phenyliethyl 4-suiphophenyl carbonate salt. The precursor of Claim 1 wherein the compound is 3- (l,1I-dine thylpiperdin i Lm) ‘-sulphophenyl carbonate salt.

16. The precursor of Claim 1 wherein the compound is 4-C2,,l-dimethylpipericdinium) 4-sulphophenyl carbonate salt,

17. A bleaching-detergent composition comprising: from 1 to 60% of a peroxygen compound capable of yielding h’.,drogen peroxide in an aqueous solution; from 0.1 to 40% of a bleach precursor having the formula: ZR 2 Q -R 4 -oci 08L wherein: Rjj R. 2 and P1 3 are each a radic-al of alkyl, alkaznyl, alkynyl, cycloalkyl, Ycloalkenyl, alkaryl, aryl, phenyl, hydroxyalkyl, polyoxyalkylene or R 4 OCOL; or two or more of R 1 R 2 and R 3 together form an alkyl-substituteci or unsubstituted, nitrogen-containing heterocyclic ring system; or at least one of Rl, R 2 and R 3 is attached to R to form an alkyl-substituted or unsubstituted, nitrogen- containing heterocyclic ring system; Ris selected from a bridging group of alkylene, cycloalkylone, alkylenephenylene, phenylene, arylene, or polyalkoxylene and wherein the bridging group can be unsubstituted. or substituted with Cl-0 2 0 atoms selected from alkyl, alkenyl, benzyl, phenyl or aryl. radicals; Zis a monovalent or multivalent anion leading to charge neutrality when combined with Q+ in the approriate ratio and wherein Z_ is sufficiently oxidatively stabl1e not to interfere significantly with ble~iching by a peroxy carbonic acid; Q is ni~trogen L is a leaving group of which the conjugate acid has a pka in the range from 6 to 33, and is R 5 Y r%»R 5 Y Y 0 0 0 UQ -N C R 6 -O-C RIS -N NH, I Y 0 I I OCH C CH Cl 2 ,or C CHR 7 wherein;, R 5 and R 6 are a C 1 -Cl2 alkyl group, R 7 is H or R 5 and Y is H or a solubiJlizing group, selected from -so -COO- M 4 t-S0 4 M 5 3 N0 2 01i, or 0 (4 N(RS) 2 or I.%-‘rtixtures thereof; M+ is a hydrogen, alkall metal, ammonium or xQ?’%I, t4 40 alkyl or hydroxyalkyl-substituted ammonium cation, X is a halide, hydroxide, phosphate, sulphate, methyl sulphate or acetate anion; (iii) from 0 to 50% of a surfactant; and (iv) from 0 to 70% of a detergent builder,

18. The composition of Claim 17 wherein the surfactant ranges from 4 to 50% and the detergent builder ranges from to 80% by weight.

19. The composition of Claim 17 or 18 wherein L has the formula: Q 0 -S0 3 -M+ wherein M+ is a sodium, potassium or ammonium cation. The composition of any one of Claims 17 to 19 wherein Q i nt–ogen-a-nd R 1 R 2 and R 3 are each the same or different and selected from CI-C 20 atom radicals of alkyl, alkylaryl, benzyl, hydroxyalkyl, or heterocycllc rings containing the quaternary nitrogen where R 1 and R4 or R 1 and R2 are joined together, or mixtures of groups thereof.

21. The composition of Claim 20 wherein R 1 is selected from short-chain Cl-C 4 alkyl radicals.

22. The composition of Claim 21 wherein R 2 and R 3 are each a longer chain C 7 -C 20 alkyl or alkylaryl radical.

23. The composition of Claim 22 wherein said longer chain radical is a benzyl, lauryl and stearyl group.

24. The composition of any one of Claims 17 to 23 wherein R 4 is selected from a bridging group of C 2 -C 2 0 alkylene, C6-Cl2 phenylene, C 5 -C 20 cycloalkylene, or C8-C20 /f 3.4Nylphenylene groups. 4.1ij The composition of Claim 24 wherein the R 4 bridging group is a C 2 -C 6 alkylene or C 6 -C 1 2 phenylene group.

26. The composition of any one of Claims 20 to wherein said heterocyclic rJ~ng is selected from pyridine, morpholine, pyrrolidone, piperidine or piperazine.

27. The composition of Claim 17 wherein Y is a sulphonic acid salt.

28. The composition of Claim 17 whe~rein the precursor is 2- (N,N,N-trimethylammonium) ethyl. sod um 4-sulphopheny. carbonate salt.

29. The composition of Claim 17 wherein the precursor is 2- (N-benzyl~-N,N-dirnethylamxnonium) ethyl sodium. 4- sulphophenyl carbonate salt, The composition of Claim 17 wherein the precursor is 2-(N-butyl-N,N-dimethylammoniun) ethyl sodium 4- sulphopheny], carbonate salt. 31, The composition of Claim 17 wherein the precursor is 4- (N,N,N–trtmethylarnmonium)phenylI ethyl sodium 4- sua.phophenyj. carbonate salt.

32. The composition of Claim 17 wherein the precursor is sodium 3 (1 1-dime thyp,perldinium) 4-sulphopheny. carbonate salt. 433, The composition of Claim 17 wherein the precursor is sodium 4 ,1 -dime thylpiperidinium) 4-sulphophenyl carbonate salt. 34 A bleach precursor substantially as hereinbefoze described with reference to any one of the foregoing ,,-,,examples. 4^ A bleaching-detergent composition substantially as hereinbefore described with reference to any one of the foregoing examples. Dated this 2nd day of January, 1991 UNILEVER PLC By its Patent Attorneys: GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia. 1Si.N

AU13125/88A
1987-03-17
1988-03-15
Quaternary ammonium or phosphonium peroxycarbonic acid precursors and their use in detergent bleach compositions

Ceased

AU613900B2
(en)

Applications Claiming Priority (2)

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US027278

1987-03-17

US07/027,278

US4751015A
(en)

1987-03-17
1987-03-17
Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions

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1988-09-15

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1991-08-15

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1987-03-17
1988-03-15
Quaternary ammonium or phosphonium peroxycarbonic acid precursors and their use in detergent bleach compositions

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KR
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KR930009821B1
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AU
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AU613900B2
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BR8801185A
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CA1324379C
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DE
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DE3886969T2
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ES2061625T3
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MY104103A
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Machine dishwash detergent

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not_active
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1988

1988-03-08
ES
ES88200430T
patent/ES2061625T3/en
not_active
Expired – Lifetime

1988-03-08
EP
EP88200430A
patent/EP0284132B1/en
not_active
Expired – Lifetime

1988-03-08
DE
DE88200430T
patent/DE3886969T2/en
not_active
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CA
CA000561158A
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PH
PH36625A
patent/PH24209A/en
unknown

1988-03-15
AU
AU13125/88A
patent/AU613900B2/en
not_active
Ceased

1988-03-16
ZA
ZA881870A
patent/ZA881870B/en
unknown

1988-03-16
BR
BR8801185A
patent/BR8801185A/en
not_active
Application Discontinuation

1988-03-16
MY
MYPI88000269A
patent/MY104103A/en
unknown

1988-03-16
JP
JP63063075A
patent/JPH07103075B2/en
not_active
Expired – Lifetime

1988-03-17
KR
KR1019880002819A
patent/KR930009821B1/en
not_active
IP Right Cessation

1988-03-17
TR
TR00203/88A
patent/TR26863A/en
unknown

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Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide

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Unilever Plc
Bleach activation and bleaching compositions

Also Published As

Publication number
Publication date

EP0284132A2
(en)

1988-09-28

KR930009821B1
(en)

1993-10-11

BR8801185A
(en)

1988-10-25

AU1312588A
(en)

1988-09-15

CA1324379C
(en)

1993-11-16

MY104103A
(en)

1993-12-31

ZA881870B
(en)

1989-11-29

KR880011091A
(en)

1988-10-26

EP0284132A3
(en)

1990-06-13

JPH07103075B2
(en)

1995-11-08

DE3886969D1
(en)

1994-02-24

JPS63258447A
(en)

1988-10-25

US4751015A
(en)

1988-06-14

TR26863A
(en)

1994-08-19

PH24209A
(en)

1990-04-10

DE3886969T2
(en)

1994-04-28

EP0284132B1
(en)

1994-01-12

ES2061625T3
(en)

1994-12-16

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