Stable copper hydroxide is prepared by removing ferrous ion from the beginning cupric solution. The ferrous ion is oxidized to ferric ion, and the ferric ion is precipitated by raising the pH of the solution to 3-4. The utilization of phosphate ion both increases the efficiency of oxidation and simultaneously precipitates ferric ion. A second raising the pH of the purified solution precipitates highly pure copper hydroxide that can be harvested.

1. Field of the Invention
The invention pertains to highly stable cupric hydroxide compounds obtained by removing iron impurities from the starting copper solution.
2. Description of the Related Art
Stable copper hydroxide is a product that is difficult to obtain, even when employing a highly purified copper salt as a starting material. This is because even small amounts of ferrous (FeII) impurities can catalyze the decomposition of cupric hydroxide to cupric oxide:
Thus, a spray application of ppm FeII ion can catalyze the dehydration of Cu(OH)2 to CuO.
However, the production of Cu(OH)2 requires starting materials that are very low in iron content. These materials are both difficult to find and are expensive, because ferrous ion is very widely distributed in any starting material. As a result, there is a need to rapidly and efficiently remove ferrous ions from the raw materials used in cupric hydroxide production.
Copper compounds, including copper hydroxide, are used to treat plant fungi. Pathogenic fungi cause a substantial reduction in expected crop yields. Further losses result from fungi during the storage of harvested crops. Although there are over 100,000 known species of fungi, no more than 200 are known to cause serious plant disease.
The classes of fungi associated with important diseases in plant crops include Phycomycetes, Asomycetes, Basidiomycetes and Deuteromycetes. Examples of Phycomycetes include Phytophthora infestans (potato late blight) and Plasmopara viticola (downy mildew of grape). Examples of Ascomycetes include Erysiphe graminis (powdery mildew of wheat/barley), Podosphaera leucotricha (apple powdery mildew) and Pyricularia oryzae (rice blast). Examples of Basidiomycetes include Puccinia spp. (leaf rust of wheat and oats), Rhizoctonia spp. (sheath blight of rice) and Ustiliago spp. (corn smut). Examples of Deuteromycetes include Alternaria spp. (tobacco brown spot), Botrytis spp. (gray mold of grape), Cercospora spp. (leaf spot of sugar beet), Fusarium spp. (wheat blight), Helminthosporium spp. (leaf spot of corn), Pseudocercosporella herpotrichoides (eyespot of wheat), Septoria nodorum (blotch of wheat) and Septoria tritici (wheat leaf blotch).
The fungicides can be classified into systemic and nonsystemic fungicides. The systemic fungicides can penetrate the seed or plant and are then redistributed within to unsprayed parts or subsequent new growth, rendering protection from fungal attack or eradicating a fungus already present. The nonsystemic fungicides have a protectant mode of action and must be applied to the surface of plant generally before infection takes place. The inorganic salts are generally classified as nonsystemic fungicides.
The use of copper as a fungicide is well known. Copper sulfate was used from treating the seed-borne disease wheat bunt (Tilletia spp.) as early as the eighteenth century. In 1882, it was observed that grapevines that had been coated with a mixture of copper sulfate and lime to deter grape pilferage were not infected with grape downy mildew (Plasmopara viticola). This observation resulted in the development of a fungicide called Bordeaux mixture. Copper fungicides currently available for a wide variety of applications include the hydroxides, sulfates (Bordeaux mixture), oxides and oxychlorides and a variety of organic salts such as copper naphthenates and copper quinolinates. Crops protected using copper compounds include vines, fruit, coffee, cocoa and vegetables. Most copper fungicides work by inhibiting fungal spore germination. Sensitive fungi are affected by the uptake of copper salts and its subsequent accumulation, which then complexes with amino, sulfhydryl, hydroxyl or carboxy groups of enzymes resulting in the inactivation of the fungus. Fungicides are discussed in the Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed. (1994), Volume 12 at pages 204-227.
Copper compounds are also effective against bacterial plant diseases. A common bacterial plant disease amenable to treatment by copper compounds, including cupric hydroxide, is citrus canker. When environmental conditions are favorable for the spread of the disease, chemical control measures are not entirely effective. However, materials containing copper (Bordeaux mixture, copper hydroxide, basic copper chloride, copper oxychloride, and tribasic copper sulfate) are the most effective bacterial sprays for protecting leaves and fruit. These materials can reduce the incidence of disease, but they will not eliminate established infections. Extensive use of copper may also cause phytotoxicity problems in treated groves.
Copper hydroxide is also used to treat tomato bacterial spot (Xanthomonas campestris pv. vesicatoria). Copper hydroxide is applied at the first sign of disease and repeated at 10- to 14-day intervals when warm, moist conditions prevail. Copper is strictly a protectant and must be applied before an infection period occurs. Coverage is 4 lb of copper hydroxide per acre.
The most common copper fungicide incorporating copper hyhdroxide is Bordeaux mixture (CuSO4xcexa93Cu(OH)2xcexa93CaSO4). The standard formula for Bordeaux mixture is four pounds of copper sulfate, four pounds of hydrated lime and 50 gallons of water. Mix four pounds of the lime in four gallons of water. Do the same for the copper sulfate. Strain the lime mixture through cheesecloth, add to 42 gallons of water, and then add the sulfate mixture. Use immediately. Small amounts can be made by mixing four ounces of hydrated lime in 2 gallons of water. Mix four ounces of copper sulfate in 1 gallon of water. Pour the copper sulfate mixture into the lime mixture. Bordeaux mixture can cause damage to plants if used improperly. Damage or injury results more in humid weather and when the mixture doesn""t dry quickly. Bordeaux mixture will leave a bluish-white deposit on the plant.
Once made, Bordeaux mixture is not stable. Poorly stirred Bordeaux mixture has little value as the active copper compound is not sufficiently finely divided. Other materials are frequently added to Bordeaux mixture in order to increase the stability. If other materials are to be used in the mixture, they may then be added with further agitation. White oil may be used at around 500 mL/100 L of spray or similar amounts of calcium caseinate (500 g/100 L) or molasses (500 mL/100 L). White oil or summer spraying oil may be used at the rate of 500 mL/100 L spray to enhance penetration of the spray under bud scales. Similarly calcium caseinate and molasses have been recommended from time to time for various crops. These are reported to improve the weathering ability of the spray by producing a surface layer on tile leaves which protects the copper particles from being dislodged by rain or irrigation.
Fungicides such as Bordeaux mixture are also characterized by sticking poorly to the plant. The sticking ability of Bordeaux mixture can also be improved by the addition of polymers. However, polymer additives tend to be expensive.
For Burgundy mixture, the slaked lime is replaced by the fully soluble washing soda (sodium carbonate). In other respects, the procedure is the same and the end results are similar although the mixture is said to stick better than Bordeaux but is also more likely to burn sensitive foliage. The main advantage of Burgundy mixture is the ease of use of the washing soda compared with slaked lime. Fresh soda should be used; old material may have less water of crystallization and it is difficult to judge the amount required.
To make an equivalent Burgundy mixture to that described above for Bordeaux, replace the 1 kg of slaked lime with 1.5 kg of washing soda. If the normally crystalline washing soda appears white and powdery, use only 1 kg and then check the made-up mixture for pH before use.
Although the conventional art recognizes the applicability of copper compounds as a fungicide, the conventional art also recognizes that the copper fungicides have disadvantages that need to be rectified. Typical of the conventional art copper technology is that of the ""253 patent to LeFiles et al. (U.S. Pat. No. 5,298,253) and the ""738 patent to LeFiles et al. (U.S. Pat. No. 5,462,738) which pertain to a copper hydroxide dry flowable bactericide/fungicide and a method of making and using same. The bactericide/fungicide of the ""253 and ""738 patents is made by forming a homogeneous aqueous slurry containing between approximately 5% and 20% by weight (based on the total weight of all dry ingredients) of a first dispersant selected from the group consisting of partially neutralized polyacrylic acid having a pH 5-10 and an average molecular weight of between 1,000 and 10,000 and lignin sulfonate. A second dispersant is used for bentonite clay. A slurry is formed with phosphate stabilized cupric hydroxide and the slurry is spray dried the slurry to thereby form a dry free flowing granular bactericide/fungicide product. Although phosphate stabilized cupric hydroxide is mentioned, this solution is obtained from an aqueous slurry using polyacrylic acid as a dispersant.
The ""681 patent to Pasek (U.S. Pat. No. 5,492,681) pertains to a method for producing copper oxide. In the method, a copper bearing material, aqueous ammonia, and a sufficient amount of an ammonium salt to double the rate of production of copper oxide in the absence of the salt are placed in a single vessel. The vessel is closed, and oxygen is fed into the vessel. The mixture is stirred and heated to a temperature of between approximately 70xc2x0 and 130xc2x0 C. to dissolve the copper bearing material into aqueous ammoniacal copper ion. The aqueous ammoniacal copper ion is reacted with the oxygen in the vessel to form solid copper oxide particles, which are then recovered. The ""681 patent is a process based upon ammoniacal copper.
The ""533 patent to Browne (U.S. Pat. No. 5,310,533) pertains to a method of producing copper compounds involves contacting metallic copper with oxygen or an oxygen-containing gas, with an aqueous solution consisting essentially of water in solution in which is a soluble ammonium salt NH4X, where X is the anion of the salt, and with ammonia in an amount such that the solution is initially alkaline. As a result of such contact the metallic copper is initially dissolved to form a copper amine Cu(NH3)4X and the formation of the amine continues until the saturation concentration of the amine is reached. Subsequently, the amine continuously breaks down to form 3Cu(OH)2xcexa9CuX2 and the water soluble products of the amine decomposition continuously reform the amine by further reaction with the metallic copper and the oxygen on oxygen-containing gas. The ""533 patent is a production of copper compounds using ammoniacal copper, and the presence phosphate is not indicated.
The ""935 patent to Langner et al. (U.S. Pat. No. 4,944,935) pertains to a process of producing blue copper hydroxide, wherein copper metal is treated with an ammonium ion-containing aqueous solution with stirring and with a simultaneous introduction of an oxygen-containing gas and the reaction product is separated from the copper metal. A particulate, floatable copper (II) hydroxide is produced in that a material which contains copper metal is treated at a temperature of 0xc2x0 to 40xc2x0 C. with a solution which contains 0.1 to 10 g/l ammonium salt (calculated as NH4), 0 to 10 g/l ammonium hydroxide (calculated NH3) and, if desired, 0 to 5 g/l copper (II) salt and the resulting copper (II) hydroxide is separated. The ""935 patent pertains to the production of copper hydroxide using ammonium-based compounds. Example 6 discusses ammonium salts selected from chlorides, sulfates, phosphates, nitrate, and acetate. However, a non-ammonia based process is not disclosed.
The ""406 patent to Brinkman (U.S. Pat. No. 4,808,406) pertains to a method for producing finely divided stable cupric hydroxide composition of low bulk density comprising contacting solutions of an alkali metal carbonate or bicarbonate and a copper salt, precipitating a basic copper carbonate-basic copper sulfate to a minimum pH in the range of greater than 5 to about 6, contacting the precipitate with an alkali metal hydroxide and converting basic copper sulfate to cupric hydroxide, within the pH range of 7 to 11. The ""406 patent pertains to the production of cupric hydroxide from a mixture of basic copper carbonate and basic copper sulfate. Phosphates are not present in the ""406 patent technology.
The ""337 patent to Nakaji et al. (U.S. Pat. No. 4,940,337) provides a stirring apparatus for mixing, with metallic iron masses, a concentrated strongly acidic ferric chloride waste fluid containing iron and one or more other heavy metals in which the content of nickel is highest, the stirring apparatus being characterized by comprising a rotating mechanism for rotating a container, and a passage which is disposed in a rotary shaft and through which excess gas and liquid generated during stirring is discharged into the outside. The ""337 patent pertains to the separation of metals from ion chloride waste. The production of a purified copper hydroxide is not disclosed.
The ""169 patent to Ploss et al. (U.S. Pat. No. 4,404,169) pertains to a process of producing cupric hydroxides having stability in storage if phosphate ions are added to a suspension of copper oxychloride in an aqueous phase. The copper oxychloride is then reacted with alkali metal hydroxide or alkaline earth metal hydroxide, and the cupric hydroxide precipitated as a result of the suspension is washed and then re-suspended and subsequently stabilized by the addition of acid phosphate to adjust a pH value of 7.5 to 9. The suspended copper oxychloride is preferably reacted in the presence of phosphate ions in an amount of 1 to 4 grams per liter of the suspension and at a temperature of 20xc2x0 to 25xc2x0 C. and the resulting cupric hydroxide is stabilized with phosphate ions in an amount of 3 to 6grams per liter of the suspension. The ""169 patent reacts copper oxide oxychloride in the presence of phosphate.
As has been shown, there are significant disadvantages associated with the poor stability of conventionally prepared cupric hydroxide. Even small amounts of ferrous ion will catalyze the decomposition of cupric hydroxide to cupric oxide. This poor stability inhibits the utilization of cupric oxide as a bactericide and fungicide. Additional uses of highly pure cupric hydroxide are in the fabrication of superfine metallic copper, in the preparation of catalysts and in superconductors. These disadvantages can be eliminated and the advantages attained by the development of a process that can readily produce purified and stable cupric hydroxide.
The invention, in part, pertains to a stable cupric hydroxide.
The invention, in part, pertains to a cupric solution substantially free from aluminum, ferric and ferrous ions.
The invention, in part, pertains to the removal of iron from a copper solution by oxidation and precipitation of ferric solution.
The invention, in part, pertains to the utilization of phosphate ion to increase the oxidation efficiency and to simultaneously precipitate out the formed ferric ion.
The invention, in part, pertains to the manufacture of cupric hydroxide from impure raw materials such as mother liquor from copper sulfate production.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
Advantages of the present invention will become more apparent from the detailed description given herein after. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Copper can take on the cuprous Cu+ and cupric Cu2+ oxidation states. The cupric hydroxide, also called copper(II) hydroxide compounds of the invention are represented by formula I:
Cu(OH)2 xe2x80x83xe2x80x83(I)
Copper(II) hydroxide is prone to decomposition to the oxide, as is represented by formula II:
Cu(OH)2xe2x86x92CuO+H2Oxe2x80x83xe2x80x83(II)
The inventors found that this decomposition is catalyzed by metal species such as iron. The inventors believe that the true catalytic species is Fe2+ occluded (interstitially) in the crystal lattice of Cu(OH)2, which changes its molecular structure on being oxidized to Fe3+ and destroys the Cu(OH)2 crystal to form more stable product, CuO. Furthermore, the CuO produced catalyzes the dehydration reaction forming more CuO. Therefore, inhibition of this reaction is necessary to obtain a stable product.
Copper(II) hydroxide is described in the Kirk Othmer Encyclopedia of Chemical Technology as being produced by a reaction of a copper salt solution and sodium hydroxide to form a blue, gelatinous, voluminous precipitate of limited stability. Efforts are concentrated at stabilizing the product, especially in industrial production. Usually ammonia or phosphates are incorporated into the hydroxide to produce a color-stable product. The ammonia processed copper hydroxide is almost stoichiometric and copper content as high as 64% is not uncommon. The phosphate-produced material is lower in copper and has a finer particle size and higher surface area than ammonia processed hydroxide. Other methods of production generally rely on the formation of an insoluble copper precursor prior to the formation of the hydroxide. (Kirk Othmer Encyclopedia of Chemical Technology, Fourth Ed., Vol. 7, p. 508 (John Wiley and Sons 1993)). However, the products produced by these methods are not stable enough to dry by use of spray drying.
Copper hydroxide is almost insoluble in water (3 xcexcg/L) but readily dissolves in mineral acids and ammonia forming salt solutions or copper amine complexes. The hydroxide is somewhat amphoteric dissolving in excess sodium hydroxide solution for form trihydroxycuprate Cu(OH)3xe2x88x92 and tetrahydrocuprate Cu(OH)4xe2x88x92.
Copper(II) hydroxide has been conventionally prepared by the addition of sodium hydroxide, NaOH, to a salt of copper and decomposing at a temperature above 100xc2x0 C. In the presence of excess alkali, the decomposition occurs at temperatures above 50xc2x0 C.
When ferrous impurities are present in copper-containing raw materials, the inventors have found it feasible to precipitate out the ferrous ion an aqueous solution by oxidizing it to ferric ion, especially to ferric phosphate. The ferrous ion is oxidized using common oxidants such as H2O2, hypochlorite (bleach), Cl2, O2, O3, etc. The possible range of oxidizing agents includes singlet oxygen, triplet oxygen, singlet or triplet oxygen containing gas, ozone, ozone containing gas, chlorine, chlorine containing gas, chlorine dioxide, chlorine dioxide containing gas, hypochlorite ion, and chlorite ion. Blowing air through the solution will also oxidize ferrous ion to ferric ion, but the oxygen in air oxidizes the ion rather slowly. Mixtures of oxidizing agents can also be used.
Moreover, the oxidation of ferrous ion proceeds slowly. Therefore, heating of the reaction mixture is preferable to elevate the conversion efficiency. The heating temperature can range from about 20xc2x0 C. to 130xc2x0 C. A preferred heat temperature range is about 80-100xc2x0 C. A preferable temperature is about 100xc2x0 C.
Utilization of the appropriate counterion will make the oxidation more efficient and promote precipitation of the ferric salt. The utilization of phosphate ion both increases the efficiency of oxidation and simultaneously precipitates ferric ion. Alternatively, fluoride ion has been found to be effective.
It is known that aqueous cupric ion precipitates forming a basic salt such as tribasic cupric sulfate CuSO43Cu(OH)2, cupric oxychloride CuCl23Cu(OH)2, cupric basic carbonate CuCO33Cu(OH)2, etc. by increasing the solution pH. The inventors found that the formation of the basic salts begins at a pH of about 3.5 and is complete at a pH of about 7. The preferable pH for obtaining the basic copper salt is a pH of about 6. However, the precipitation of ferric ion as ferric oxide or phosphate is the more efficient at the higher pH. As a result, the pH best suited for the precipitation of ferric ion is concluded to be a pH of about 1-4 and preferably about 3.5. Most common bases can be used to raise the pH to the 1-4 range. Preferred bases include aqueous NH3, Na2CO3, K2CO3 and KHCO3.
The hardly soluble ferric compounds such as ferric oxide and ferric phosphate in copper hydroxide do not greatly decrease the stability of copper hydroxide against the decomposition to form CuO and H2O. However, it is preferable to remove the precipitate formed from the oxidized cupric solution in order to obtain a purer product.
Next, a base is added to the filtrate to bring the pH to about 6. The basic copper salts, such as CuSO43Cu(OH)2, CuCl23Cu(OH)2, CuCO33Cu(OH)2, etc., precipitate out. These salts can then be harvested.
When the pH of the reaction mixture or a suspension of basic salt is elevated to a pH of about 8 or more, the basic salts suspended in the solution are converted to cupric hydroxide. The complete conversion to copper hydroxide product is attained by adding additional base until the pH rises to about 12. The bases used to precipitate the cupric hydroxide can be an alkali metal hydroxide and/or an alkaline earth metal hydroxide. Examples of the bases include KOH, NaOH, LiOH, Ca(OH)2, Mg(OH)2, etc. The bases used to precipitate the cupric hydroxide can also be a carbonate such as K2CO3 or Na2CO3. Also, the basic copper salts (CuSO43Cu(OH)2, CuCl23Cu(OH)2, CuCO33Cu(OH)2, etc.) can be converted to copper hydroxide by rinsing the salts and adding a base.
A strong base such as NaOH or KOH is apt to give an unstable product against the dehydrating decomposition reaction, presumably caused by the drastic pH change at the interface of added base solution and the copper containing solution forcing unselective precipitation to the existing species. As a result, a weak base such as sodium carbonate or bicarbonate and NH3is preferable.
The removal of ferrous ion is highly satisfactory when copper sulfate is used as the raw material. However, copper chloride solutions are more difficult to purify and copper sulfate solutions. The reason for the difficulty associated with copper chloride may be in view of the notably higher coordination potential of chloride ion compared to sulfate ion, which leads to soluble coordination products, especially in chloride concentrations greater than about 2 M.
Copper hydroxide can be prepared by using the mother liquor left after crystallization of copper sulfate using the ferrous removal method of the invention. The ferric hydroxide product was sufficiently stable so that the product can be dried by spray drying.
Removal of solids formed during the process, which can be either ferric ion or cupric hydroxide product, can be performed using a number of methods. Solids can be removed using filtration, centrifugation or decantation. On an industrial scale, filter presses or drum centrifuges can be used.

Process for producing stable cupric hydroxide and basic cupric salts


Detergent mixtures comprising (a) an oligomeric esterquat which is the product of the process which comprises reacting a mixture of a mono-carboxylic acid and a dicarboxylic acid with an alkanolamine to form an alkanolamine oligoester and reacting the alkanolamine oligoester with an alkylating agent and (b) the product of the process which comprises reacting an alkylene oxide and a fatty acid amidoamine, wherein the weight ratio of components (a) to (b) is from about 10:90 to about 90:10; and wherein the oligomeric esterquat has at least two cationic centers.

1. Field of the Invention
This invention relates to detergent mixtures containing oligomeric esterquats and alkoxylated fatty acid amidoamines and to the use of the mixtures for the production of fabric softeners and hair-care compositions.
2. Statement of Related Art
As a result of increased biodegradability requirements, quaternary fatty acid alkanolamine ester salts, so-called xe2x80x9cesterquatsxe2x80x9d, have displaced tetraalkyl ammonium compounds as cationic surfactants both for the production of fabric softeners and for the conditioning of hair. Overviews on this subject have been published, for example, by R. Puchta et al. in Tens. Surf. Det., 30, 186 (1993), by M. Brock in Tens. Surf. Det. 30, 394 (1993), by R. Lagerman et al. in J. Am. Oil. Chem. Soc., 71, 97 (1994) and by l. Shapiro in Cosm. Toil. 109, 77 (1994). However, there is a demand on the market for products with further improved properties.
Accordingly, the complex problem addressed by the present invention was to provide detergent mixtures which would have improved conditioning and antistatic properties and complete biological degradability, could be dissolved quickly and completely, even in cold water, would have a sufficiently high viscosity but would not thicken or form gels in storage and, finally, would dissolve clearly in any ratio with water without any need for alcohols.
The present invention relates to detergent mixtures containing
(a) oligomeric esterquats obtainable by condensation of mixtures of mono-and dicarboxylic acids with alkanolamines and subsequent quaternization of the alkanolamine oligoesters and
(b) products of the addition of alkylene oxides onto fatty acid amidoamines.
It has surprisingly been found that the mixtures according to the invention not only are highly concentrated and water-clear, they also have an advantageously high and stable viscosity. The preparations can be diluted with water in any quantities and may then be immediately used as fabric softeners or hair-care compositions. They provide both synthetic and natural fibers with a particularly pleasant soft feel and, in addition, reduce the static charging between the fiber filaments to a quite considerable extent. Another advantage is that they can be dispersed particularly easily in cold water and, in addition, are readily biodegradable.
Oligomeric esterguats
The oligomeric esterquats have at least two cationic centers and, accordingly, differ from other known esterquats which have only one quaternary nitrogen. The production and use of these substances is known from DE-C1 19539846 (Henkel). In simple terms, the synthesis principle consists in linking several, but preferably exactly two, polyfunctional alkanolamines by means of a dicarboxylic acid, completely or partly esterifying the free hydroxyl groups with monocarboxylic acids and then quatemizing the nitrogen atoms present in the oligomeric or dimeric ester by methods known per se.
Typical examples of monocarboxylic acids, which may be used as one of the two acid components of the oligomeric esterquats, are fatty acids and oxocarboxylic acids containing 6 to 22 carbon atoms such as, for example, caproic acid, caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid, isotridecanoicacid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and the technical mixtures thereof obtained, for example, in the pressure hydrolysis of natural fats and oils, in the reduction of aldehydes from Roelen""s oxosynthesis or in the dimerization of unsaturated fatty acids. Technical fatty acids containing 12 to 18 carbon atoms, for example coconut, palm, palm kernel or tallow acid, preferably in hydrogenated or partly hydrogenated form, are preferred. Examples of suitable dicarboxylic acids, which may be used as a second bridging carboxylic acid component, are succinic acid, maleic acid, glutaric acid, 1,12-dodecanedioic acid and, more particularly, adipic acid. Oligomeric esterquats based on fatty acids containing 6 to 22 carbon atoms and adipic acid are preferably used. To produce the oligomeric esterquats, the mono-and dicarboxylic acids may be used in a molar ratio of 1:1 to 3:1 and preferably 1.5:1 to 2.5:1.
The alkanolamine component of the oligomeric esterquats may be derived from methyl diethanolamine, but is preferably derived from tri-ethanolamine and from mixtures of the two. To produce the compounds, the mono-/dicarboxylic acids on the one hand and the alkanolamines on the other hand may be used in a molar ratio of 1:1 to 3:1 and are preferably used in a molar ratio of 1.5:1 to 2:1.
The esterification may be carried out in known manner, as described for example in International patent application WO 91101295 (Henkel). The esterification is advantageously carried out at temperatures of 120 to 220xc2x0 C. and, more particularly, 130 to 170xc2x0 C. and under pressures of 0.01 to 1 bar. Suitable catalysts are hypophosphorous acid and alkali metal salts thereof, preferably sodium hypophosphite, which may be used in quantities of 0.01 to 0.1% by weight and are preferably used in quantities of 0.05 to 0.07% by weight, based on the starting materials. In the interests of 30 particularly high color quality and stability, it has proved to be of advantage to use alkali metal and/or alkaline earth metal borohydrides such as, for example, potassium, magnesium and in particular sodium borohydride. The co-catalysts are normally used in quantities of 50 to 1000 ppm and more particularly 100 to 500 ppm, again based on the starting materials. Corresponding processes are also the subject of German patents DE-C1 4308792 and DE-C1 4409322 (Henkel), to which reference is specifically made here. Mixtures of the fatty acids and dicarboxylic acids may be used or the esterification may be carried out with the two components in succession.
The quaternization of the fatty acid/dicarboxylic acid alkanolamine esters may be carried out in known manner. Although the reaction with the alkylating agents can be carried out in the absence of solvents, it is advisable to use at least small quantities of water or lower alcohols, preferably isopropyl alcohol, for the preparation of concentrates which have a solids content of at least 80% by weight and, more particularly, at least 90% by weight. Suitable alkylating agents are alkyl halides, for example methyl chloride; dialkyl sulfates, for example dimethyl sulfate or diethyl sulfate; or dialkyl carbonates such as, for example, dimethyl carbonate or diethyl carbonate. The esters and the alkylating agents are normally used in a molar ratio of 1:0.95 to 1:1.05, i.e. in a substantially stoichiometric ratio. The reaction temperature is normally in the range from 40 to 80xc2x0 C. and more particularly in the range from 50 to 60xc2x0 C. After the reaction, it is advisable to destroy unreacted alkylating agent by addition of, for example, ammonia, an (alkanol)amine, an amino acid or an oligopeptide, as described for example in German patent application DE-A1 4026184 (Henkel).
In the reaction of the alkanolamines with the mixtures of mono-and dicarboxylic acids, complex mixtures predominantly containing dimers, i.e. species in which two alkanolamines are bridged by a dicarboxylic acid and of which the free hydroxyl groups are partly esterified with monocarboxylic acids, are obtained. According to gel permeation chromatography, the mixtures also contain oligomeric esters where 3 to 4 quaternary centers are present. Monomeric compounds containing only one quaternary nitrogen are undesirable for performance-related reasons because they adversely affect clear solubility. Although they cannot be completely prevented from occurring, their content can be reduced to below 5% by weight through the presence of a sufficient quantity of dicarboxylic acid. The dimeric compounds corresponding to formula (I):
in which R1CO is an aliphatic, linear or branched, saturated or unsaturated acyl group containing 6 to 22 corbon atome, R2 is an alkyl group containing 1 to 4 carbon atoms, R3 and R5 independently of one nother represent alkyl or hydroxyalkyl groups containing 1 to 4 carbon atoms, R4 is hydrogen or has the same meaning as R1 CO, n1, n2, n3 and n4 independently of one another have a value of 1 to 5 and m has a value of 1 to 10. Dimeric esterquats with particularly advantageous properties correspond to formula (I) where R1CO is a linear saturated acyl group containing 12 to 18 carbon atoms, R2is a methyl group, R3 and R5 each represent hydroxyethyl groups, R4 has the same meaning as R1 CO n1, n2, n3 and n4 each have a value of 2 and m has a value of 4. The oligomeric esterquats preferably contain 20 to 90% by weight and more preferably 40 to 80% by weight of dimers, 10 to 80% by weight and more preferably 20 to 60% by weight of oligomers and less than 5% by weight of monomers, with the proviso that the quantities mentioned add up to 100% by weight.
Alkoxylated Fatty Acid Amidoamines
Alkoxylation products of fatty acid amidoamines are also known from the literature and preferably correspond to formula (II):
in which R6CO is an aliphatic, linear or branched, saturated or unsaturated. acyl group containing 6 to 22 carbon atoms, R7and R8 independently of one another represent hydrogen or an optionally hydroxysubstituted alkyl group containing 1 to 4 carbon atoms, R9 is hydrogen, an alkyl group containing 1 to 4 carbon atoms or has the same meaning as R6CO, R10 and R11 independently of one another represent hydrogen or a methyl group, A is a linear or branched alkylene group containing 2 to 4 carbon atoms, p and q independently of one another have a value of 1 to 3, y has a value of 1 to 3 and z has a value of 1 to 20.
They are normally produced from dialkylenetriamines or trialkylene-tetramines which are first esterified with 1 to 2 moles of carboxylic acid and then reacted in known manner with alkylene oxides, preferably ethylene oxide, for insertion into the free NH bonds. Typical examples of suitable oligoamines are diethylenetriamine, dipropylenetriamine, triethylene-tetramine and tripropylenetetramine and mixtures thereof. Suitable car-boxylic acids are the fatty acids containing 6 to 22 carbon atoms such as, for example, caproic acid, caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, paimitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and emucic acid and the technical mixtures thereof obtained, for example, in the pressure hydrolysis of natural fats and oils, in the reduction of aldehydes from Roelen""s oxosynthesis or in the dimerization of unsaturated fatty acids. Technical fatty acids containing 12 to 18 carbon atoms, for example coconut, palm, palm kernel or tallow acid, preferably in hydrogenated or partly hydrogenated form, are preferred. It has proved to be of particular advantage to use the carboxylic acids in such quantities that, on average, diamides are obtained. In addition, alkoxylated fatty acid amidoamines corresponding to formula (II), where R6CO is a linear saturated acyl group containing 12 to 18 carbon atoms, R7, R8, R10 and R11 represent hydrogen, R9 has the same meaning as R6CO, A is an ethylene group, p and q each have a value of 2, y has a value of 1 and z has a vlaue of 5 to 10, are particularly preferred for applicational reasons.
The alkoxylation may be carried out in known manner, i.e. ethylene oxide, propylene oxide or mixtures thereof are added in the presence of acidic, but preferably basic catalysts, for example sodium methylate or calcined hydrotalcite. Nonionic compounds are formed, but are quickly protonated in acidic solution and then show pseudocationic behavior.
According to the invention, the detergent mixtures may contain components (a) and (b) in a ratio by weight of 10:90 to 90:10, preferably 25:75 to 75:25 and more preferably 40:60 to 60:40.
The present invention also relates to the use of the detergent mixtures for the production of fabric softeners and hair-care preparations in which they may be present in quantities of 1 to 50% by weight, preferably 5 to 35% by weight and more preferably 10 to 25% by weight. Apart from the possibility of directly using the mixtures for the stated purpose, the most simple form of use consists in diluting them with water to the required in-use concentration.
Surfactants
In this connection, other additives, more particularly other surfactants, which are compatible with components (a) and (b) may also be added to the preparations. The surfactants in question are, above all, other nonionic or cationic or amphoteric or zwitterionic surfactants. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partly oxidized alk(en)yl oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolyzates (particularly wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysor-bates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution, although they preferably have a narrow-range homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds and monomeric esterquats, more particularly quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwifterionic surfactants are alkylbetaines, alkylamidobetaines, amino-propionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are all known compounds. Information on their structure and production can be found in relevant synoptic works, cf. for example J. Falbe (ed.), xe2x80x9cSurfactants in Consumer Productsxe2x80x9d, Springer Verlag, Berlin, 1987, pages 54 to 124 or J. Falbe (ed.), xe2x80x9cKatalysatoren, Tenside und Mineraldladditive (Catalysts, Surfactants and Mineral Oil Additives)xe2x80x9d, Thieme Verlag, Stuttgart, 1978, pages 123-217.
Auxiliaries and additives
Depending on the application envisaged, i.e. fabric softening or hair conditioning, the preparations obtainable using the detergent mixtures may contain other typical auxiliaries and additives, such as oil components, emulsifiers, superfatting agents, pearlizing waxes, stabilizers, consistency factors, thickeners, cationic polymers, silicone compounds, biogenic agents, antidandruff agents, film formers, preservatives, hydrotropes, solubilizers, UV filters, insect repellents, self-tanning agents, perfume oils, dyes and the like.
Suitable oil components are, for example, Guerbet alcohols based on fatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms, esters of linear C6-22 fatty acids with linear C6-22 fatty alcohols, esters of branched C6-22 carboxylic acids with linear C6-22 fatty alcohols, esters of linear C6-22 fatty acids with branched alcohols, more particularly 2-ethyl hexanol, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C6-10 fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-18 fatty acids, esters of C6-22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C6-22 alcohols (for example Finsolv(copyright) TN), dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons.
Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:
(1) products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 50 moles of propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group;
(2) C12/18 fatty acid monoesters and diesters of addition products of 1 to 30 moles of ethylene oxide onto glycerol;
(3) glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide adducts thereof;
(4) alkyl mono- and oligoglycosides containing 8 to 22 carbon atoms in the alkyl group and ethoxylated analogs thereof;
(5) addition products of 15 to 60 moles of ethylene oxide onto castor oil and/or hydrogenated castor oil;
(6) polyol esters and, in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy-istearate or polyglycerol dimerate. Mixtures of compounds from several of these classes: are also suitable;
(7) addition products of 2 to 15 moles of ethylene oxide onto castor oil and/or hydrogenated castor oil;
(8) partial esters based on linear, branched, unsaturated or saturated C6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose);
(9) mono-, di and trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates;
(10) wool wax alcohols;
(11) polysiloxanelpolyalkyl polyether copolymers and corresponding derivatives;
(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and/or mixed esters of fatty acids containing 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol, and
(13) polyalkylene glycols.
The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol monoesters and diesters and sorbitan monoesters and diesters of fatty acids or onto castor oil are known commercially available products. They are homolog mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C2/18 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as refatting agents for cosmetic formulations from DE-PS 20 24 051.
C8/18 alkyl mono- and oligoglycosides, their production and their use as surfactants are known from the prior-art literature. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols containing 8 to 18 carbon atoms. So far as the glycoside component is concerned, both monoglycosides where a cyclic sugar unit is attached to the fatty alcohol by a glycoside bond and oligomeric glycosides with a degree of oligomerization of preferably up to about 8 are suitable. The degree of oligomerization is a statistical mean value on which a homolog distribution typical of such technical products is based.
Other suitable emulsifiers are zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example coconutalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example coconutacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and coconutacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C8/18 alkyl or acyl group, contain at least one free amino group and at least one xe2x80x94COOHxe2x80x94 or xe2x80x94SO3Hxe2x80x94 group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut-alkylaminopropionate, cocoacylaminoethyl aminopropionate and C12/18 acylsarcosine. According to the invention, other suitable emulsifiers besides ampholytic surfactants are quaternary emulsifiers, those of the esterquat type, preferably. methyl-quatemized difatty acid triethanolamine ester salts, being particularly preferred.
Superfaffing agents may be selected from such substances as, for example, lanolin and lecithin and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the fatty acid alkanolamides also serving as foam stabilizers.
Suitable pearlizing waxes are, for example, alkylene glycol esters, particularly ethylene glycol distearate; fatty acid: alkanolamides, especially coconut acid diethanolamide; partial glycerides,: especially stearic acid monoglyceride; esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols containing 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty compounds, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which contain a total of at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides containing 12 to 22 carbon atoms with fatty alcohols containing 12 to 22 carbon atoms and/or polyols containing 2 to 15 carbon atoms and 2 to 10 hydroxyl groups; and mixtures thereof.
The consistency factors mainly used are fatty alcohols containing 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides. A combination of these substances with alkyl oligoglucosides and/or fatty acid-N-methyl glucamides of the same chain length and/or polyglycerol poly-12-hydroxystearates is preferably used. Suitable thickeners are, for example, polysaccharides, more especially xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol mono-esters and diesters of fatty acids, polyacrylates (for example Carbopols(copyright) [Goodrichl] or Synthalens(copyright) [Sigma]), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylol propane, narrow-range fatty alcohol ethox-ylates or alkyl oligoglucosides and electrolytes, such as sodium chloride and ammonium chloride.
Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400(copyright), cationic starch, copolymers of diallyl ammonium salts and acrylamides, quatemized vinyl pyrrolidone/vinyl imidazole polymers such as, for example, Luviquato (BASF), condensation products of polyglycols and amines, quatemized collagen polypeptides such as, for example, Lauryidimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat(copyright)L/Grinau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylamino hydroxypropyl diethylenetriamine (Cartaretine(copyright)/Sandoz), copolymers of acrylic acid with dimethyl diallyl ammonium chloride (Merquat(copyright) 550/ Chemviron), polyaminopolyamides as described, for example, in FR-A 2 252 840 and crosslinked water-soluble polymers thereof, cationic chitin derivatives such as, for example, quatemized chitosan, optionally in micro-crystalline distribution, condensation products of dihaloalkys, for example dibromobutane, with bis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationic guar gum such as, for example, Jaguar(copyright)CBS, Jaguar(copyright)C-17, Jaguar(copyright)C-16 of Celanese, USA, quatemized ammonium salt polymers such as, for example, Mirapol(copyright) A-15, Mirapol(copyright) AD-1, Mirapol(copyright) AZ-1 of Miranol, USA.
Suitable silicone compounds are, for example, dimethyl polysilox-anes, methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds which may be both liquid and resin-like at room temperature. Typical examples of fats are glycerides while suitable waxes are inter alia beeswax, camauba wax, candelilla wax, montan wax, paraffin wax or microwaxes, optionally in combination with hydrophilic waxes, for example cetyl stearyl alcohol or partial glycerides. Metal salts of fatty acids such as, for example, magnesium, aluminium and/or zinc stearate or ricinoleate may be used as stabilizers. In the context of the invention, biogenic agents are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, proteolytic enzymes and, vitamin complexes. Suitable antidandruff agents are climbazol, octopirox and zinc pyrithione. Typical film formers are, for example, chitosan, microcrystalline chitosan, quatemized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof and similar compounds. Suitable swelling agents for aqueous phases include montmorillonites, clay minerals, Pemulen and alkyl-modified Carbopol types (Goodrich).
UV filters in the context of the invention are, for example, organic substances which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat. UV-B filters can be oil-soluble or water-soluble. The following are examples of oil-soluble substances:
3-benzylidene camphor and derivatives thereof, for example 3-(4-methylbenzylideneycamphor;
4-aminobenzoic acid derivatives, preferably 4-(dimethylamino)-benzoic acid-2-ethylhexyl ester, 4-(dimethylamino)-benzoic acid-2octyl ester and 4-(dimethylamino)-benzoic acid amyl ester;
esters of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethylhexyl ester, 4-methoxycinnamic acid isopentyl ester, 2-cyano-3-phenylcinnamic acid-2-ethylhexyl ester (Octocrylene);
esters of salicylic acid, preferably salicylic acid-2-ethylhexyl ester, salicylic acid4-isopropylbenzyl ester, salicylic acid homomenthyl ester;
derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzo-phenone, 2-hydroxy4-methoxy4xe2x80x2-methylbenzophenone, 2,2xe2x80x2-dihydroxy-4-methoxybenzophenone;
esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di-2-ethylhexyl ester;
triazine derivatives such as, for example, 2,4,6-trianilino-(p-carbo-2xe2x80x2-ethyl-1xe2x80x2-hexyloxy)-1,3,5-triazine and Octyl Triazone;
propane-1,3-diones such as, for example, 1-(4-tert.butylphenyl)-3-(4xe2x80x2-methoxyphenylypropane-1,3-dione;
Suitable water-soluble substances are
2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof;
sulfonic acid derivatives of benzophenone, preferably 2-hydroxy4-methoxybenzophenone-5-sulfonic acid and salts thereof; sulfonic acid derivatives of 3-benzylidene camphor such as, for example, 4-(2-oxo-3-bomylidenemethyl)-benzene sulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts thereof.
Typical UV-A filters are, in particular, derivatives of benzoyl methane such as, for example 1-(4xe2x80x2-tert.butylphenyl)-3-(4xe2x80x2-methoxyphenyl)-propane- 1,3-dione or 1-phenyl-3-(4xe2x80x2-isopropylphenyl)-propane-1,3-dione. The UV-A and UV-B filters may of course also be used in the form of mixtures. Besides the soluble substances mentioned, insoluble pigments, i.e. finely dispersed metal oxides or salts, for example titanium dioxide, zinc oxide, iron oxide, aluminium oxide, cerium oxide, zirconium oxide, silicates (talcum), barium sulfate and zinc stearate, may also be used for this purpose. The particles should have a mean diameter of less than 100 nm, preferably between 5 and 50 nm and more preferably between 15 and 30 nm. They may be spherical in shape although ellipsoidal particles or other non-spherical particles may also be used. Besides the two groups of primary UV filters mentioned above, secondary UV filters of the antioxidant type may also be used. Secondary UV filters of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin. Typical examples are Superoxid-Dismustase, tocopherols (vitamin E) and ascorbic acid (vitamin C).
In addition, hydrotropes such as, for example, ethanol, isopropyl alcohol or polyols may be used to improve flow behavior. Suitable polyols preferably contain 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are
glycerol;
alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of 100 to 1,000 dalton;
technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as, for example, technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
methylol compounds such as, in particular, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and dipentaerythritol;
lower alkyl glucosides, particularly those containing 1 to 8 carbon atoms in the alkyl group, for example methyl and butyl glucoside;
sugar alcohols containing 5 to 12 carbon atoms such as, for example, sorbitol or mannitol;
sugars containing 5 to 12 carbon atoms such as, for example, glucose or sucrose and
aminosugars such as, for example, glucamine.
Suitable preservatives are, for example, phenoxyethanol, formalde-hyde solution, parabens, pentanediol or sorbic acid. Suitable insect repellents are N,N-diethyl-m-toluamide, pentane-1,2-diol or Insect Repellent 3535. A suitable self-tanning agent is dihydroxyacetone.
Examples of perfume oils include the extracts of blossoms (lavender, rose, jasmine, neroli), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamon, costus, iris, calmus), woods (sandalwood, pockwood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and, branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, for example musk, civet and beaver, may also be used. Suitable synthetic and semisynthetic perfume oils are Ambroxan, eugenol, isoeugenol, citronellal, hydroxycitronellal, geraniol, citronellol, geranyl acetate, citral, ionone and methyl ionone.
Suitable dyes are any of the substances suitable and approved for cosmetic purposes as listed, for example, in the publication xe2x80x9cKosmetische Fxc3xa4irbemittellxe2x80x9d of the Farbstoffkommission der Deutschen Forschungs-gemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. These dyes are normally used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
The total percentage content of auxiliaries and additives may be from 1 to 50% by weight and is preferably from 5 to 40% by weight, based on the particular composition. The compositions may be prepared by 15 standard cold or hot processes and are preferably produced by the phase inversion temperature method.

Detergent mixtures containing oligomeric esterquats


Carboxy-functionalized polyphenylene ethers containing structural units with a carboxyalkyl group in the 2-position are prepared by redistribution of a polyphenylene ether with a 2-carboxyalkylphenol such as 2-(3-carboxypropyl)phenol (melilotic acid), or by oxidative coupling of a suitable phenol with such a 2-carboxyalkylphenol. The products form compatibilizing copolymers with polymers containing carboxylic acid-reactive functional groups, such as polyesters, polyamides and epoxy resins.

This invention relates to polyphenylene ethers, and more particularly to functionalized polyphenylene ethers useful for the compatibilization of copolymer blends.
Polyphenylene ethers are a widely used class of thermoplastic engineering resins characterized by excellent properties including hydrolytic stability, dimensional stability, toughness, heat resistance and dielectric properties. It is of continuing interest to introduce these desirable properties into polymer blends by incorporating the polyphenylene ethers as blend constituents. This is often difficult, however, since the polyphenylene ethers are incompatible with many other polymers.
A strategy frequently used to compatibilize polyphenylene ethers with other polymers is to introduce into the polyphenylene ether functional groups which are reactive with said other polymers, enabling the formation of copolymer-containing compositions in which the copolymers serve as compatibilizers. For example, polyphenylene ethers containing carboxylic acid functional groups or derivatives thereof can form copolymers with such other polymers as polyamides, hydroxy-terminated polyesters and epoxy group-containing polymers.
Carboxy or carboxy-derived groups (e.g., anhydride groups) have been introduced into polyphenylene ethers by reaction through the hydroxy end groups with such compounds as trimellitic anhydride acid chloride, by grafting reactions with such compounds as maleic anhydride or fumaric acid, and by redistribution with acidic compounds such as p-hydroxyphenylacetic acid. Redistribution reactions are often of particular interest since they may be conducted under relatively mild conditions, typically including temperatures not substantially greater than 100xc2x0 C. and the presence of non-destructive catalysts such as diaryl peroxides and quinones and relatively inert solvents such as toluene. The redistribution reaction results in a breakup of polymer molecules into lower molecular weight molecules containing the desired carboxylic acid or other functional groups.
Redistribution with the aforementioned acidic compounds is somewhat difficult, however, since said compounds are not adequately soluble in solvents such as toluene. Moreover, the mechanism of the redistribution reaction is such that only low levels of such compounds can be incorporated in the polyphenylene ether, owing in part to substitution in the para position which makes that position unavailable for reaction.
U.S. Pat. No. 5,880,221 discloses attempts at redistribution of polyphenylene ethers with various aryl-substituted alkanoic acids. It was found that whereas carboxy phenols bearing two phenolic hydroxyl groups and alkyl substituents ortho to the phenolic hydroxy groups, such as 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)pentanoic acid, did incorporate, simple phenols such as p-hydroxyphenyloctanoic acid did not. Interest continues, therefore, in the development of improved functionalization strategies employing other carboxylic acids, especially those of simpler molecular structure than the aforementioned bisphenolic acid.
Japanese Kokai 5/59,270 and 5/59,272 disclose reaction products of epoxy- and carboxy-functionalized olefin polymers with copolyphenylene ethers in which a portion of the structural units contain a xe2x80x94(CH2)3OH group. Said copolyphenylene ethers are produced by copolymerization via oxidative coupling of two phenols, one containing and one not containing said group. There is no disclosure of a copolyphenylene ether containing a carboxyalkyl group.
The present invention is based on the discovery that certain o-hydroxyaromatic-substituted aliphatic carboxylic acids are capable of incorporation under mild conditions into polyphenylene ethers, either by copolymerization or by redistribution. The conditions employed include use of a single solvent in which the polyphenylene ether has high solubility.
One aspect of the invention, therefore, is carboxy-functionalized polyphenylene ethers comprising structural units of the formulas
wherein each Q1 is independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each Q2 and Q3 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q1; and R is an alkylene radical containing at least 1 carbon atom.
A further aspect of the invention is a method for preparation of such functionalized polyphenylene ethers which comprises redistributing a polyphenylene ether with a 2-carboxyalkylphenol of appropriate formula (corresponding to formula II) in the presence of a redistribution catalyst.
Another aspect of the invention is a method for production of such functionalized polyphenylene ethers which comprises oxidatively coupling at least one monohydroxyaromatic compound with said 2-carboxyalkyiphenol.
These carboxy-functionalized polyphenylene ethers are reactive and readily form copolymers with other reactive polymers. Therefore, a still further aspect of the invention is resinous compositions comprising copolymers of said functionalized polyphenylene ethers with at least one polymer containing carboxylic acid-reactive functional groups.
The polyphenylene ethers which are functionalized according to the invention are known polymers having structural units of formula I. Both homopolymer and copolymer polyphenylene ethers are included. The preferred homopolymers are those containing 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include random copolymers containing such units in combination with (for example) 2,3,6-trimethyl-1,4-phenylene ether units. Also included are polyphenylene ethers containing moieties prepared by grafting onto the polyphenylene ether in known manner such materials as vinyl monomers or polymers such as polystyrenes and elastomers, as well as coupled polyphenylene ethers in which coupling agents such as low molecular weight polycarbonates, quinones, heterocycles and formals undergo reaction in known manner with the hydroxy groups of two polyphenylene ether chains to produce a higher molecular weight polymer, provided a substantial proportion of free OH groups remains.
The polyphenylene ethers generally have an intrinsic viscosity greater than about 0.25, most often in the range of about 0.25-0.6 and especially 0.4-0.6 dl./g., as measured in chloroform at 25xc2x0 C.
The polyphenylene ethers are typically prepared by the oxidative coupling of at least one monohydroxyaromatic compound such as 2,6-xylenol or 2,3,6-trimethylphenol. Catalyst systems are generally employed for such coupling; they typically contain at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with various other materials.
Particularly useful polyphenylene ethers for many purposes are those which comprise molecules having at least one aminoalkyl-containing end group. The aminoalkyl radical is covalently bound to a carbon atom located in an ortho position to the hydroxy group. Products containing such end groups may be obtained by incorporating an appropriate primary or secondary monoamine such as di-n-butylamine or dimethylamine as one of the constituents of the oxidative coupling reaction mixture. Also frequently present are 4-hydroxybiphenyl end groups and/or biphenyl structural units, typically obtained from reaction mixtures in which a by-product diphenoquinone is present, especially in a copper-halide-secondary or tertiary amine system. A substantial proportion of the polymer molecules, typically constituting as much as about 90% by weight of the polymer, may contain at least one of said aminoalkyl-containing and 4-hydroxybiphenyl end groups.
It will be apparent to those skilled in the art from the foregoing that the polyphenylene ethers contemplated for use in the present invention include all those presently known, irrespective of variations in structural units or ancillary chemical features.
The functionalized polyphenylene ethers of the invention contain, in addition to structural units of formula I, those of formula II in which Q1-3 are as previously defined. The units of formula II are characterized by a carboxyalkyl group in the 2- or 3-position, preferably the 2-position, relative to the oxygen atom and a Q2 moiety in the other of the 2- and 3-positions. The R radical in said carboxyalkyl group is an alkylene radical containing at least 1 and preferably 2-6 carbon atoms; it may be linear or branched and is usually linear. Particularly preferred is the ethylene radical, whereupon the corresponding carboxylic acid is 2-(3-carboxypropyl)phenol (melilotic acid).
The first method of the invention for preparation of the functionalized polyphenylene ethers is by redistribution of a conventional polyphenylene ether with the appropriate 2-carboxyalkylphenol; i.e., the compound corresponding to formula II (hereinafter sometimes simply xe2x80x9cacidxe2x80x9d for brevity). Redistribution may be effected as described, for example, in U.S. Pat. Nos. 3,367,978, 4,234,706 and 5,213,886 and in White et al. J. Org. Chem., 34, 297-303 (1969), the disclosures of which are incorporated by reference herein.
The redistribution reaction typically involves heating the polyphenylene ether in solution in a relatively inert solvent, most often an aromatic hydrocarbon such as toluene or xylene, with the acid and a redistribution catalyst at a temperature in the range of about 50-110xc2x0 C. Suitable redistribution catalysts include peroxides such as benzoyl peroxide, cumyl peroxide, t-butylperbenzoic and t-butylalkanoic acids and quinones such as 3,3xe2x80x2,5,5xe2x80x2-tetramethyl-4,4xe2x80x2-diphenoquinone (TMDQ).
Redistribution is accompanied by cleavage of the polymer molecule by the acid, which is incorporated in the cleaved molecules, most often as an end group at the head of the molecule. The proportion of acid is determined by the degree of functionalization desired coupled with the overall molecular weight desired in the product; high proportions of acid result in a high degree of functionalization and a lower average polymer molecular weight, while low proportions afford a higher molecular weight polymer with a low degree of functionalization. In general, acid levels are in the range of about 1-10% and preferably about 2-5% by weight based on polyphenylene ether. The promoter is most often employed in the amount of about 1-10% by weight based on polyphenylene ether.
The second preparative method of the invention is copolymerization of the acid in suitable proportions with at least one monohydroxyaromatic compound, i.e., the one corresponding to formula I, in an oxidative coupling reaction. The conditions of said reaction are the art-recognized ones, typically including the presence of a catalyst of oxidative coupling as previously described. An advantage of this method of preparation may be the ease of preparing functionalized polyphenylene ethers of relatively high molecular weights.
The resinous compositions of the invention may be prepared by effecting reaction between the carboxy-functionalized polyphenylene ether and any polymer containing one or more functional groups which are reactive with carboxylic acids. Illustrative groups of this type are hydroxy, amino and epoxy groups. Said polymer may be thermoplastic or thermosetting. Examples of suitable polymers are hydroxy-terminated polyesters, amine-terminated polyamides, and epoxy resins including glycidyl ethers of bisphenols, epoxy-functionalized olefin polymers, epoxy novolaks and alicylic epoxy resins.
The reaction of the polymer with the carboxy-functionalized polyphenylene ether may take place under any suitable conditions, including solution and melt reaction conditions. Where appropriate, they may be conducted in the presence of suitable catalysts, as illustrated by phase transfer catalysts and epoxy cure catalysts. Other materials, both reactive and non-reactive, may be present. Illustrative materials are impact modifiers, hardeners, fillers, pigments and stabilizers.
The invention is illustrated by the following examples. All parts and percentages are by weight. Molecular weights are weight average unless otherwise indicated and were determined by gel permeation chromatography. Inherent viscosities were determined in chloroform at 25xc2x0 C. Carboxy incorporation was determined by proton nuclear magnetic resonance spectroscopy.

Method for making carboxy-functionalized polyphenylene ethers, and blends containing them