MXPA00001178A - Process for preparing ether-capped poly(oxyalkylated) alcolhol surfactants - Google Patents

Abstract

A process for preparing an ether-capped poly(oxyalkylated)alcohol surfactant is provided. The alcohol has the formula:R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2 wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms;R3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms;x is an integer having an average value from 6 to 15, wherein when x is 2 or greater R3 may be the same or different;further wherein when x is 15 or greater and R3 is H and methyl, at least four of R3 are methyl, further wherein when x is 15 or greater and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, further wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof;comprising the steps of:(a) providing a glycidyl ether having formula (I) wherein R2 is defined as above;(b) providing an ethoxylated alcohol having formula (II) wherein R1, R3 and x are defined as above;and (c) reacting the glycidyl ether with the ethoxylated alcohol to form the surfactant.

Description

PROCEDURE FOR PREPARING SURELY ALCOHOL ASSAYS POLIOXIA QUILADO OF BLOCKED EXTREMES WITH ETHER TECHNICAL FIELD The present invention relates to a process for preparing low-foaming nonionic surfactants, and more particularly to a process for preparing ether-capped alcohol-alkyl ether surfactants having superior benefits of spot and film reduction in Dishwashing and hard surface cleaning applications, as well as foam suppression in detergent compositions.

BACKGROUND OF THE INVENTION Dishwashing and cleaning hard surfaces, in particular automatic dishwashing in household appliances, is a very different technique than washing fabrics. Domestic fabric washing is usually done on purposely made machines that have a rotating action. These are very different from household appliances for automatic dishwashing by spray action. The spray action in the latter tends to foam. The foam can easily flood the lower solerails of domestic dishwashers and slowing down the spray action, which in turn reduces the cleaning action. Thus, in the different field of automatic domestic dishwashing, the use of detergent surfactants for laundry that produce foam is normally restricted. These aspects are but a brief illustration of the unique formulation restrictions in the fields of automatic household dishwashing and hard surface cleaning. One solution to this problem of foaming has been to include a foam suppressant, typically a silicone foam suppressant.

However, this solution, although it works to a certain degree in compositions for washing fabrics, fails in domestic dishwashers. The high shear forces involved in household dishwashers degrade the silicone foam suppressors, so any foam suppressant present at the start of washing disappears before concluding. Silicone foam suppressors are not strong enough to survive in the environment of a domestic dish washer. Even in laundry applications, although less shear than in a domestic dish washing machine, there is still a decrease in foam suppression towards the end of the wash cycle, due to the degradation of the silicone foam suppressant. An alternative would be to increase the amount of the silicone foam suppressant present; however, the cost of silicone foam suppressors and the fact that they have a tendency to redeposite on hydrophobic surfaces such as plastic, makes this an undesirable solution. The need remains today for a viable and cost-effective alternative to a silicone foam suppressant suitable for use in automatic dishwashers as well as in clothes washers. Due to the previous technical restrictions, as well as the needs and demands of consumers, these compositions undergo continuous changes and improvements. In addition, environmental factors such as phosphate restriction, the desire to provide even better cleaning results with less product, provide less thermal energy and use less water to facilitate the washing process, have led to the need to obtain improved compositions. However, many compositions proposed so far for washing dishes and hard surfaces have had aesthetic and technical disadvantages, one being the presence of undesirable spots and films on the cleaned surfaces. These undesirable spots and films can be caused by redeposition of soils and cleaning agents such as surfactants having low water solubility. In addition, there continues to be a need for better cleaning, especially to reduce the formation of stains and films and, in some cases, to remove greasy dirt. This need arises from consumer demand to improve the performance of the stain and film removal benefits of cleaning compositions, as well as the removal of greasy soils.

There is also a need to obtain low foaming surfactants that can provide improved stain and film reduction benefits, while providing removal of greasy soils, as well as providing foam suppression that is strong enough to survive in the wash environment in which it develops.

BACKGROUND OF THE PREVIOUS TECHNIQUE Patent of E.U.A. No. 4,272,394, issued June 9, 1981; patent of E.U.A. No. 5,294,365; issued on March 15, 1994; patent of E.U.A. No. 4,248,729, issued February 3, 1981; patent of E.U.A. No. 4,284,532, issued August 18, 1981; patent of E.U.A. No. 4,627,927, issued December 9, 1986; patent of E.U.A. No. 4,790,856, issued December 13, 1988; patent of E.U.A. No. 4,804,492, issued February 14, 1989; patent of E.U.A. No. 4,770,815, issued September 13, 1989; patent of E.U.A. No. 5,035,814, issued July 30, 1991; patent of E.U.A. No. 5,047,165, issued September 10, 1991; patent of E.U.A. No. 5,419,853, issued May 30, 1995; patent of E.U.A. No. 5,294,365, issued March 15, 1994; GB application No. 2,144,763, published March 13, 1985; GB application No. 2,154,599, published September 9, 1985; WO application No. 9,296,150, published April 16, 1992; WO application No. 94/22800, published October 13, 1994; application WO 93/04153, published March 4, 1993; WO application No. 97/22651, published June 26, 1997; EP Application No. 342,177, published November 15, 1989 and "Glyceril Bisether Sulfates, 1: Improved Synthesis", Brian 5 D. Condom; Journal of the American Chemical Society, Vol. 71, No. 7 (July 1994).

BRIEF DESCRIPTION OF THE INVENTION This need is met by the present invention, in which a process for preparing a non-ionic low foaming surfactant is provided. The low foaming nonionic surfactant, either alone or in combination with other surfactants, provides improved stain reduction performance and films, as well as improved cleaning performance on oily soils and foam suppression in certain applications. While not intended to be limited by theory, it is believed that the alcohol surfactants of the present invention provide superior stain and film reduction benefits through an extension action. improved. As for the improved cleaning performance in greasy soils, said benefits are shown when the alcohol surfactants of the present invention are used in conjunction with a high-cloud point nonionic surfactant as described in detail in the present. Finally, the alcohol surfactants of the present invention also act to reduce foam or foaming associated with food stains or various other cleaning agents, and allow the use of soluble surfactants, which are highly volatile. foam, such as amine oxides. In accordance with a first aspect of the present invention, there is provided a process for preparing a polyoxyalkylated alcohol surfactant with ether-blocked ends. The alcohol has the formula: R10 [CH2CH (R3) O] xCH2CH (OH) CH2OR2 wherein R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from about 1 to about 30 carbon atoms. carbon; R3 is H or a linear aliphatic hydrocarbon radical having from about 1 to about 4 carbon atoms; x is an integer having an average value of 1 to about 30, where when x is 2 or more, R3 can be identical or different, independently H, or Ci to C in any molecule, and also where when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl , and wherein in addition R2 may optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof. The method comprises the steps of: (a) providing a glycidyl ether having the formula: *? - «-firm-i jftl? Ff -,,? AM« «t¿ = &-J ^" ^ ^ "" ^ ?? ^^ where R is as described above, (b) provide a ethoxylated alcohol that has the formula: where R1, R3 and x are as previously defined; and (c) reacting the glycidyl ether with the ethoxylated alcohol to form the surfactant. R1 and R2 are aliphatic, straight or branched, saturated or unsaturated hydrocarbon radicals, having from about 6 to about 22 carbon atoms and x is an integer having an average value of from 6 to about 15. The step of reacting the ether glycidyl with ethoxylated alcohol can be carried out in the presence of a catalyst such as mineral acid, Lewis acid and mixtures thereof. Preferably the catalyst is a Lewis acid selected from the group consisting of TiCl 4, Ti (O'Pr), ZnCl, SnCl, AICI 3, BF 3 -OEt 2 and mixtures thereof, with SnCl being the most preferred. The step of reacting glycidyl ether with ethoxylated alcohol is preferably carried out at a temperature of about 50 ° C to about 95 ° C, and most preferably 60 ° C to about 80 ° C.

The step of providing glycidyl ether may further comprise the step of reacting a linear aliphatic or aromatic alcohol having the formula R2OH and an epoxide having the formula: Figure imgb0002 where R2 is as previously defined and X is a leaving group. This reaction can also be carried out in the presence of a catalyst as defined above. The catalyst is normally employed at levels of from about 0.1 mol% to about 2.0 mol%, and Preferably, it is carried out in the absence of a solvent at temperatures of from about 40 ° C to about 90 ° C. As already mentioned, surfactants have advantages including superior stain and film formation reduction benefits, as well as excellent excellent film removal performance. greasy dirt, good tableware care performance, good foam suppression performance and good general cleaning. Accordingly, it is an aspect of the present invention to provide a process for producing a low foaming nonionic surfactant that has superior lowering benefits. stain and film formation, as well as good performance of excellent removal of greasy dirt, good tableware performance, good foam suppression performance and good general cleaning. Another aspect of the present invention is to provide a method for ^^^? J? ^^ To produce a polyoxyalkylated alcohol surfactant of ether-blocked ends. These and other aspects, features and advantages will be apparent from the following description and the appended claims. All parts, percentages and ratios used herein are expressed as percent by weight, unless otherwise specified. All the cited documents are incorporated, in a relevant part, in the present as reference.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Again, the present invention is directed to a process for producing a low foaming nonionic surfactant for use in detergent compositions. The novel surfactants of the present invention comprise ether-blocked polyoxyalkylated alcohols having the formula: R 10 [CH 2 CH (R 3) 0] x [CH 2] kCH (OH) [CH 2] jOR 2 wherein R 1 and R 2 are aliphatic hydrocarbon radicals or aromatic, linear or branched, saturated or unsaturated, having from about 1 to about 30 carbon atoms; and R3 is H, or a linear aliphatic hydrocarbon radical having from about 1 to about 4 carbon atoms; x is an integer that has an average value of 1 to approximately 30, where when x is 2 or more, R3 • ¿^ Í2 ^ ¿j¿j ^^ can it be the same or different?, ykyj are integers having an average value of from about 1 to about 12, and more preferably from 1 to about 5, where when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes 5 H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, wherein R2 may be optionally alkoxylated, wherein said alkoxy is selected from ethoxy , propoxy, butyloxy, and mixtures thereof. R1 and R2 are preferably aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having around 6 to about 22 carbon atoms, with more than about 8 to about 18 carbon atoms being preferred. In addition, R2 can be selected from hydrocarbon radicals that are ethoxylated, propoxylated and / or butoxylated. For R3, H or a linear aliphatic hydrocarbon radical having from about 1 to about 2 is more preferable. carbon atoms. Preferably, x is an integer having an average value of from about 1 to about 20, most preferably from about 6 to about 15. As described above when, in the preferred embodiments, and x is greater than 2, R3 may be same or different. That is, R3 can vary between any of the alkylenoxy units as described above. For example, if x is 3, R3 may be selected to form ethyleneoxy (EO) or propyleneoxy (PO), and may vary in order of (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). i-Aáfc, i a,? ** & ... JU ^^, In fact, the integer 3 is chosen only as an example, and the variation can be much larger as a larger integer value for x and include, for example, multiple units (EO) and a very small number of units (PO) . However, when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, where when x is 15 or more, and R3 includes H and from 1 to 3 methyl groups, then at least an R3 is ethyl, propyl or butyl. Particularly preferred surfactants as described above, include those having a low cloud point of less than about 20 ° C. These low-cloud point surfactants can then be used in conjunction with a high-point cloud surfactant as described in detail below for superior fat cleaning benefits. In accordance with the present invention, surfactants are preferred wherein k is 1 and j is 1, so that the surfactants have the formula: R 10 [CH 2 CH (R 3) 0] x CH 2 CH (OH) CH 2 OR 2 wherein R 1, R 2 and R 3 are as defined above, and x is an integer with an average value of from about 1 to about 30, preferably from about 1 to about 20, and even more preferably from about 6 to about 18. Surfactants are preferred in where R1 and R2 vary from about 9 to about 15, R3 is H-forming ethyleneoxy, and x ranges from about 6 to about 15.

Basically, the alcohol teflsioactive agents of the present invention comprise three general components, namely linear or branched alcohol, an alkylene oxide and ends blocked with alkyl ether. The ends blocked with alkyl ether and alcohol function as the liposoluble hydrophobic portion of the molecule, while the alkylene oxide group forms the water-soluble hydrophilic portion of the molecule. It has surprisingly been discovered in accordance with the present invention, that significant improvements in the characteristics of reduction of film formation and formation of spots and, when used in conjunction with high-cloud point surfactants, in the removal of soils greases with respect to conventional surfactants are provided by the polyoxyalkylene alcohol surfactants of ether-blocked ends of the present invention. It has surprisingly been found that the ether-blocked polyoxyalkylene alcohol surfactants of the present invention, in addition to providing superior cleaning benefits, also provide good foam control. This foam control can be clearly seen in the presence of high foaming surfactants, such as amine oxides or in the presence of high foaming soils, such as egg or proteinaceous soils. Generally speaking, the polyoxyalkylene alcohol surfactants of ether-blocked ends of the present -_-_! GjÜ? ^ ^^ i ^^^ ß &J. invention can be produced by reacting an aliphatic alcohol with an epoxide to form an ether, which is reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. The process comprises the first step of providing a glycidyl ether having the formula: wherein R2 is as defined above. Various glycidyl ethers are available from a number of commercial sources including the Aldrich Chemical Company. Alternatively, the glycidyl ether can be formed from the reaction of a linear or branched aromatic or aliphatic alcohol of the formula R2OH, where R2 is as defined above, and an epoxide of the formula: where X in a suitable leaving group. Although a number of leaving groups can be used in the present invention, X is preferably selected from the group consisting of halides including chloride, bromide and iodide, tosylate, mesylate and brosylate, with chloride and bromide being more preferred, and chloride still more preferred. (for example, epichlorohydrin).

The temperature of the linear or branched alcohol and the epoxide are preferably reacted at ratios ranging from about 0.5 equivalents of alcohol to 2.5 equivalents of epoxide with 0.95. equivalents of alcohol per 1.05 equivalents of epoxide, usually under acidic conditions for catalysis purposes. Acids which can be used as a catalyst include mineral acids including, but not limited to, H2SO4 and H3P04, and Lewis acids including, but not limited to, TiCl4, Ti (0'Pr) 4, ZnCl4, SnCl4, AICI3 and BF3 -OEt2. Preferred catalysts include Lewis acids, with SnCl4 and BF3-OE_2 being more preferred. The catalysts are preferably used in amounts of about 0.1 mol% to about 2.0 mol%, more typical of 0.20 mol% to about 1.0 mol%. Although the reaction can be carried out in the presence of a suitable solvent such as benzene, toluene, dichloromethane, tetrahydrofuran, diethyl ether, tert-butyl methyl ether or the like, the reaction is preferably carried out in pure form or in the presence of solvent . Finally, the reaction is carried out at temperatures ranging preferably from about 40 ° C to about 90 ° C, most preferably from about 50 ° C to about 80 ° C. After concluding the reaction, the mixture is treated with a basic material to form the glycidyl ether. The basic material is preferably a strong base such as a hydroxide. Preferred hydroxides include alkali metal hydroxides, with sodium being the typical choice. However, one skilled in the art will recognize that other basic materials may also be used: The basic material is preferably added at levels of from about 0.5 equivalents to about 2.5 equivalents, with 0.95 equivalents being equivalent to 2.0 equivalents. The product, glycidyl ether, can be collected after optional filtration, drying and distillation, according to methods well known in the art. However, it is not necessary to isolate / purify the product especially when symmetrical ethoxylated alcohol is to be formed. To form the surfactant, an ethoxylated alcohol having the formula: wherein R1 and x are as defined above in an amount of from about 0.80 to about 2.0 equivalents, is combined with a catalyst as described above, and heated to a temperature ranging from about 50 ° C to about 95 ° C, and most preferably from about 60 ° C to about 80 ° C. The glycidyl ether is then added to the mixture, and reacted for about 0.5 hour to about 30 hours, and most preferably about 1 hour to about 24 hours. The polyoxyalkylated alcohol surfactant product of ether-blocked ends is then collected by means ? & £££? *? »??? Ma M¡ * ~ * a * .j? to mM common in the art, such as? acyón. If so desired, the surfactant can be further treated by separation, distillation or various other means before use. The surfactants obtained by the process described herein, may contain related impurities, which will not affect the performance. A representative synthesis route is demonstrated by the following diagram and examples.

EXAMPLE 1 Preparation of C12 / .3 alkyl glycidyl ether Neodol® 23 (100.00 g, 0.515 moles, available from Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmoles, available from Aldrich) are combined in a 500 ml three-necked round-bottomed flask adapted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C. HE -SÉKflí 'adds dropwise epichlorohydrin (47. ^ g, 0 * 515 moles, available from Aldrich) to maintain the temperature between 60-65 ° C. After stirring for another hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%), while stirring mechanically. After the addition is complete, the mixture is heated at 90 ° C for 1.5 h, cooled and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO, filtered and concentrated. Distillation of the product mixture at 100-120 ° C (0.1 mm Hg) provides the glycidyl ether as an oil.

EXAMPLE 2 Preparation of alkyl aryl ether of Ca / n Neodol® 91 (100.00 g, 0.632 moles, available from Shell Chemical Co.) and tin (IV) chloride (0.82 g, 3.20 mmol, available from Aldrich) are combined in a 500 ml three-necked flask and bottom round adapted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 65 ° C. HE dropwise added epichlorohydrin (58.46 g, 0.632 moles, available from Aldrich) to maintain the temperature between 60-65 ° C. After stirring for another hour at 60 ° C, the mixture is cooled to room temperature and treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%). After After the addition is complete, the mixture is heated at 90 ° C for 3.0 h, cooled and treated with water to dissolve all white solids. The organic phase is dried over MgSO 4, filtered and concentrated. Distillation of the product mixture at 100 ° C (0.1 mm Hg) provides the glycidyl ether as an oil.

EXAMPLE 3 Preparation of alkyl glycidyl ether of C .2 .4 The procedure of Example 1 is repeated, with the replacement of Neodol® 23 by fatty alcohol of C-? 2..4.

EXAMPLE 4 Preparation of alkyl glycidyl ether of C.4.5 The procedure of Example 1 is repeated, with the replacement of Neodol® 23 by Neodol® 45.

EXAMPLE 5 Preparation of alkyl glycidyl ether of C- / .s The procedure of Example 1 is repeated, with the replacement of Neodol® 23 by Tergitol® 15-S-15. ferW? £ 06 Preparation of alcohol surfactant with etched ends with ethoxylated alkyl ether of C. 2/14-algane of C9 / 11 Neodol® 91-8 (16.60 g, 0.0325 moles, from Shell) is placed Chemical Co.) in a 250 ml three-necked round bottom flask adapted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The contents of the flask are dried under vacuum at 75 ° C for 15 minutes after establishing an argon atmosphere. Tin (IV) chloride (0.25 ml, 2.1 mmol Aldrich) is added to the flask by syringe. The mixture is heated to 60 ° C, at which point glycidyl C 12/4 alkyl glycidyl ether (10.00 g, 0.039 mol) is added dropwise over 15 minutes, while maintaining the temperature at 75 to 80 ° C, after stirring for 18 hours at 60 ° C. The mixture is stirred for another hour at 75 ° C., until the glycidyl ether is consumed, as determined by TLC. The mixture is cooled to room temperature and diluted with 1 ml of water. The solution is passed through 170 g of silica gel (Aldrich, 227196, diameter 7x12), while eluting with dichloromethane-methanol at 5% (40 ml). The filtrate is concentrated by rotary evaporation, and then separated in a Kugeirohr oven (70 ° C, 0.1 mm Hg for 30 minutes) to give the product as an oil.

EXAMPLE 7 Preparation of alcohol surfactant agent of etched ends with ethoxylated alkyl ether of C? 2? 4-alkyl-C .... 5 Tergitol® 15-S-15 (2820.0 g, 3.275 moles, from Union is melted) Carbide) in a 12-L three-necked flask with a round bottom adapted with a condenser, argon inlet, addition funnel, mechanical stirrer and internal thermometer. The contents of the flask are dried at 75 ° C for 30 minutes under vacuum. An argon atmosphere is established. Tin (IV) chloride (25 ml, 0.214 mmol, Aldrich) is added to the flask by syringe. The mixture is heated to 85 ° C. C12 / 4 alkyl glycidyl ether (1679.48 g, 6.549 mol) is added dropwise over 1 hour while maintaining the reaction temperature. After stirring for another 15 minutes at 75 ° C, the reaction is quenched with the addition of water (75 ml). The reaction is diluted with 500 ml of 5% dichloromethane-methanol. The mixture is cooled to room temperature, and then separated in a Kugeirohr oven (70 ° C, 0.1 mm Hg for 30 minutes) to produce the surfactant as an oil. Of the surfactants mentioned above, it is possible to design a cleaning composition, and in particular, a tableware or hard surface cleaning composition. The compositions may optionally include one or more auxiliary detergent materials or other materials to increase or improve cleaning performance, treatment of the i.- "^^ tAgs" substrate that will be washed, or Imile the aesthetics of the detergent composition (for example, perfumes, dyes, stains, etc). The following are illustrative examples of said auxiliary materials. The detersive or auxiliary ingredients optionally included in the compositions herein may include one or more materials to aid or increase the cleaning performance, the treatment of the substrate to be cleaned, or may be designed to improve the aesthetic appearance of the compositions. . Auxiliaries that can be included in the compositions of the present invention, at the conventional levels established by the art to be used, (generally, the auxiliary materials constitute, in total, from about 30% to about 99.9%, preferably from about 70% to about 95% by weight of the compositions) include other active ingredients such as phosphatized and phosphate builders, chelating agents, enzymes, dispersing polymers (eg from BASF Corp. or Rohm &Haas), colored specks , silver care agents, anti-rust and / or anti-corrosion agents, silicates, dyes, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids, pigments and agents for pH control. Depending on whether a greater or lesser degree of compaction is required, filler materials may also be present in The compositions of the invention! These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts of 20% by weight. up to about 70%, preferably from 0% to about 40% of the composition. The preferred filler material is sodium sulfate, especially in suitable grades that have when more low levels of trace impurities. The sodium sulfate used herein is preferably of sufficient purity to ensure that it does not react with the bleach; This can also be treated with low levels of sequestrants, such as phosphonates or EDDS in the form of magnesium salt. It should be noted that the preferences, in terms of sufficient purity to avoid bleach decomposition, also apply to the ingredients of the component to adjust the pH, specifically including any silicate used herein. The compositions of the invention may optionally contain an alkyl phosphate ester foam suppressant, a silicone foam suppressant or combinations thereof. In general, the levels are from 0% to approximately 10%, preferably from approximately 0.001% to approximately 5%. However, Generally preferred compositions (based on cand / or deposition considerations) do not contain foam suppressors, ie they are completely free of foam suppressors, or contain foam suppressants only The low levels, for example, decrease by approximately 0.1% of active foam suppressant, hydrotrope materials such as sodium benzenesulfonate, toluenesulfonate, and so on. sodium, sodium cumenesulfonate, etc., may be present, for example, to more uniformly disperse the surfactant, bleach-stable perfumes (stable as to flavor), and bleach-stable dyes such as those described in U.S. Patent 4,714,562, Roselle et al, issued December 22, 1987 may also be added to the compositions herein in appropriate amounts, since the compositions herein may contain water-sensitive ingredients or ingredients that may be -reaction when placed together in an aqueous medium, it is desired to keep the free moisture content to a minimum, for example 7% or less, preferably 5% or less of the compositions, and to provide the package It is substantially impermeable to water and carbon dioxide. The coating measures have been described herein to illustrate a way to protect the ingredients from each other and from air and moisture. Plastic bottles, including refillable or re-circulatable types, as well as conventional cartons or barrier boxes are other useful means of ensuring maximum shelf-storage stability. As indicated, when the ingredients are not highly compatible, it would also be desirable to coat at least one such low foaming nonionic surfactant to protect it. There are numerous waxy materials that can easily be used to form appropriate coated particles of any of the other incompatible components; however, the formulator prefers those materials that do not have a marked tendency to deposit or to form films on the tableware including those of construction of plastic material. The following non-limiting examples further illustrate the compositions of the present invention. ^^ jg ^ jj ^ j ^ jg EXAMPLE 8 A detergent composition for dishwashing is prepared automatic as follows: Ingredients% by weight AB Sodium tripolyphosphate (STPP) 24.0 45 Sodium carbonate 20.0 13.5 Silicate 2.0r hydrated 15 13.5 Nonionic surfactants1 2.0 2.0 Nonionic surfactant Tergitol 1.0 1.0 15S92 Polymer3 4.0 - Protease (4% active) 0.83 0.83 0.25 Amylase ( 0.8% active) 0.5 0.5 Perborate monohydrate (AvO 15.5% 14.5 14.5 active) 4 Catalyst cobalt5 0.008 - Water, sodium sulfate and several others rest 1 Poly alcohol (oxyalkylated) end blocked with ether of example 6 2Alcohol secondary alcohol supplied by Union Carbide (turbidity point = 60 ° C). 3 Terpolymer selected from either 60% acrylic acid / 20% maleic acid / 20% ethyl acrylate or 70% acrylic acid / 10% maleic acid / 20% ethyl acrylate. 4The AvO level of the previous formula is 2.2%. 5 Pentaaminacetatecobalt nitrate (III).

The ADDs of the foregoing dishwashing detergent composition examples can be used to wash plastic and ceramic stained with lipstick, cups stained with tea, plates soiled with starch and spaghetti, glasses soiled with milk, flat dishes soiled with starch, cheese, egg or baby food, and plastic spatulas stained with tomato, putting the dirty dishes in a domestic appliance for automatic dishwashing and washing using either cold fill washing cycles, maximum peak 60 ° C, or washing cycles between 45-50 ° C uniformly with a product concentration of the example compositions of about 1 , 000 to 10,000 ppm, with excellent results. The following examples further illustrate accumulated phosphate ADD compositions containing a bleach / enzyme particle, but are not intended to be limiting thereof. All the percentages indicated are by weight of the finished compositions, unlike the perborate component (monohydrate), which is listed as AvO. __-_, ._-.,, .. J ^ * »- - ^^^ a ^ _ EXAMPLES 9 - 10 9 10 Catalyst1 0.008 0.004 Savinase ™ 12T - 1.1 Protease D 0.9 ~ Duramyl ™ 1.5 0.75 STPP 31.0 30.0 Na2CO3 20.0 30.5 Polymer2 4.0 ~ Perborate (AvO) 2.2 0.7 Dibenzoyl peroxide 0.2 0.15 Silicate 2 R (SiO2) 8.0 3.5 10 Paraffin 0.5 0.5 Benzotriazole 0.3 0.15 Ag. Non-ionic surfactant 1.0 1.0 Sodium sulphate, moisture the rest the rest 1 pentaamine acetate ethobamate (lll); it can be replaced by MnTACN. 2 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers. 3 A nonionic surfactant prepared according to Example 6.

In the compositions of Examples 9 and 10, respectively, the catalyst and the enzymes are introduced into the compositions as particles of mixed material of 200-2400 microns which are prepared by spraying operations, fluidized bed granulation, forming discs, pills or flake / grinding. If desired, the protease and amylase enzymes can be formed separately in their particles of mixed catalyst material / respective enzymes, for reasons of & s_8s ___ M ^ s M? * * * stability, and these separate mixed materials are added to the compositions EXAMPLES 11 AND 12 Granulated dishwashing detergents are like follow: H 12 Mixed material particle 1.5 0.75 10 Savinase ™ 12T 2.2 ~ Protease D - 0.45 STPP 34.5 30.0 Na2CO3 20.0 30.5 Acusol 480N 4.0 - Perborate (AvO) 2.2 0.7 Silicate 2R (SiO2) 8.0 3.5 Paraffin - 0.5 15 Benzotriazole - 0.15 Surfactant nonionic1 1.0 1.0 LF4042 1.0 0.75 Sodium sulfate, moisture the remainder residue 1 Prepared according to example 6. 2A mixture of ethoxylated / propoxylated nonionic surfactants available from BASF.

EXAMPLE 13 The formulas for light duty liquid dishwashing detergents are prepared as follows: Composition Ingredient ABC% by weight Surfactant1 1.00 2.00 1.50 AES 32.00 33.00 29.00 Surfactant 5.00 4.50 6.00 amine oxide Surfactant 3.00 5.00 1.75 betaine Perfume 0.18 0.18 0.18 Water and minors remainder remainder remainder 1 Prepared in accordance with example 6 EXAMPLE 14 A detergent tablet is prepared for automatic washing of crockery from the composition as follows: Ingredients% by weight AB Sodium tripolyphosphate (STPP) 50.0 47.0 Sodium carbonate 14.0 15 Hydrated 2-hydrated resin 8.0 5.0 Non-ionic surfactant1 0.4 2.0 Non-ionic surfactant 10 1.0 1.0 Tergitol 15S92 Polymer3 4.0 - Protease (4% active) 2.0 1.50 Amylase (0.8% active) ~ 0.5 Perborate monohydrate (AvO 1.5 1.5 15.5% active) 4 Catalyst cobalt5 0.008 - 15 TAED - 2.2 Benzotriazole 0.3 ~ Paraffin oil 6 0.5 ~ Water, sodium sulfate, and several others rest 1 Poly (oxyalkylated) alcohol end blocked with ether of example 6. 2 Ethoxylated secondary alcohol supplied by Union Carbide (turbidity point = 60 ° C). 3 Polyacrylate polymer mixed with HEDP. 4The AvO level of the previous formula is 2.2%. 5 Pentaaminacetatocobalt Nitrate (III). 6Winog 70 available from Wintershall, Salzbergen, Germany.

»*** - • - JW" ** ^ - The ADDs of the examples of the above detergent dishwashing composition can be used to wash plastic and ceramic materials stained with lipstick, cups stained with tea, dishes stained with starch and spaghetti, glasses soiled with milk, flat plates soiled with starch, cheese, egg or baby food, and plastic spatulas stained with tomato, introducing the dirty dishes in a domestic washing machine to wash dishes and washing using washing cycles and either with cold filling, 60 ° C peak, or 45-50 ° C uniformly with a product concentration of the example compositions of about 1,000 to 10,000 ppm with excellent results.

EXAMPLE 15 Illustrates a hard surface cleaning composition of the present invention as follows: % by weight Ingredients 18 19 20 21 22 23 Surfactant1 0.25 3.5 5.5 6.5 6.1 9.5 Sodium hypochlorite 0.9 1.4 1.4 0.5 Calcium Hypochlorite sodium dichlorocyanurate - tetrapotassium pyrophosphate 1.2 2.0 6.0 ~ 13.0 - Thppotassium Phosphate 2.0 - 12.0 - Sodium Tripolyphosphate 1.6 - ~ Calcium Carbonate - 39.0 1.1 Calcium Oxide - 2.8 - Perlite-based Abrasive 6.5 ~ 22.5 0.5 Sodium Hydroxide 0.8 1.6 1.8 0.8 1.1 1.0 Potassium hydroxide 0.85 - ~ Dyes 0.75 0.28 0.28 0.28 Lanolin 2.1 Carboxymethylcellulose 2.6 Water / several the rest the rest the rest the rest the rest the rest 1 poly (oxyalkylated) alcohol of end blocked with ether of example 6.

Bátsa -__ ii -__ i i &j = jiil aí um EXAMPLE 16 The liquid dishwashing liquid dishwashing detergent compositions according to the present invention are prepared as follows: Detergent builder based on STPP 17.5 16 Potassium carbonate 8 - Sodium carbonate ~ 1.5 Potassium hydroxide 2 2.0 Potassium silicate 4 1.5 Sodium silicate 2 3 Thickener 1 1 Nitric acid 0.02 0.02 Aluminum tristearate 0.1 ~ Polymer dispersant2 0.5 - Sodium benzoate 0.8 0.5 Surfactant 1.0 1.0 2.0 Perborate 2.2 Sodium hypochlorite 1.5 ~ Water and less rest the rest Poly (oxyalkylated) alcohol end blocked with ether of Example 6. Sodium polyacrylate of molecular weight 4,500.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for preparing a poly (oxyalkylated) alcohol surfactant of ends blocked with ether having the formula: R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2 wherein R 1 and R 2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer having an average value of 6 to 15, where when x is 2 or more, R3 may be identical or different; wherein in addition when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, wherein when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then at least one R3 is ethyl, propyl or butyl, and wherein R2 can also be optionally alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy, and mixtures thereof; said method comprises the steps of: (a) providing a glycidyl ether having the formula: wherein R2 is as described above; (b) provide an ethoxylated alcohol having the formula: where R1, R3 and x are as previously defined; and (c) reacting the glycidyl ether with the ethoxylated alcohol to form said surfactant.

2. The process according to claim 1, further characterized in that said step of providing said glycidyl ether also comprises the step of reacting an aliphatic or aromatic alcohol, linear or branched, having the formula R2OH and an epoxide having the formula: where R2 is as previously defined and X is a leaving group.

3. The method according to claim 2, further characterized in that said step of reacting a linear alcohol with an epoxide is carried out in the absence of a solvent.

4. The process according to any of claims 1 to 3, wherein R1 and R2 are aliphatic hydrocarbon radical, linear or branched, saturated or unsaturated, having from 6 to 22 carbon atoms.

5. The process according to any of claims 1 to 4, wherein x is an integer having an average value of about 6 to 15.

6. The method according to any of claims 1 to 5, further characterized in that said step of reacting glycidyl ether with ethoxylated alcohol is carried out in the presence of a catalyst.

7. The process according to any of claims 1 to 6, further characterized in that said catalyst is selected from the group consisting of mineral acids, Lewis acids and mixtures thereof.

8. The process according to any of claims 1 to 7, further characterized in that said catalyst is a Lewis acid selected from the group consisting of TiCl, Ti (O'Pr) 4, ZnCI, SnCl4, AICI3, BF3- OEt2 and mixtures thereof.

9. The process according to claim 8, further characterized in that said catalyst is SnCl.

10. The process according to any of claims 1 to 9, further characterized in that said step of reacting glycidyl ether with ethoxylated alcohol is carried out at a temperature of about 50 ° C to 95 ° C. | j ^^ Ü &S: ___- 9 £ __ £ _ i2f_ ^ y & is aMH_fl _ ^ __________ ^ B__l __ ^ H __ ^ r- SUMMARY OF THE INVENTION A process for preparing an ether-blocked poly (oxyalkylated alcohol) surfactant is provided; the alcohol has the formula: R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2, wherein R 1 and R 2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 6 to 15, where when x is 2 or 10 more, R3 may be identical or different; and also where when x is 15 or more and R3 is H and methyl, at least four of R3 are methyl, where in addition when x is 15 or more and R3 includes H and from 1 to 3 methyl groups, then less one R3 is ethyl, propyl or butyl, and wherein R2 may also optionally be alkoxylated, wherein said alkoxy is selected from Etoxy, propoxy, butyloxy, and mixtures thereof; said method comprises the steps of: (a) providing a glycidyl ether having the formula (I) 20 wherein R2 is as described above; (b) providing an ethoxylated alcohol having the formula (II) ___M »_a ^ ..-- 2_» á ____- B £ _ £ B_ £ ___. ~ ^ ^ ». - - _ ^ .. ^^ _? S & __ ^^ s ^ a ^ M sapfae ^ where R2 it is as described above; (b) providing an ethoxylated alcohol having the formula (II) where R1, R3 and x are as previously defined; and (c) reacting the glycidyl ether with the ethoxylated alcohol to form the surfactant. P00 / 127F