MXPA97009529A - Process for preparing amidas in n-alkyl polyhydroxylamilic ami - Google Patents

Abstract

The N-alkyl polyhydroxyalkyl amines are reacted, for example N-methyl glucamine having a Color Gardner of less than 1, with sources of fatty acyl groups such as methyl esters, anhydrides and / or fatty acids, which have more than 98% trasnmittance. at 560 nm in hydroxiorganic solvents, such as methanol, to prepare N-alkyl polyhydroxy amines of good color. The N-alkyl polyhydroxy amines can be purified by crystallization and / or subjected to reductive bleaching to provide a better color. The preferred reaction is carried out at low temperature for short periods of time and with low levels of catalyst in order to decrease the formation of cyclic products. The resulting amide products can be further purified by the treatment of anionic and cation exchange resins to remove soap and amine impurities. The anionic ion exchange resin can be easily regenerated by acidifying it after washing with an organic solvent.

Description

PROCESS FOR PREPARING N-AQUIL AMIDAS POLYHIDROXIALQÜILAMIHAS FIELD OF THE INVENTION The present invention relates to an improved process for preparing amides of N-alkyl polyhydroxyalkylamines, especially those having good color and low levels of unwanted by-products.

BACKGROUND OF THE INVENTION The manufacture of N-alkyl polyhydroxyalkylamines (N-alkyl polyhydroxy amines), such as N-methylglucamine and the fatty acid amides thereof, has been known for many years and these materials are commercially available. Recently, there has been occasion to employ N-alkyl polyhydroxy amines, for example, in reaction with, for example, fatty acid esters to prepare detergent surfactants for polyhydroxy fatty acid esters which are employed in cleaning products. It has been determined that care must be taken in preparing the N-alkyl polyhydroxyamines and the amides to provide amides with a better color. The present invention allows access to high polyhydroxy fatty acid amide surfactants.

P548 quality. The present invention provides means for preparing N-alkyl polyhydroxyamine amides in high yields which are almost as clear as water, in particular N-methylglucamine amides and, more specifically, N-methylglucamine amides containing low levels of cyclic materials, such as It is exposed below.

PREVIOUS TECHNIQUE Reductive glucose amination processes are disclosed in U.S. Patent No. 2,016,962, Flint et al., Issued October 8, 1935. U.S. Patent No. 1,985,424, to Piggott, issued on December 25, 1934, he discloses the manufacture of "textile adjuvants" by reacting (a) the heating product of glucose and aqueous methylamine in the presence of hydrogen and a hydrogenation catalyst under pressure with (b) an organic carboxylic acid as per example stearic acid or oleic acid.

The condensation product prepared at about 160 ° C is said to be "predominantly, if not exclusively, an amide" and is determined from the formula R-CO-NRX-CH2- (CHOH) 4-CH2OH, wherein R is an alkyl radical containing at least 3 carbon atoms, while R ^ is hydrogen or an alkyl radical. U.S. Patent No. 2,016,962, P548 granted on October 8, 1935, exposes a process to prepare glucamines and related products. U.S. Patent No. 2,703,798, Sch. Artz, issued March 8, 1955, states that the compositions produced by reacting fatty acids or acid anhydrides with N-alkylglucamines (apparently as in the process shown by Piggott) have poor detergency properties and poor color. In this way, Schwartz shows problems associated with the formation of condensation products of N-monoalkylglucamines and fatty acids, with regard to detergent properties and undesirable color characteristics. According to Schwartz, approximately equimolar proportions of N-monoalkylglucamines can be reacted with fatty alkyl esters, by heating to 140 ° C-230 ° C, preferably 160 ° C-180 ° C, at normal, reduced or superatmospheric pressure, by a period "a little over an hour", during which time two initially immiscible phases combine to form a product that is said to be a useful detergent. Suitable N-monoalkylglucamines are illustrated by N-methylglucamine, N-ethylglucamine, N-isopropylglucamine and N-butylglucamine. Suitable fatty alkyl esters are illustrated by the reaction product of a C5-C30 fatty acid with an aliphatic alcohol, for example laurel acid methyl ester. The most recent processes include those described in United States Patent NO. 5,334,764, Schiebel, Connor, Shumate, and St. Laurent; 5,338,486, Connor, Scheibel, and Kao; 5,338,487, Connor, Scheibel, and Kao; and 5, 380, 892, Connor, Scheibel, and Kao, all incorporated herein by reference. According to Thomas Hedley &; Co. Ltd. (nowadays Procter &Gamble Ltd.), British Patent No. 809,060 published February 18, 1959, the compounds made by the process herein are useful as surfactants for laundry detergents, such as those having a granular shape. Hildreth (supra) mentions the use of compounds present in the field of biochemistry as detergent agents for the solubilization of plasma membranes and EP-A 285,768, published on December 10, 1988 describes the application of these compounds as a thickener In this way, these compounds or compositions containing them can highly desired surfactants. Yet another process for making the compositions comprising the amide compounds of this invention is included in the aforementioned discussion of improved thickeners. Refer to EP-A 285,768. Also refer to H. Kelkenberg, Tenside Surfactants Detergents 25 (1988) 8-13, among others for the additional exposure of processes for the preparation of N-alkylglucamines. All patents and prior publications are incorporated herein by reference.

SUMMARY OF THE INVENTION The present disclosure relates to a series of improvements that relate to processes for the preparation of amides of N-alkyl polyhydroxylamines (N-alkylamino polyols). The N-alkyl polyhydroxyamines and the source of fatty acyl groups, for example esters, which are used to form the amides, are selected to have good color, the reaction conditions are selected to avoid the formation of color materials and the precursors for colored materials; and / or the amide product is treated with an ion exchange resin, mixtures of ion exchange resins, or combinations thereof, and / or a reducing "bleach" to prepare the best color amides. The combination of all improvements is required in order to achieve amides with the optimum color for the formulation of detergent compositions, especially liquid compositions which are "clear as water" and which contain low levels of cyclic materials. The invention provides a process for preparing polyhydroxy fatty acid amide surfactants, which comprises reacting a member selected from the group consisting of fatty acids, fatty acid anhydrides and fatty acid esters, especially fatty acid esters, which have more 98% transmittance at 460nm with an N-alkylamino polyol having a Color Gardner of less than 1 (<0.1 absorbance at 440nm), for example triglyceride methyl esters. The crystallization of N-alkylamino polyol can be used to provide adequate purity and color. The N-alkylamino polyol with this Color Gardner is "stable" for three hours at 130 ° C. The N-alkylamino polyol is considered stable if it has a Gardner Color of 4 or less, after three hours under these reaction conditions. A less pure N-alkylamino polyol will be dark brown after three hours under these conditions. Also, in order to prepare the optimum color amides, the dehydration of the N-alkylamino polyol should be carried out at a temperature of between about 110 ° C and 160 ° C for a period of less than about three hours, more preferably at a temperature between about 120 ° C and 140 ° C for a period of less than about one half hour, and more preferably at a temperature between about 130 ° C and about 135 ° C, for a shorter period of time to about an hour. Without However, for commercial practice, good results can be obtained with dehydration times of between approximately four and eight hours, preferably between approximately five and six hours, to conform to the limits of commercial equipment. A purest N-alkylamino polyol can be achieved with crystallization from the aqueous solution, either with or without an organic solvent present. The dehydrated N-alkylamino polyol is then reacted with, for example, fatty acid esters and especially triglycerides, to form polyhydroxy fatty acid surfactants. The polyhydroxy fatty acid surfactants are subsequently treated with an ion exchange resin, a mixture of ion exchange resins or combinations of ion exchange resins and / or bleach reducing agents such as NaBH 4, etc., or for example hydrogenation in a catalyst, as shown below and, optionally, combinations of various treatments. A particularly effective subsequent treatment is the hydrogenation of a solution of the polyhydroxy fatty acid surfactant on a hydrogenation catalyst such as nickel, palladium, copper chromite, etc. In a preferred process, the fatty acid ester is a methyl ester of alkyl or alkenyl fatty acid C? Or? 18 a triglyceride, and the N-alkylamino polyol is selected from N-methyl glucamine, N-methyl fructamine, N-methyl maltamine and N-methyl glycerol amine.

DETAILED DESCRIPTION OF THE INVENTION The processes of the invention employ selected reagents, N-alkylamino polyols and sources of fatty acyl groups with good color, especially with colors that are stable at temperature. The "color" referred to herein is Color Gardner, for example N-alkylamino polyol, N-alkylamino amide of fatty acid, etc. "The Gardner Color" is the standard Gardner measurement known in this field. A Color Gardner reading close to zero (solution) represents a practically colorless solution ("transparent as water"). Gardner Colors that are below 1 are required for the N-alkylamino polyol reagents and it is preferred that they have Gardner Colors close to 0. The Gardner Color is determined by A.O.C.S. (American Oil Chemists Society) Official Method number la-64, entitled COLOR Gardner 1963 (Standards for Glass) established in 1978 and revised in 1982. Equipment and standards for determining Color Gardner can be purchased from Delta Scientific, Box 5728, Long Island, New York 20014, or Gardner Laboratory, Silver Spring, Maryland, USA In the sense used here, Color Gardner limits typically refer to the color that results from the color bodies that are present, or that are the result of the reactions described, and not to the deliberately added color materials. The odor characteristics of the N-alkylamino polyol reagent and its amide are essentially free of amine or "fishy" odor (once any excess N-alkylamine is removed) and also essentially free of the typical caramelization odors of sugar.

The N-alkylamino polyols. Suitable N-alkylamino polyols can be prepared by processes similar to those described in copending United States Patent Application Serial No. 07 / 907,382, filed July 8, 1992, in the name of Junan Kao et al. FOR PROCESS FOR PREPARING N-ALKYLAMINES IN AQUEOUS SOLVENTS / HYDROXY, the application is incorporated herein by reference, especially page 6, line 14, page 23, line 3 and EXAMPLES I to VI and IX to XIV. The polyhydroxyamine used to form the polyhydroxy acid amide can be made by any process that will provide the desired color. As discussed below, N-alkylamino polyols with good color are achieved by careful selection of reaction conditions. The reaction for the preparation of N-alkylamino polyols (also referred to herein as "polyhydroxyamines" or "N-alkyl polyhydroxy amine") can be determined by the reaction "R1" and illustrated by the formation of N-methylglucamine , where R * is methyl.

Adduct processes. In the first variation of reaction R-1, the process involves pre-reacting the amine with the reducing sugar to form an adduct. water and / or organic solvent, for example methanol R1NH2 + glucose? Adduct + H2O The adduct has the following formula (I): _0_ RiNH - CH - (CH0H) 3 - CH - CH20H Catalyst Adduct + H2 R1NHCH2 (CHOH) CH2OH The reactants, solvents and catalysts used in the R-1 reaction are all good materials Known PS48, although normally not used in the purified form for the manufacture of detergent surfactants, and are available, at least in some forms, from a variety of commercial sources. The following are non-limiting examples of the materials that may be used herein. Aminating Material - The "N-alkylamines" used to form the N-alkylamino polyols include primary amines of the formula R ^ NH2, where R ^ is, for example, alkyl, for example C ^ -C ^ s, especially I rent C1-C4, or the corresponding hydroxyalkyls, for example hydroxyalkyl C1-C4. Examples include methyl, ethyl, propyl, hydroxyethyl and the like. Non-limiting examples of the amines useful herein include methylamine, ethylamine, propylamine, butylamine, 2-hydroxypropylamine, 2-hydroxymethylpropyl, 2-hydroxyethylamine; 1-methoxypropyl and methylamine. C1-C3 alkylamines are preferred and more preferred is N-methylamine. All these amines together are called "N-alkylamines". The amine may be either anhydrous or dissolved in solvent, for example an aqueous solvent, in a concentration of between about 30% and about 90%, preferably between about 40% and about 70%. Material Polyhydroxy - A preferred source of PS48 polyhydroxy materials useful in all reactions R-l comprise reducing sugars or reducing sugar derivatives. By "sugars" is meant present reducing sugars such as glucose, fructose, mannose, lactose, maltose, xylose and the like. The term "sugars" that is used herein also includes glyceraldehyde. These "sugars" can include materials that break down to form sugars, such as plant syrups, such as sugar cane syrup, corn syrup, sugar syrups derived from potato starch, sugars derived from sugar pulp, Hydrolyzed wood and similar. Syrups with high fructose content, high glucose content and high maltose content are economical and are preferred, especially if your Color Gardner is satisfactory. The reactive sugar material comprises, for this first variation, an adduct with the amine such as for example methylamine. The species are determined (measured) by the g.c. (gas-liquid chromatography, or "g.l.c.") using the Hewlett-Packard 5890 Series 2 equipment in column injection using DBL of 15 meters, film thickness 0.25 m, ID 250 m. A particular advantage of the "adduct" process is that the "adduct" can be formed in the presence of water. Consequently, raw materials such as corn syrup and the like can be used as the source of P548 sugar. However, the sugar solution can be prepared from granulated sugar, powder, etc., by dissolving the sugar in the solvent, preferably the aqueous solvent. The sugar concentrations in the solvent, for example water, are usually around 40% and 90%, preferably between about 50% and 70% (Normally, 71% is the upper limit). It is of paramount importance that the color of the starting sugar material for preparing all N-alkylamino polyols be less than about one on a Gardner Color scale, preferably less than about 0+, and more preferably almost as light as water. . Typical color materials that are present in the starting sugar materials negatively accept the catalyst and the reaction yield. These colored materials all contribute to the eventual color of the N-alkylamino polyols. These colors can be removed, if present, by procedures such as "carbon bleaching" where the colored materials are adsorbed. The sugar material is preferably handled without excessive heating and / or under non-oxidizing conditions to prevent degradation. Of course, the use of sugars that have low Gardner colors (for example 0 or <1, ie clear syrups such as water) to form the N-alkylamino P548 polyols will help ensure that N-alkylamino polyols having desirably low Gardner Colors are produced. Put another way, the use of Color Gardner sugars low (0 to 1) (preferably white solids or clear solutions such as water) and the use of the reaction sequence disclosed herein results in N-alkylamino polyols of Color Gardner low. Catalysts - A variety of hydrogenation catalysts can be employed in the reaction R-1. Included among these catalysts are nickel (preferably when treated as discussed below), platinum, palladium, iron, cobalt, tungsten, various hydrogenation alloys, and the like. The catalyst used in the hydrogenation step is preferably a particulate nickel catalyst, Raney nickel, nickel, other nickel catalysts attached to the substrate materials such as for example silica or alumina. Catalysts that can be removed more easily (for example by filtration) are preferred. Most preferred catalysts herein include "United Catalyst G49B", "United Catalyst G96", and "UCI C46" which are nickel catalysts in silica-supported particles, which are obtained from United Catalysts, Inc., Louisville, Kentucky, and the WR Raney type catalysts Grace & Co. , from Baltimore, Maryland, as for example P548 RA4200 and RA3100. Achieving good color also requires the optimization and maintenance of the activity of the preferred nickel catalysts, including any of the conventional nickel Raney catalysts or "supported" nickel well known in the art. The conventional nickel in the brand RANEY NICKEL 4200 and 3200 (Grace Chemicals) is quite suitable for use in the present. The UCI (United Catalyst, Inc.) G-96B and G-49B and G-49C are also suitable. Regarding the nickel catalyst, it is believed that removing nickel oxides from the catalyst prevents or prevents the dissolution of the nickel ions within the reaction medium and thus results in the formation of reaction products having a desirable content. low nickel. In addition, it has been found that the pre-treated nickel catalyst and preferably the post-treated with pressurized hydrogen can be reused in many subsequent reactions, thus yielding substantial overall cost savings. In general, nickel catalysts, such as those that are commercially available, are typically contaminated with, for example, nickel oxides, organic materials, excess caustic compounds and / or fine particles of alumina, especially after shipping and storage. The nickel catalysts that are used in the process P548 of the present are preferably free from amounts inhibiting the catalytic activity of nickel oxides, organic materials, caustic materials, and fine alumina powders, etc. Therefore, it is desired to wash the catalyst with one or more solvents to remove the organic compounds and / or water-soluble materials, preferably at a lower pH and / or treat the catalyst with a strong reducing agent, for example low hydrogen gas. high pressure and / or high temperature, in order to destroy or remove the nickel oxides. Once the catalyst is "cleaned", the catalyst is desirably maintained under a non-reactive atmosphere, for example, of nitrogen gas or more desirably, of a reducing gas, for example hydrogen. Any exposure to the normal atmosphere should occur desirably for short periods of time and while the temperature is low. The activity of the catalyst can be substantially increased by the reduction or removal of these impurities, even when they are present in very small amounts. The resulting catalyst also provides amines and, therefore, amides with a good color. When the nickel catalyst is in contact with either the adduct or N-alkyl polyhydroxyalkylamine, the hydrogen pressure must be maintained to decrease the solubilization of the catalyst. Similarly, a high hydrogen pressure, for example, between P548 about 100 psig at about 3500 psig, preferably about 500 psig to about 1500 psig, and a temperature between about 20 ° C to about 135 ° C, preferably between about 40 ° C to 85 ° C, will reduce the level of the nickel ion dissolved in the N-alkyl polyhydroxyalkylamine and, by depositing the nickel again on the catalyst, regenerates its activity. A combination of hydrogen gas and selected pressure / temperature conditions can reduce this solubilization and, in fact, reverse the process to deposit the nickel and regenerate the catalyst. The decrease of the soluble Ni content in the N-alkyl polyhydroxyamine product to less than about 10 ppm, preferably less than about 5 ppm, more preferably less than about 2 ppm, effectively regenerated the catalyst. When the catalyst is separated from the N-alkyl polyhydroxyalkylamine, the temperature should be less than about 135 ° C, preferably less than about 85 ° C, and the separation, typically filtration, must be achieved under hydrogen pressure. Regeneration of the catalyst can be achieved using the step described for the initial activation. The N-alkylamino polyol reagent of the P548 present, which is "substantially nickel free" contains no more than about 20 parts per million (ppm) of nickel, and preferably less than about 5 ppm of nickel (Ni ++). Nickel can be conveniently measured by conventional atomic absorption spectroscopy using diluted samples (5/1 dilution to reduce interference). Solvent - The formation of the adduct in the process R-1 is conveniently carried out in water and / or an organic solvent, especially polar, and more preferably hydroxy solvents. Typical examples of organic solvents useful herein in forming the amine-sugar adduct include methanol (which is preferred, ethanol, 1-propanol, isopropanol, butanols, ethylene glycol, 1,2-propylene glycol (preferred), 1,3-propylene glycol, glycerol and the like The amine itself can also function as a solvent, typically at molar ratios of amine: sugar of between about 4: 1 to about 30: 1. The hydrogenation reaction of the reaction Rl it can also be carried out in the presence of an organic or aqueous solvent which dissolves the adduct.The hydrogenation solvents are conveniently polar solvents, especially hydroxy, ie of the same type as those mentioned above which are used in the formation of the P548 adduct. When substantially anhydrous organic solvents are used, the unreacted amine is removed with the water after the step of forming the adduct. However, when an aqueous solvent is used, the amine and the solvent are not removed until the catalyst removal stage. Water is the preferred solvent for the hydrogenation reaction. Methanol is a preferred organic solvent that is used in the hydrogenation reaction. General Conditions of the Reaction R-1 - The reaction conditions for the reaction R-1 are as follows. Step (a) - Adduct Formation - The step (a) of the preference process is carried out at a temperature between about 0 ° C and 80 ° C, preferably between about 10 ° C and 60 ° C, for processes using organic hydroxy solvent and below about 70 ° C, preferably less than about 50 ° C more preferably less than about 30 ° C, more preferably about 15 ° C to 25 ° C, for aqueous solvents. The reaction time that is used for the adduct formation will typically be in the range of a few minutes to about 20 hours, depending to some extent on the reaction temperature that is selected and / or on the ratio of the amine to the sugar.

P548 In general, for the organic solvent, lower reaction temperatures in the range of 0 ° C to 80 ° C require longer reaction times and vice versa. In general, for the organic solvent, in a preferred reaction temperature range of 10 ° C to 60 ° C, good yields of the adduct are obtained, for example, more than 90%, preferably more than about 95%, achieves in 1 to 10 hours for the organic solvent. For a lower reaction temperature range, from 0 to 70 ° C, preferably from 0 to 30 ° C, which produces a good color, especially in water, the reaction time can also be up to 10 hours, but usually the Balancing is practically achieved within approximately 4 hours or less, especially with higher proportions of amine: sugar. The temperature and reaction time are selected to provide an adduct with a Color Gardner preferably less than about 1. The good color of the adduct is necessary to obtain good reactions and colors in any subsequent hydrogenation reaction and maintain the activity of the catalyst. Below a Gardner Color of about 1, the resulting N-alkyl polyhydroxyamine and, consequently, the resulting amide, have good color. The colored bodies can be removed, for example, by bleaching with charcoal, as used for the sugar solution.

P548 The adduct also has a very low glucose level. The glucose level, as a percentage of the adduct, is preferably less than about 1%, and more preferably less than about .5%. The glucose interferes with the hydrogenation reaction step to form N-alkyl polyhydroxyamine. The excess amine may also help reduce the glucose level and decrease the formation of sorbitol during hydrogenation. In general, the temperature will rise during the formation of the adduct since the reaction is exothermic. Therefore, keeping temperatures below about 30 ° C, as required in batch processes, involves providing cooling of the reactants and / or the reaction mixture. Temperatures above about 50 ° C require reaction times of less than about 10 minutes to avoid excessive color formation. These short times are usually not feasible except in a continuous reaction. Even with that continuous reaction, the backmixing must be decreased, for example, by the use of piston-type expenditure conditions, to avoid excessive exposure of the adduct at higher temperatures. Ideally, the adduct is reacted rapidly with hydrogen to form the corresponding N-alkyl polyhydroxyamine to decrease PS48 degradation. However, temperatures less than about 30 ° C, preferably less than about 20 ° C, allow the adduct to be handled and / or stored for at least several hours, which facilitates the use of the batch process. At 0 ° C, the adduct is stable for 24 hours. The surface temperatures, for example, when the preheating of the adduct for the hydrogen reaction process is carried out, should be kept below 100 ° C, preferably below about 70 ° C. Reagent concentrations may vary. Molar proportions of amine sugar not greater than about 7: 1 are preferably used, although proportions of up to about 30: 1 can be used when the amine is used as a solvent, at least in part. Generally, the desired adduct formation is achieved at a molar ratio of amine: sugar with an excess of amine, eg molar proportions of > 1: 1, preferably greater than about 1.1: 1, and the like, for example, greater than about 1.3: 1. Typical reagent concentrations in the water and / or hydroxy solvent are between 10 to 80%, typically between 40 and 50% (by weight). The adduct formation can be carried out at atmospheric or super atmospheric pressures.

P548 Step (b) Reaction with Hydrogen - Step (b) must be achieved in order to avoid prolonged exposure of the adduct to the catalyst when the hydrogen pressure is less than about 500 psig, and preferably when the hydrogen pressure must be at least about 1000, and more preferably at least about 1500 psig. Keeping this time below about one hour, and preferably less than about half an hour, decreases the amount of the catalyst metal, for example, nickel, which is converted to the water soluble ion. These ions are undesirable for several reasons, including their involvement in color formation, incompatibility with other materials, safety, etc. Step (b) can be carried out in either a pulp or a fixed bed process. Step (b) is preferably carried out at a temperature between about 20 ° C to about 120 ° C, preferably between about 50 ° C to about 100 ° C for organic hydroxy solvent processes. Step (b) preferably it is carried out in two stages for the aqueous solvent processes. The first stage is carried out at a temperature that is sufficiently low to prevent the formation of the corresponding reduced sugar, for example sorbitol in the case of glucose and other P548 unwanted byproducts. Typically, this is carried out between about 20 ° C to 70 ° C, more preferably between about 40 ° C and 65 ° C, and still more preferably between about 50 ° C and 60 ° C. In the second step, after the reduction (hydrogenation) of the adduct to give the N-alkyl polyhydroxyamine has been completed by about 80%, preferably at least about 90%, and more preferably at least about 95 %, the temperature rises to at least about 75 ° C, preferably at least about 80 ° C, and up to about 135 ° C, preferably 130 ° C, so that the remaining adduct and any other material that can forming color bodies are present in a minimum concentration and the adduct has become at least about 95%, preferably at least about 98% and more preferably at least 99.9% at the corresponding N-alkyl amino polyol. This second step is essential for the preparation of N-alkyl polyhydroxyamine with a good stable color during heating. The thermal stability is improved for the N-alkylamino polyol using excess amine in the preparation step and a higher temperature in the heat treatment step. During Stage (b) it is greatly preferred P548 avoid localized overheating, for example, on the surfaces of the heating element or the heat exchanger. These surface or "film" temperatures should be below about 180 ° C, preferably below about 100 ° C, and even more preferably be less than about 70 ° C, during the first stage and less than approximately 100 ° C during the second stage. The reaction with hydrogen is preferably carried out with limited initial water when the solvent is an organic hydroxy solvent, although even in those cases the water (for example up to 1: 1 by weight H2O: alcohol) may be present. Optional removal of water from the adduct prepared in Step (a) can be effected by the use of drying agents or by simply removing water and solvent from the adduct, and then redissolving the adduct in fresh solvent free of water. The hydrogen reaction can typically be carried out as, for example, at temperatures of 20 ° C-120 ° C to 50-1,000 psi, or for example at 50 ° C-90 ° C at 100-500 psi for periods of 0.1 to 35 hours, in general from 0.5 to 8 hours, typically between 1 to 3 hours when the organic solvent is used. When the solvent comprises water, the hydrogenation reaction is carried out in two stages as discussed above.

P548 The adduct / solvent solution used in the hydrogen reaction is typically 10-80%, typically 40 to 50%, (by weight) solute level. It will be appreciated that the selection of the hydrogen reaction conditions will depend to some extent on the type of pressure equipment available to the formulator, so that the aforementioned reaction conditions may vary without departing from this invention. However, as already mentioned, the hydrogen pressure should preferably be between about 500, preferably 1000, more preferably about 1500 psig when the adduct and the catalyst, especially the preferred nickel catalyst, are both present. The use of low pressures less than about 100 psig will require either a separate step to remove the Ni ion, or a more prolonged after-treatment, as discussed below, to achieve a very low Ni content. The levels of the hydrogen reaction catalyst typically range from about 1% to about 100%, preferably between about 2% (preferably about 5%) and about 30% (preferably 20%), more preferably between about 5%. % (preferably 10%) up to about 15% (preferably about 20%) of P548 solids by weight, calculated based on the weight of the catalyst: weight of the reducing sugar substituent. Step (c) Finishing. - The catalyst is then separated from the product after the reaction is complete. The catalyst is removed from the product of Step (c) that after preference it is dried by crystallization or by purification of the solvent / water or by means of effective drying agents. This helps avoid the inversion of the sugar starting material. Step (c), when it involves solvent / water purification, is preferably carried out in a continuous film evaporator. Steps (a) - (c) of the process R-1 are preferably carried out under non-oxidizing conditions (for example H2 or inert gas) to provide a good color. The removal of the catalyst in Step (c) of the process is preferably carried out under hydrogen pressure to prevent Ni (catalyst) dissolution or at least under inert conditions.

Process of Addition of Glucose. Another suitable process for preparing polyhydroxyamine uses glucose addition (The Process of "Addition of Glucose") after pre-mixing the catalyst and the amine in a simplified reaction, which P548 can achieve good results as long as the glucose is added under a hydrogen pressure of at least about 100 psig, preferably at least about 500 psig, and more preferably at least about 1000 psig, at a temperature of less than about 80 ° C, preferably less than about 70 ° C, and more preferably less than about 60 ° C C. The materials and the conditions of the rest of the reaction are the same as those detailed above for the adduct process. The preparation of N-alkylaminol polyols by any of the processes can be carried out in any of the pressure vessels with good agitation, suitable for carrying out hydrogenation reactions. In a convenient form for the "Glucose Addition" process, a pressure reactor with a separate storage vessel is employed. The container (which itself may be pressurized) communicates with the reactor by suitable pipes or the like. During use, the stirred paste or suspension of the nickel catalyst is "cleaned" first, which includes being treated with hydrogen to remove traces of the nickel oxides. This can be conveniently done in the reactor. (Alternatively, if the manufacturer has access to a source free of nickel catalyst oxide, it is not P548 necessary pre-treatment with H2. However, for most manufacturing processes some traces of the oxides will inevitably be present, so H2 treatment is preferred). After removal of excess paste or suspension medium (water), N-alkylamine is introduced into the reactor. Subsequently, the sugar is introduced from the storage tank into the reactor, either under hydrogen pressure or by means of a high-pressure pumping system, and the reaction is allowed to proceed. The progress of the reaction can be monitored by periodically withdrawing samples from the reaction mixture and analyzing them to determine the amount of unreacted sugar, using gas chromatography ("gc") or heating the sample at approximately 100 ° C for 30 to 60 minutes in a sealed vial to verify color stability. Typically, for a reaction of about 8 liters (about 2 gallons) the initial stage (until 95% of the reducible compounds are exhausted) requires about 60 minutes, depending in some way on the catalyst level and temperature. The temperature of the reaction mixture can then be raised to complete the reaction (until 99.9% of the reducible compounds are exhausted).

PS 8 Crystallization of Polyhydroxyamines. The color quality, the stability and / or the purity of the N-alkylamino polyol can be further improved by a crystallization process of N-alkylamino polyol from an aqueous solution or a suitable mixture of organic solvent / water. The crystallization is carried out by cooling the aqueous mixture of the N-alkylamino polyol from Step (b) to 0-10 ° C, or more, preferably concentrating the aqueous mixture to about 70% solids before cooling, and more preferably adding from about 10 to 200 parts of organic solvent, for example methanol, acetone, etc. either to the aqueous feed solution or, more preferably, to the concentrated solution. High purity crystals of N-alkylamino polyol are formed, and these can be isolated from the supernatant solution by filtration and / or centrifugation. To obtain crystals with the highest possible purity, the filter cake or the centrifuge cake should be washed with between about 0.25 to about 1.25 parts of cold solvent (0-5 ° C). The wet cake can then be used to produce polyhydroxy fatty acid amides with reduced color. The crystallization method provides a surprisingly improved amide product.

P548 Formation of Fatty Acid Polyhydroxyamides. The N-alkylamino polyol compound prepared by any of the aforementioned reactions and having the required Color Gardner can be used in an overall process for preparing polyhydroxy fatty acid amides as surfactants, which includes an amide forming reaction comprising reacting a source of fatty acyl groups, for example fatty acids, fatty acid anhydrides and fatty acid esters, especially fatty acid esters having more than 98% transmittance at 460 nm with an N-alkylamino polyol having a Color Gardner from less than 1 (<0.1 abs at 440 nm), more preferably esters that have been distilled in the presence of about 0.05% to about 2% alkali metal oxide, for example, those prepared in the above manner, an organic hydroxy solvent in the presence of the base catalyst. The formation of these surfactants with high purity and low color is a special beneficial result of this process when an organic hydroxy solvent is used, since the detergent formulator can pump and / or incorporate the polyhydroxyamide of the fatty acid, which is the product of reaction, plus the reaction solvent such as 1,2-propane diol, (propylene glycol), glycerol or alcohol (for example in P548 liquid detergents) directly into the final detergent formulation. This offers economic advantages since it is necessary a final step of solvent withdrawal, particularly when ethanol or anhydrous glycols are used. The polyhydroxyamine products of any of the aforementioned reactions of R-1, preferably when the water has been substantially removed, can be further employed in an amide-forming reaction which will be referred to herein as the reaction "R-2". A typical reaction of amide R-2 formation of the present can be illustrated as follows: R2COOMe + R3N (H) CH2 (CHOH) 4CH2OH > Basic catalyst, for example, methoxide R2C (0) N (R3) CH2 (CHOH) 4CH2OH + MeOH wherein each R 2 is C 1 or C 20 alkyl and each R 3 is C 1 -C 4 alkyl, C 1 alkoxyalkyl or a hydroxyalkyl group. In this way, the present process can encompass a global process for the preparation of polyhydroxy fatty acid surfactants comprising, optionally, an R-1 process as described above and then reacting the polyhydroxyamine P548 with a color of less than Gardner 1 with a fatty acid ester having at least 98% transmittance at 460nm in an organic hydroxy solvent (preferably methanol) in the presence of a basic catalyst to form the polyhydroxyamide surfactant of fatty acid (at a temperature between about 40 ° C and 135 ° C for a time of less than about three hours, more preferably at a temperature between about 40 ° C and about 100 ° C, and even more preferably at a temperature of between about 50 ° C to about 80 ° C for a time of less than about 2 hours); and optionally removing the solvent. The resulting amide product is treated with an ion exchange resin, more preferably a mixture of acidic and basic resins or, optionally, with a reducing bleach to produce a product that is essentially "clear as water". In a more preferred embodiment, the amide surfactant is first treated with an acid ion exchange resin to convert any soap into a fatty acid and remove any residual amine that has not been converted to amide. Then, the amide surfactant is treated with a basic ion exchange resin to remove the fatty acid. The two resins remove part of any body of color that has already formed.

P548 R-2, or the combination of the reactions R-1 and R-2 hereof, can be used to prepare polyhydroxy fatty acid surfactants of the formula (II) in the following form: R2 - C (0) - N (R1) -Z wherein: each R-1- is H, C1-C4 hydrocarbyl, C1-C4 alkoxyalkyl, hydroxyalkyl, for example 2-hydroxyethyl, 2-hydroxypropyl, etc., preferably C1-C4 alkyl, more preferably C2 alkyl or C 2, and more preferably C 1 alkyl (ie methyl) or methoxyalkyl; and R2 is a C5-C31 hydrocarbyl entity, preferably straight-chain C7-C9 alkenyl or alkyl, more preferably straight-chain alkenyl or C11-C17 alkyl, or mixtures thereof, and Z is a polyhydroxyhydrocarbyl entity having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycityl entity. Z will preferably be selected from the group consisting of -CH2- (CHOH) n- CH2OH, -CH (CH2OH) - (CHOH) n-CH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2OH, where n is an integer from 3 to 5, inclusive and R1 is P548 H or a mono- or cyclic polysaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2- (CHOH) 4-CH2O. The mixtures of the previous Z entities are those that are desired. In Formula (II), R-1 may be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxyethyl, N-1 -methoxypropyl or N-2-hydroxypropyl. R2-CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallow amide, etc. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxy-thiotriotyl, etc. The following reagents, catalysts and solvents can be conveniently used in the R-2 reaction herein, and are listed only by way of exemplification and not by way of limitation. These materials are well known and are routinely available from a variety of commercial sources. Reagents - Various fatty esters can be used in the R-2 reaction, including mono-, di- and triesters (ie triglycerides). Methyl esters, ethyl esters, and the like are also quite suitable.

F548 Polyhydroxyamine reagents include reagents available from the above-described reaction R-1, such as for example N-alkyl and N-hydroxyalkyl polyhydroxy amines with the N-substituent group such as CH 3 -, C 2 H 5 -C 3 H 7 -, HOCH 2 CH 2 - and the like. (The polyhydroxyamines obtained from the Rl reaction are preferably not contaminated with the presence of residual amounts of metal hydrogenation catalysts, although a few parts per million (for example 10-20 ppm) may be present. Mixtures of polyhydroxyamine reagents can also be used Catalysts - Catalysts used in the R-2 reaction are basic materials such as alkoxides (preferred), hydroxides (less preferred due to possible hydrolysis reactions), carbonates and the like. preferred alkoxide include alkali metal C1-C4 alkoxides such as sodium methoxide, potassium ethoxide and the like The catalysts can be prepared separately from the reaction mixture, or can be generated in situ using an alkali metal such as sodium. the in situ generation, for example sodium metal in the methanol solvent, was prefi It is important that no other reagents are present until the generation of the catalyst is complete. He P548 catalyst is typically used at a level of between about 5 to 8 mole% of the ester reagent. The mixtures of the catalysts can also be used. Solvents - The organic hydroxy solvents used in the R-2 reaction include, for example, methanol, ethanol, propanol, isopropanol, the butanols, glycerol, 1,2-propylene glycol, 1,3-propylene glycol and the like. Methanol is a preferred alcohol solvent and 1,2-propylene glycol is a preferred diol solvent. Solvent mixtures can also be used. Reaction Conditions R-2 General - It is also an optional objective here to prepare the desired products while decreasing the formation of cyclized by-products, for example, the ester amides and the bodies of color. Reaction temperatures of less than about 135 ° C, typically in the range of about 40 ° C to 100 ° C, preferably between 50 ° C to 80 ° C, are used to achieve this objective, especially in batch processes in where the reaction times are typically of the order of P548 approximately 0.5 to 2 hours, or even up to 6 hours. Slightly higher temperatures can be tolerated in continuous processes, where residence times may be shorter.

Purification of fatty acid polyhydroxyamides. The polyhydroxy fatty acid surfactant prepared by the processes herein is in a very pure state and has very good color. However, for products that are not colored, or that are clear, less colored or even purer surfactants are required. Accordingly, the polyhydroxy fatty acid surfactant is preferably further treated with an ion exchange resin, a mixture of ion exchange resins or combinations of ion exchange resins and / or a reduction bleaching such as NaBH4, etc., or hydrogenation over a catalyst. The treatment with ion exchange resins can be very effective if the treatment is carried out carefully. Since the minor contaminants present are both cationic in nature, for example amines and / or anionics in their nature, for example soaps and / or fatty acids, it is desired to treat both with anionic and cationic ion exchange resins.

P5 8 (acid and basic). A particularly effective treatment is to treat a solution of the polyhydroxy fatty acid surfactant first with acidic ion exchange resin to remove the amine and convert any fatty acid soap into fatty acid and then treat it with a basic ion exchange resin to remove the acid fatty. Another particularly effective subsequent treatment is the hydrogenation of a solution of the polyhydroxy fatty acid surfactant on a hydrogenation catalyst such as nickel, palladium, copper chromite, etc. Surprisingly, hydrogenation is effective to remove color bodies and precursors from colored bodies without detrimentally affecting the structure of the surfactant. The hydrogenation is typically carried out in a batch reactor. A catalyst, typically made of nickel or palladium, is suspended in a solution of the polyhydroxy fatty acid surfactant and reacted under conditions which will achieve the desired improvement. Typical reaction conditions are hydrogen pressure of between about 150 to about 1000, preferably between about 300 to about 500 psi; the temperature of between about 50 to 120, preferably between P548 about 50 to 65 ° C, to limit the potential soap formation, and the reaction time of between about one to about four hours, preferably between about one to two hours. The color of the surfactant is measured as% transmittance at 420 nanometers, against a 50/50 mixture by weight, of the methanol blank / distilled water. The surfactant is diluted to 50% by weight with the blank solution and read on a spectrophotometer. The typical color of commercial production varies from about 55% to about 70% transmittance, as measured before. For clear products, the minimum transmittance must be at least approximately 70%. The catalyst load to achieve 70% transmittance depends on the type of catalyst used and the desired level of color improvement. For nickel catalysts, fillers vary between about 2% to 10%, preferably about 2% to 5%, expressed as the weight of the catalyst based on the surfactant in solution. These catalyst levels will raise the transmittance from about 40 to 48% to about 70 with 2% catalyst and up to about 80-85% with 10% catalyst. Subsequent hydrogenation with palladium catalyst produces superior color with less catalyst. He PS48 use of the palladium catalyst varies between approximately 0. 005% to approximately 0.15% with resultant transmissions ranging from approximately 85% to approximately 90%, when they start with colors having transmissions of approximately 60%. For comparison, a transmittance of about 42% was raised to about 75% for nickel catalyst and up to about 93% for palladium catalyst, using conditions from about 120 ° C to about 360 psi of hydrogen. Another optional reducing bleaching stage uses a reducing material such as: NaBH4, LIAIH4, etc.

It has been found that the pH should be between about 10 to about 10.9, preferably between about 10.1 to about 10.6, more preferably about 10.4. This pH range provides excellent bleaching at a good rate, without excessive generation of fatty acid soaps by the hydrolysis of the amide. The following examples are intended to illustrate the practice of the R-2 reaction using N-polyhydroxy-amines prepared by the reaction R-l described above (H 2 O having been removed). It is desired to use concentration ranges of reagents and solvents to provide a "concentrated 70%" reaction mixture PS48 (in relation to the reagents). This 70% concentrated mixture provides excellent results, since high yields of the desired polyhydroxy fatty acid product are quickly ensured. Indeed, the indications are that the reaction is completed substantially in one hour or less. The consistency of the reaction mixture at the 70% concentration provides ease of handling. However, even better results are assured at 80% and 90% concentration levels, since the chromatography data indicates that even less of the unwanted cyclized byproducts are formed at these higher concentrations. At the higher concentrations of the reaction systems, it is more difficult to work the reactions, and a more efficient agitation is required (due to its initial viscosity) and the like, at least in the early stages of the reaction. Once the reaction proceeds to any appreciable degree, the viscosity of the reaction system decreases and mixing is facilitated. All percentages, proportions and ratios that are expressed herein are given by weight, unless otherwise specified. All limits and numerical values hereof are approximate, unless otherwise stated.

P548 EXAMPLE I Standard Reaction. A reaction mixture consisting of approximately 214 g of C12 fatty acid methyl ester (Procter &; Gamble CE1295); about 195 g of N-methyl-D-glucamine, dry powder; about 10.8 g of 25% sodium methylate; and about 37.7 g of propylene glycol as a solvent are used in this reaction. The reaction vessel comprises a reactor which is a one-liter, four-necked round-bottomed flask, a 300-mm spiral condenser, a 250-ml round bottom flask; several adapters, an agitator with a variable speed motor, a blanket connected to a Therm-O-Watch® for temperature control and a vacuum water vacuum for vacuum. The methyl ester is added to the reactor and, with stirring, is heated to about 60 ° C. The propylene glycol and the N-methylglucamine (powder) are added with sufficient stirring to keep the solids suspended. The temperature is raised to approximately 80 ° C and to a vacuum of approximately 100 mmHg absolute, if more 0.1% moisture is present, in order to remove moisture. The pressure is raised with nitrogen and sodium methylate is added. The temperature is adjusted to approximately 80 ° C and the time is set to zero. The P548 pressure is reduced to approximately every thirty minutes from about 500 to 350 to 200 to 100 mmHg. The pressure is again raised with nitrogen and a sample is taken for GC analysis. The above standard reaction results in about 200 to 600 ppm of cyclic material, which is considered undesirable. In a standard reaction the level of the cyclic material is 250 ppm while the conversion percentage is 91%, as the reaction temperature decreases to about 70 ° C the level of cyclics is lowered to about 80 ppm and the conversion to approximately 88%, the decrease in the reaction time to about one hour decreases the content of cyclic materials to about 50 ppm and the conversion to about 89%; cutting the level of catalysts in half reduces the cyclic materials to approximately 90 ppm and raises the conversion to approximately 93%; the removal of methanol in 30 minutes reduces the cyclic materials to less than about 50 ppm and raises the conversion to about 90%; and reducing the vacuum to a maximum of approximately 200 mmHg reduces the cyclic materials to approximately 40 ppm while reducing the conversion to approximately 87%.

P548 The reduction of time to remove methanol and reduce the vacuum has the most significant impact on the reduction of cyclic formation. The color improvement is obtained using reagents with better color. The methyl ester and the polyhydroxyamine must both have a Gardner color of less than about 1, the amine being the most important. The use of an excess of amine in the reaction R-1, for example of approximately 100% excess and / or higher heat treatment temperatures, provide improvements in the color of the amine. The use of a crystallization step further improves the color. The amide is preferably treated with an ion exchange resin or, more preferably, with both anionic and cation exchange resins to remove colored bodies. This treatment is achieved in the following way.

EXAMPLE II A global process at the 80% reagent concentration level for the amide synthesis is as follows. A reaction mixture consisting of approximately 84.87 g of methyl ester of C? 2 fatty acid (methyl ester Procter &Gamble CE1270), approximately 75 g of N-methyl polyhydroxyamine of Example I, above, P548 about 1.04 g of sodium methoxide and a total of about 39.96 g of methyl alcohol (about 20% by weight of reaction mixture) are employed for this reaction. The reaction vessel comprises a standard reflux arrangement adapted with a dryer tube, condenser and a mechanical stirring blade. The N-methylglucamine / methanol is heated with stirring under nitrogen (reflux). After the solution has reached the desired temperature, the ester and the sodium methoxide catalyst are added. The reaction mixture is refluxed for about 6 hours. The reaction is completed essentially in about 1.5 hours. After removal of methanol, the recovered product weighs approximately 105.57 grams. Chromatography indicates the presence of only traces of the undesired ester-amide by-product and there are no detectable cyclized byproducts. While the above discussion is generally related to an auxiliary or solvent method for preparing N-methyl polyhydroxyamines, such as N-methylglucamine, as well as its fatty acid amide derivatives using fatty methyl esters, it should be understood that variations are available that they do not depart from the spirit and scope of this invention. Therefore, reducing sugars such as fructose, galactose, mannose, P548 maltose and lactose, as well as sugar sources such as high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup, and the like, can be used to prepare the polyhydroxyamine material (for example to replace glucamine) in the reaction. Surprisingly, a wide variety of fats and oils can be employed herein. (triglycerides) in place of the fatty esters exemplified above and a non-obvious improvement in the degree to which the reaction is completed can be provided. For example, oils and fats such as soybean oil, cottonseed oil, sunflower oil, tallow, lard, safflower oil, corn oil, cane oil, oil Peanuts, fish oil, rapeseed oil and the like or the hardened forms thereof (hydrogenated), can be used as the source of triglyceride esters for use in the present process. When triglycerides are used, the reaction proceeds so that it becomes closer to completion and there are fewer by-products to be removed. Specifically, more than about 95% of the reaction is completed, as possible. Preferred triglycerides are palm kernel oil, coconut oil, palm oil and tallow.

Purification. The surfactants produced by the process set forth above are surprisingly pure. However, for the preparation of very clear products, even greater purity is required. Therefore, it has been found necessary to treat the surfactant products herein by at least one of the treatments selected from the group consisting of: reducing bleaching and ion exchange. Reducing bleaching is well known as a reducing / eliminating method for colored bodies and / or color body precursors, which are subsequently converted into colored bodies by the action of light, oxygen, interaction with other materials, etc. However, in order to treat the N-alkyl polyhydroxyamine amide surfactant herein, it is necessary to take precautions to avoid the formation of soap, as disclosed below. The use of hydrogen and hydrogenation catalysts can also provide good reducing bleaching without excessive soap formation, although this technique is usually more complicated and requires special equipment. Preferred hydrogenation catalysts are those described above. It will be appreciated that the manufacture of detergent surfactants from these renewable resources is an important advantage of the present process. This process is particularly useful for preparing longer chain and saturated polyhydroxy fatty acid amides (eg C ^ g) and the relatively mild reaction conditions and temperatures of the present produce desired products with minimal by-product formation. A preformed portion of the fatty acid polyhydroxyamide can be used to aid in the initiation of the amide-forming reaction R-2 when the triglycerides of the long chain methyl esters are used as reagents.

EXAMPLE III Purification of N-methylglucamine, according to the following. Approximately 2500 g of aqueous solution containing about 45% by weight of commercial grade N-methylglucamine are loaded onto a rotary evaporator where they are heated to about 71 ° C under about 27.5 'Hg vacuum which is collected about 957 g of condensate corresponding to a concentration of solids in the evaporator residue of approximately 75%. The residue is mixed with about 660 g of anhydrous methanol and is rapidly cooled to about 1-2 ° C using an ice bath, whereby the N-methylglucamine crystallizes giving a white thick paste. A portion of approximately 1100 g of the paste is charged to a Waring blender, where it is mixed for about 3 to 4 minutes before it is filtered using a Büchner funnel. The sample is filtered to dryness before being washed twice with aliquots of approximately 165 g of cold methanol (approximately 5 ° C) and once with approximately 330 g of cold methanol. The final cake gives approximately 438 g of purified N-methylglucamine to about 16% volatiles to give approximately 83% solids in the original feed. The following chart illustrates the improvements in color and thermal stability that are generated by this process. The purified crystals are dissolved in distilled water to give the same concentration of solids as the original feed. The color is measured in the samples as a percentage of transmittance using a Milton Roy Spectronic 2ID spectrophotometer in cells of approximately 21 cm, at approximately 420 nm. The samples are also tested for thermal stability by subjecting the material to about 280 ° C in an oil bath under an inert atmosphere for about 1 hour. The treated samples are re-diluted to approximately 50% P548 concentration to compensate for any water loss during the heat treatment and the colors are subsequently read.

Sample Original Food Purified Crystals Initial color 71.9% T 94.8% T Color after heat treatment EXAMPLE IV-A (Preparation of Amide with Non-Crystallized Amine) An aqueous solution (approximately 332.62 g) of the commercial grade N-methyl glucamine containing about 54% by weight solids is charged into a one liter reaction flask, standard, adapted with a mechanical stirring knife, a condenser and a receiver. For about one hour and twenty minutes, the solution is gradually heated to about 132 ° C and the pressure is reduced to about 66 cm Hg of vacuum to remove the water that condenses and collects in the receiver. To the dried N-methylglucamine is added about 201.71 g of methyl ester Procter & Gamble CE-1295 and approximately 37.20 g of propylene glycol. After stirring, approximately 15.01 g of a solution of P548 sodium methoxide (approximately 25% by weight of methanol) and approximately 14 g of methanol are added to the reactor and the time is recorded. The mixture is allowed to cool to about 85 ° C as the methanol is removed by distillation under atmospheric pressure. After approximately 30 minutes that the methanol is no longer visible in the distillation, the vacuum is slowly applied to the reaction vessel to purify the remaining methanol and make the reaction complete. When the vacuum reaches 66 mm Hg without excessive foaming, the reaction is complete. After breaking the vacuum with nitrogen, approximately 126.86 g of water and 74.60 g of ethanol are added to the mixture. The resulting glucose amide solution is dark yellow in color and has approximately 54% transmittance at about 420 nm.

EXAMPLE IV-B (Crystallization of amide with crystallized amine) A reaction mixture consisting of about 121.0 g of a purified N-methylglucamine filter cake of Example III (about 16% volatiles), about 112.1 g of Procter methyl ester & Gamble CE-1295 and approximately 19.7 g of propylene glycol were charged to a one liter reaction vessel, equipped with a mechanical agitation blade, a P548 capacitor and a receiver. The mixture is heated with stirring to about 80% and kept under a slight vacuum for about 30 minutes to remove any residual moisture and methanol from the filter cake. After breaking the vacuum with nitrogen, about 8 g of a 25% sodium methoxide solution are charged to the reactor and the time recorded. The methanol is allowed to distill and collected in the receiver. After about one hour, a vacuum is slowly applied to purify the remaining methanol and bring the reaction to the end. After approximately two and a half hours the vacuum is reached and no more methanol is distilled. The vacuum is broken with nitrogen and about 39.5 g of ethanol and 65.1 g of distilled water are added to the mixture. The resulting glucose amide solution has a very pale yellow dye and has a transmittance measurement of 88.9% at about 420 nm.

EXAMPLE V The regeneration of a strong base ion exchange anion resin after exhaustion with polyhydroxy amide elution is carried out in the following manner. An ethanolic HCl solution is prepared by adding approximately 27.4 g of concentrated HCl (approximately 36.5% by weight) to approximately 972.6 g of 3A ethanol. A dilute caustic solution is prepared, dissolving approximately 15.3 g of NaOH pellets (appraisal of approximately 98%) in approximately 1484. 7 g of distilled water. Approximately four hundred and fifty milliliters of spent Amberlite IRA-410 are packed in a 500 ml graduated cylinder and washed with approximately one liter of hot distilled water to remove the residual amide. The resin is washed with about one liter of ethanolic 5% HCl solution (prepared as described above) in order to acidify, followed by a wash with approximately one liter of ethanol to complete the removal of fatty acid. The resin is then washed with about one liter of hot distilled water to rehydrate the resin. Subsequently, the resin is regenerated by slowly adding about 1 1/2 liters of a 5% aqueous NaOH solution through the resin.

The resin is then washed with distilled water until the pH is about 8. The regeneration of the strong acidic cationic ion exchange resin after exhaustion by the polyhydroxyamide elution proceeds in the following manner: An ethanolic solution of HCl by adding approximately 27.4 g of concentrated HCl (from about 36.5% by weight) to about 972.6 g of 3A ethanol. Approximately four hundred and fifty milliliters of the spent Amberlite IR-120 Plus, a strong acid cationic resin, are packed in a 500 ml graduated cylinder, wrapped in a thermal tape of approximately 50 ° C and washed with approximately one liter of hot distilled water to remove the residual amide product. The resin is acidified by eluting approximately one liter of ethanolic HCl and then washed with hot distilled water to rehydrate the resin. Regeneration is completed by slowly eluting an additional liter of approximately 5% aqueous HCl through the resin. The resin is then washed with distilled water until the pH is about 5.

EXAMPLE VI Approximately two hundred milliliters of the Regenerated Amberlite IR-120 Plus of Example VII is packaged in a 250 ml graduated cylinder, wound with a thermal tape adjusted to approximately 50 ° C. Approximately two thousand grams of glucose amide that are prepared from crystallized N-methylglucamine according to Example IV-B are eluted through the resin and collected in aliquots of approximately 200 g. Approximately 1800 g of the material eluted from the cationic column is then eluted through approximately 200 milliliters of the strong regenerated anionic resin of Amberlite IR-410 of Example VII. This column temperature is also maintained at approximately 50 ° C with the help of an electrical thermal tape. The eluted material is collected in sixteen aliquots of approximately 100 g. Before the treatment of the resin, the analysis of the amide glucose indicates the following composition and approximate quality. Transmittance at approximately 360 nm = 74.1% N-methylglucamine = 2.8% Fatty Acid / Methylester = 4.9% Amide Glucose = 55.6% Amide Ester = 0.2% After treatment of the resin, both the color quality and the product composition improve in big measure. Transmittance at approximately 360 nm = 93.3% N-methylglucamine = 0.1% Fatty Acid / Methylester = 0.6% Amide Glucose = 55.5% Amide Ester = 0.1% F548 EXAMPLE VII A second method for the regeneration of strong basic anion ion exchange resin after depletion by polyhydroxyamide elution is as follows: An ethanolic HCl solution is prepared by adding about 27.4 concentrated HCl (about 36.5% by weight) to about 972.6 g of ethanol 3A. A dilute solution of about 7 moles of the ethoxylated lauryl alcohol is prepared by dissolving about 9 g of ethoxylate in about 9 g of ethanol and about 1482 g of hot distilled water. Approximately four hundred and fifty milliliters of the spent resin are packed in a 500 ml graduated cylinder, wrapped with a thermal tape and maintained at approximately 50 ° C. The resin is washed with about one liter of hot distilled water to remove the residual amide. Approximately one liter of hot, 5% aqueous HCl is eluted through the resin to acidify. The column is allowed to stabilize for about two hours at about 50 ° C to allow the fatty acid to migrate to the surface of the resin. The column is backwashed with approximately 1 1/2 liters of hot ethoxylated solution to remove the acid PS48 fatty of the column. The resin is then regenerated by decreasing the elution to about 1 1/2 liters to about 5% aqueous NaOH solution through the resin. The resin is then washed with distilled water until the pH is about 8. The cationic resin is regenerated in the same manner as described in Example VII. When the amide glucose is prepared in the manner described in Example IV-A, having an amber color and measuring approximately 32.1% Transmittance at about 360 nm, it is passed through these ion exchange resins, the color improves to a pale straw color measured at approximately 82.2% Transmittance up to approximately 360 nm.

EXAMPLE VIII N-methylglucamine is prepared with good color stability and subsequently good quality amide glucose is produced, in the following manner. An approximately two gallon capacity autoclave is charged with approximately 360 g of Raney Grace 4200 nickel catalysts, in the form of a 50% suspension in water, approximately 920 g of 50% methylamine and approximately 100% water. He P548 reactor is pressurized to approximately 1500 psig with hydrogen. The contents of the reactor are heated to about 50 ° C with stirring. To this are charged approximately 2600g of ClearSweat ™ 99DE corn syrup and the contents are reacted at about 50 ° C for about two hours. Fresh hydrogen is added to maintain the pressure as it is consumed by the reaction. A sample is removed from the reactor at the end of approximately two hours and its composition is measured to be approximately: N-methylglucamine = 95.0% n-glucosylamine = 1.0% glucose = 1.0% sorbitol = 0.9% This material has a light yellow color and during the subsequent reaction to give the amide glucose according to the procedure described in Example IV-A a product having a very dark color is obtained. The reaction mixture remaining in the autoclave is subjected to an increase in temperature to about 50 ° C-100 ° C, for a time of about 60 minutes while the hydrogen pressure is maintained at about 1500 psig. After it reaches a temperature of approximately 100 ° C, the reactor is cooled rapidly under hydrogen pressure by introducing water from P548 cooling to the reactor coil. When the mixture is cooled to approximately 30-50 ° C, the material is discharged from the reactor. Its composition is approximately: N-methylglucamine = 97.3% n-glucosylamine undetectable undetectable glucose sorbitol = 0.8% This clear material like water is used to produce glucose amide according to the procedure used in Example IV-A and a product that has a pale yellow color.

EXAMPLE IX AMIDAS PROCESSED FROM CRYSTALLIZED N-METHYLGLUCAMINE AND ESTER TREATED WITH BASES Approximately 49.1 kg of the methyl ester of Procter & Gamble CE-1295 are charged in a 72-liter distillation flask equipped with a condenser and a receiver. Approximately 900 g of sodium methoxide solution (approximately 25% by weight of methanol) are added to the ester. At an absolute pressure of approximately less than 10 mm Hg, the ester is heated to about 140 ° C. The distillate is condensed and collected in the receiver. The first approximately 618 g that are collected in the receiver are discarded, the remaining distillate is collected P548 as a low-odor methyl laurate, "clear as water". Approximately 175.0 g of the n-methylglucamine crystals purified according to Example III are dissolved in water to yield approximately 375.0 g of aqueous solution. This solution is loaded into a standard liter reaction flask fitted with a mechanical stirring blade, a condenser and a receiver. For approximately two hours and forty minutes the solution is gradually heated to about 130 ° C and the pressure is reduced to about 26 inches of Hg vacuum to remove the water which is then condensed and collected in the receiver. To the dehydrated n-methylglucamine are added about 195.9 g of distilled methyl laurate described above and about 36.5 g of propylene glycol. After stirring, approximately 14.5 g of sodium methoxide solution (approximately 25% by weight in methanol) are added to the reactor and the time recorded. The mixture is allowed to cool to about 85 ° C as the methanol is removed by distillation under atmospheric pressure. After about 30 minutes the distillation of more methanol is no longer visible so that a vacuum is slowly applied to the reaction vessel to purify the remaining methanol and drive the reaction to completion. When the vacuum reaches approximately 25 inches of Hg P548 without excessive foaming, the reaction ends. After breaking the vacuum with nitrogen, approximately 123.0 g of water and approximately 72.3 g of ethanol are added to the mixture. The resulting glucose amide solution is "clear as water" and measures 95% Transmittance at 420nm.

EXAMPLE X PREPARED AMIDES USING TRIGLYCERIDES Triglyceride reagents include CRISCO® oil, palm oil, sunflower oil, canola oil, Corsican oil, coconut oil, palm stearin and the corresponding hydrogenated oils. The catalysts are alkali metal salts of monohydric alcohols or polyhydroxy alcohols, for example sodium methoxide. The reaction medium is a non-ionic surfactant, for example NEODOL® 10-8 or 23-3, or GENAPOL 26-L-5. The reaction is carried out in the fused state. The N-methylglucamine at a molar ratio of between about 2.3: 1 to about 2.9: 1 based on the triglyceride, the non-ionic surfactant and the triglycerides are fused together at about 120-140 ° C under vacuum in about 30 minutes. Approximately 7.5 mol%, based on the N-methylglucamine, of the sodium methoxide are added to the reaction mixture. The reaction mixture becomes homogeneous in PS48 seconds. The reaction mixture is immediately cooled to about 85 ° C. The reaction mixture is kept under vacuum for about 1 to 2 hours and is completed at this point. In an alternative process, the N-methylglucamine is mixed at room temperature with the non-ionic surfactant, the triglyceride and the catalyst. The mixture is heated to 85-90 ° C alternately under vacuum and under nitrogen. The reaction mixture becomes clear within one to one and one half hours. The reaction mixtures are maintained at about 85 ° C for about 2 to 3 hours. More specifically, approximately 127.45 g of N-methylglucamine powder is added to a 500 ml three-necked round bottom flask, equipped with an internal thermometer, a vacuum line, a nitrogen line and a mechanical stirrer. The N-methylglucamine is melted at about 130-140 ° C and dried under vacuum. The hardened palm kernel oil (approximately 156.41 g) is added to a separate, 500 ml three-necked round bottom flask equipped with an internal thermometer and a vacuum line. The separated palm seed oil is melted at about 130-140 ° C and dried under vacuum. The hardened and dried palm kernel oil and approximately 31.54 g of propylene glycol are added to the N-methylglucamine by mixing. Approximately 1.76 g of methoxide P548 sodium as a 25% mixture with methanol, added to this mixture by mixing and the methanol removed in vacuo. The mixture is homogenized in approximately 1.5 minutes, at which time the cooling is applied. The mixture is cooled to approximately 90 ° C in about seven minutes and maintained at this temperature for approximately 85 minutes. The mixture is separated by discharges and the analysis is carried out by gas chromatography. The removal of water from the reagents decreases the formation of fatty acid. Preferably, the water level is less than about 0.1%.

EXAMPLE XI AMID TREATMENT WITH BOROHIDRIDE Approximately two hundred grams of glucose amide is added to a one-liter three-necked reaction flask, adapted with a thermometer on top of a balance. The reactor is transferred to a heating blanket and connected to a mechanical stirrer. The temperature rises to approximately 38 ° C and is maintained at this temperature throughout the period of the treatment. Approximately 1.23 g of commercial sodium borohydride and approximately 0.20 g of PS 8 sodium borohydride powder, inside the reactor. There is approximately 0.49 g of sodium hydroxide in the borohydride, which raises the pH from about 8.7 to about 10.4. The starting color of the amide is about 54% transmittance at 420 nanometers and after approximately two hours of treatment the transmittance is about 76%. The final pH of the solution is decreased to approximately 8 with 31% hydrochloric acid. The pH of 10.4 results in higher soap production, but a pH of more than about 10 is required to have borohydride stability. Untreated N-methylglucamine amide typically has a soap content of about 3.09. The pH / soap content of the borohydride treated with N-methylglucamine amide varies approximately as follows: 10.1 / 3.14; 10.3 / 3.16; 10.6 / 3.17; and 11.0 / 3.41. As a result, the pH should be less than about 10.9 during the treatment.

EXAMPLE XII A solution of polyhydroxy fatty acid surfactant as in Example II, before purification, having a% transmittance of less than about 70%, is used by treating it with hydrogen in P548 a reactor stirred at high pressure, heated by an internal coil connected to a steam / water mixing apparatus. The surfactant solution contains approximately 60% surfactant, 22% water, 12% ethanol and 6% propylene glycol. Approximately 1000 g of the solution is suspended in about 1.2 g of the palladium catalyst (5% palladium on carbon) wetted at approximately 50% moisture. The reactor is sealed and the agitator starts at approximately 500 rpm. The reactor is pressurized slowly and repeatedly (five times) to approximately 200 psi and then allowed to slowly escape. Thereafter the reactor is pressurized to approximately 400 psi and the agitator increases to approximately 1200 rpm. The temperature is raised to about 66 ° C and the reaction is carried out for about two hours and the product is filtered under hydrogen pressure to remove the catalyst. The% transmittance is this time no more than 80%.

P548

Claims (9)

1. CLAIMS: 1. A process useful in the preparation of amides of N-alkylamino polyols, selected from the group consisting of: (1) a process that is carried out under non-oxidizing conditions to prepare amides of N-alkylamino polyols, comprising reacting a source of fatty acyl groups selected from the group consisting of fatty acids, fatty acid anhydrides, fatty acid esters and mixtures thereof, preferably fatty acid esters, which have more 98% transmittance at 460nm with a N-alkylamino polyol, preferably N-alkylglucamine, having a Color Gardner of less than 1, preferably an N-alkylamino polyol which has improved its purity by a crystallization process of N-alkylamino polyol from an aqueous solution or of a water / organic solvent mixture and recovering the N-alkylamino polyol, the crystallization is preferably carried out by cooling an aqueous mixture of N-alkylamino polyol at 0-10 ° C and isolating the crystals. Highly pure N-alkylamino polyol from the supernatant solution by filtration and / or centrifugation, and more preferably, wherein an aqueous mixture of N-alkylamino polyol is concentrated to at least about 70% solids before cooling , and then add PS48 about 10 to about 200 parts of an organic solvent to the concentrated solution, and optionally, but preferably, wherein the resulting filter cake or the spincake is washed with from about 0.25 to about 1.25 parts of cold solvent at 0 -5 ° C, the preferred reaction is carried out in an organic hydroxy solvent, preferably selected from the group consisting of: methanol, ethanol, propanol, isopropanol, butanol, glycerol, 1,2-propylene glycol, 1, 3- propylene glycol and mixtures thereof, in the presence of a base catalyst, the level of catalyst for the preferred fatty acid ester is at a level of between about 5 to about 8 mol% of fatty acid ester, at a temperature between about 40 ° C and 135 ° C, preferably between about 50 ° C and 80 ° C, for a period of time that is less than about three hours, preferably less than about two hours; (2) a process for removing an impurity selected from the group consisting of amine, fatty acid and mixtures thereof, preferably amine, and optionally fatty acid, and more preferably N-alkylamino polyol, from an aqueous detergent surfactant , preferably N-alkyl polyhydroxyamine amide, solution comprising treating the surfactant solution with P548 ion exchange resin; (3) a process for removing the colored body, a color body precursor or mixtures thereof from the N-alkyl polyhydroxyamine amide, which comprises treating the N-alkyl polyhydroxyamine amide with a reducing bleach, preferably a borohydride, and the preferred treatment is carried out at a pH of between about 10 to about 10.9, more preferably between about 10.1 to about 10.6; (4) a process for regenerating a strong basic ion exchange resin containing fatty acyl anion groups comprising acidifying the resin to form fatty acids corresponding to the fatty acyl anion groups and removing the fatty acids by dissolving them in organic solvent; and (5) mixtures of these processes.
2. 2. The process according to claim 1, wherein the resulting N-alkyl polyhydroxyamine amide is treated with ion exchange resin, preferably a mixture of acidic and basic resins, and then optionally, but preferably, N-alkyl polyhydroxyamine Amide is first treated with the acid ion exchange resin to convert any soap, which is present, into fatty acid and remove any amine P548 residual that could be present and then treated with basic ion exchange resin to remove the fatty acid.
3. 3. The process according to claim 1 or 2, wherein the N-alkyl polyhydroxyamine amide is treated with a reducing bleach.
4. The process according to claim 1, 2 or 3, wherein the pressure is maintained at a vacuum of less than about 200 mm Hg and the solvent is removed from the reaction product in less than about one hour, preferably less than about half an hour.
5. The process according to claim 1, wherein the impurity comprises fatty acid soap and the solution is first treated with acid ion exchange resin to remove the amine and convert the fatty acid soap into fatty acid and then treat it with a resin of basic ion exchange to remove the fatty acid.
6. The process according to claim 1, wherein the reducing bleach is hydrogen and the treatment is carried out in the presence of the hydrogenation catalyst, which is preferably selected from the group consisting of: nickel and palladium catalysts.
7. The process according to claim 1, wherein the fatty acyl groups contain from about 6 to about 30 carbon atoms, P548 preferably from about 10 to about 20 carbon atoms, and more preferably from about 12 to about 16 carbon atoms.
8. 8. The process according to claim 1 or 7, wherein the solvent is ethanol. The process according to claim 1, which is carried out under non-oxidizing conditions, to prepare amides of N-alkylamino polyols, comprising at least the step selected from the group consisting of: (1) reacting a source of fatty acyl groups selected from the group consisting of fatty acids, fatty acid anhydrides, fatty acid esters and mixtures thereof, which has more than 98% transmittance at 460nm with an N-alkylamino polyol having a Color Gardner of less of 1; (2) removing from an aqueous solution of the amide of N-alkylamino polyols, an impurity selected from the group consisting of amine, fatty acid and mixtures thereof by a step comprising treating the solution with ion exchange resin and then, when the ion exchange resin is a strong basic ion exchange resin, containing fatty acyl anion groups, regenerating the strong basic ion exchange resin by a process comprising acidifying the resin to form the fatty acids corresponding to the groups of fatty acyl anion P548 and remove the fatty acids by dissolving them in the organic solvent; and (3) removing the colored body, the color body precursor or mixtures thereof from the N-alkylamino polyol amides, which comprises the step of treating the N-alkylamino polyol amides with a reducing bleach. P548