KR100274687B1 - Process for preparing amides of n-alkyl polyhydroxyalkyl amines - Google Patents

Abstract

In organic hydroxy solvents such as methanol, N-alkyl polyhydroxy alkyl amines such as N-methyl glucamine having a Gardner color of less than 1 have a transmittance of more than 98% at methyl esters, anhydrides and / or 460 nm. Reaction with a raw material of fatty acid acyl groups such as fatty acids produces N-alkyl polyhydroxy amine amides with good color. N-alkyl polyhydroxyamines can be purified by crystallization, and / or reducing bleaching to provide excellent color. The reaction is preferably carried out at low temperatures for a small amount of time with a low level of catalyst which inhibits the formation of cyclic products. The resulting amide product can be further purified by treatment with anionic and cationic ion exchange resins to remove soap and amine impurities. The anionic ion exchange resin can be easily regenerated by acidifying it and then washing with an organic solvent.

Description

[Name of invention]

Method for preparing amide of N-alkylpolyhydroxyalkyl amine

[Technical Field]

The present invention relates to a process for the preparation of amides of N-alkyl polyhydroxyalkyl amines, especially of amides having a good color and few undesirable side products.

[Background]

The preparation of N-alkyl polyhydroxyalkyl amines (N-alkyl polyhydroxyamines), such as N-methylglucamine, fatty acid amides thereof, has been known for many years and such materials are commercially available. In recent years, for example, a fatty acid polyhydroxy amide cleaning surfactant prepared by reacting a fatty acid ester with an N-alkyl polyhydroxyamine has been used for detergents. It is clear that care must be taken to prepare amides of N-alkyl polyhydroxyamines of good color.

The present invention provides high quality polyhydroxy fatty acid amide surfactants. The present invention provides a high yield of a nearly watery white N-alkyl polyhydroxyalkyl amine amide, in particular an amide of N-methylglucamine, and in particular contains little N-methyl as described below. Provided is an apparatus for making amides of glucamine.

[Prior art]

A method of glucose reductive amination reaction is disclosed in US Pat. No. 2,016,962 (patented to Flint et al., October 8, 1935).

U.S. Patent No. 1,985,424 (patented Dec. 25, 1934 to Picot et al.) Discloses that (a) a heated product of glucose and aqueous methylamine, under pressure, in the presence of hydrogen and a hydrogenation catalyst, (b) an organic carboxyl Disclosed are "fabric auxiliaries" prepared by reacting with acids such as stearic acid or oleic acid. The concentrated product, prepared at about 160 ° C., is called “exclusive or otherwise exclusive amide” and wherein the formula R—CO—NR ₁ —CH ₂ — (CHOH) ₄ —CH ₂ 0H, wherein R is at least 3 carbons An alkyl radical containing an atom, and R ₁ is hydrogen or an alkyl radical.

U.S. Patent No. 2,016,962, issued Oct. 8, 1935, discloses a process for preparing glucamine and related products.

U. S. Patent No. 2,703, 798 (patented by Schwartz, March 8, 1955) shows that compositions prepared by reacting fatty acids or acid anhydrides with N-monoalkylglucamine (e.g., estimated by the picot method) have poor color. It is assumed that the washability is poor. Thus, Schwarz points out the problems associated with the formation of condensation products of N-monoalkylglucamines and fatty acids with regard to their undesirable color properties and washability.

According to Schwarz, approximately equal moles of N-alkylglue are heated by heating to a temperature of 140-230 ° C., preferably 160-180 ° C., under atmospheric pressure, reduced pressure or pressure during a period of “more than one hour”. Carmine can be reacted with fatty acid alkyl esters, during which two initial immiscible phases are fused to produce a product that is a useful detergent.

Suitable N-monoalkylglucamines are exemplified by N-methylglucamine, N-ethylglucamine, N-isopropylglucamine and N-butylglucamine. Suitable fatty acid esters are exemplified by the reaction of C ₆ -C ₃₀ fatty acids with methyl esters of fatty alcohols such as lauric acid.

More recent methods include U.S. Patent Nos. 5,334,764 (Siebel, Conno, Schumate and St Laurant); 5,338,486 (Konno, Siebel, and Cao); 5,338,487 (Konno, Siebel and Cao); And 5,380,892 (Konno, Siebel, and Cao), which form part of the invention for reference.

Thomas Hedley & Co., Ltd. According to British Patent No. 809,060 (published February 18, 1959) of Procter & Gamble Ltd., the compounds prepared by this method are useful as detergents for detergents such as those having a granular form. Hildreth (supra) states that it is useful as a compound in the biochemical field as a detergent for plasma membrane dissolution, and EP-A 285,768 (December 10, 1988) describes such compounds as thickeners. Thus, such compounds or compositions containing them may be very preferred surfactants.

Other methods for preparing compositions comprising the amide compounds of the present invention are included in the above disclosure of improved thickeners. See EP-A 285,768. See, for example, H. Kelkenberg, Tenside Surfactants Detergents 25 (1988) 8-13, for further description of the preparation of N-alkylglucamines. The above patents and publications form part of the present invention by reference.

[Summary of invention]

The present invention relates to a series of enhancements to the process for the preparation of amides (N-alkylaminopolyols) of N-alkyl polyhydroxy amines. The raw materials, such as esters, of N-alkyl polyhydroxy amines and fatty acid acyl groups, used in the amide production, are chosen to have a good color, and the reaction conditions are chosen to avoid the formation of chromophores and precursors for chromophores. And / or the amide product is treated with an ion exchange resin, a mixture of ion exchange resins, or a combination thereof and / or a reducing "bleach" to produce the best color amide. Combinations of all of these improvements are required to obtain amides with the best color to prepare detergent compositions, particularly liquid detergent compositions that are “water white” and low in cyclic material.

The present invention relates to fatty acids, fatty acid anhydrides and fatty acid esters, particularly those selected from the group consisting of fatty acid esters having a transmittance of more than 98% at 460 nm, such as methyl esters or triglycerides, having a Gardner color of less than 1 (at 440 nm of <0.1). Absorption rate) The present invention relates to a method for producing a polyhydroxy fatty acid amide surfactant comprising reacting an N-alkylamino polyol. Crystallization of the N-alkylamino polyols can be used to provide the proper purity and color. N-alkylamino polyols having this Gardner color are “stable” at 130 ° C. for 3 hours. If it has a Gardner color of 4 or less after 3 hours under these conditions, the N-alkylamino polyol is considered to be stable. Less pure N-alkylamino polyols will be dark brown after 3 hours under these conditions. Also, in order to produce the best colored amide, the dehydration of the N-alkylamino polyol is carried out at about 110 ° C. to about 160 ° C. for less than about 3 hours, more preferably at about 1 hour 30 minutes or less. At a temperature of 120 ° C. to about 140 ° C., more preferably at a temperature of about 130 ° C. to about 135 ° C. for about 1 hour. However, for commercial performance, good results can be obtained with the dehydration time of about 4 to about 8 hours, preferably about 5 to about 6 hours, accepting the limitations of commercial devices. Purer N-alkylamino polyols can be obtained by crystallization from aqueous solutions in the presence or absence of organic solvents.

The dehydrated N-alkylamino polyols are then reacted with, for example, fatty acid esters, especially triglycerides, to form fatty acid polyhydroxy amide surfactants.

The resulting polyhydroxy fatty acid amide surfactant is then worked up with an ion exchange resin, a mixture of ion exchange resins or an ion exchange resin and / or a reducing bleach such as NaBH ₄ or the like, or hydrogenation on a catalyst, as described below. And post-treatment with any combination of these treatments. Particularly effective post-treatments are the hydrogenation of polyhydroxy fatty acid amide surfactant solutions on hydrogenation catalysts such as nickel, palladium, copper chromate and the like.

In a preferred method, the fatty acid ester is a C ₁₀ -C ₁₈ alkyl or alkenyl fatty acid methyl ester, or triglyceride, and the N-alkylamino polyol is N-methyl glucamine, N-methyl furutamine, N-methyl maltamine and N- Methyl glycerol amine.

Detailed description of the invention

The process of the invention uses raw materials of selected reactants, N-alkylamino polyols and fatty acid acyl groups with good color, especially heat stable color.

"Color" referred to herein is a Gardner color such as, for example, N-alkylaminopolyol, N-alkylamino fatty acid amide, and the like. "Gardner color" is a standard Gardner measurement color known in the art. A near Gardner color (solution) represents a nearly colorless ("water-white") solution. A Gardner color of less than about 1 is an N-alkylamino polyol It is desired for the reactants and preferably has a Gardner color close to zero.

Gardner colors are determined in accordance with A.0.C.S. (American Oil Chemists Society) Agency Act 1a-64, enacted in 1978 and named COLOR Gardner 1963 (Glass Standard) as amended in 1982. Devices and standards for determining Gardner color can be purchased from Silver Spring Gardner Laboratories, Maryland, USA or 20014 Long Island Mailbox 5728 Delta Scientific, New York. Gardner color limits as used herein are typically the result of the described reactions or colors obtained from colors from existing chromophores, and are not intentionally added chromophores.

The odor characteristics of the N-alkylamino polyol reactants, amides thereof, are substantially amine-free or "fish" type odors (where any excess N-alkylamines are removed) and are also substantially free of typical brown sugar odors.

N-alkylamino polyols

US patent application Ser. No. 07 / 907,382 filed on Jul. 8, 1992, filed by Junan Kao et al., Process for preparing N-alkylamines in aqueous / hydroxy solvents. A suitable N-alkylamino polyol can be prepared in a manner similar to that described as pending in line 23, line 3 and Examples I-VI and XVII-XIV form part of this disclosure by reference. have. The polyhydroxy amines used in the preparation of the polyhydroxy acid amides can be prepared by any method that can give the desired color.

As discussed below, N-alkylamino polyols with good colors are achieved by careful selection of reaction conditions.

The reaction for the preparation of N-alkylamino polyols (hereinafter referred to as "polyhydroxyamines" or "N-alkyl polyhydroxyamines") is referred to as the "R-1" reaction and N-methyl wherein R ¹ is methyl Is eliminated by the formation of glucamine.

[Additional method]

In a first variant of the R-1 reaction, this method involves preliminarily reacting the amine and the reducing sugar to form an adduct.

Water and / or organic solvents such as ethanol

R ¹ NH ₂ + glucose → adduct + H ₂ O

The adduct has the following formula (I).

The reactants, solvents and catalysts used in the R-1 reaction are all known materials and are available at least in various forms from various sources, even if not normally used in pure form for the preparation of cleaning surfactants. Non-limiting examples of materials that can be used herein include the following.

Amine materials— “N-alkylamines” used in the formation of N-alkylamino polyols include the formula R ¹ NH ₂ , wherein R ¹ is for example alkyl, such as C ₁ -C ₁₈ , in particular C ₁ -C ₄ Primary amines of alkyl or corresponding hydroxyalkyl such as C ₁ -C ₄ hydroxyalkyl. Examples include methyl, ethyl, propyl, hydroxyethyl and the like. Non-limiting examples of amines useful herein include methylamine, ethylamine, propylamine, butylamine, 2-hydroxypropyl amine, 2-hydroxymethylpropyl, 2-hydroxyethylamine; 1-methoxypropyl and methylamine are included. C ₁ -C ₃ alkylamines are preferred, with N-methyl amine being most preferred. All these amines together are referred to as "N-alkyl amines". The amine may be anhydride or present in a concentration such as about 30% to about 90%, preferably about 40% to about 70% in a solvent such as an aqueous solvent.

Polyhydroxy Materials—Polyhydroxy in Both R-1 Reactions Preferred sources of useful polyhydroxy materials include reducing sugars or reducing sugar derivatives. Here, "sugar" means a reducing sugar such as, for example, glucose, fructose, mannose, lactose, maltose, xylose and the like. Here, the term "sugar" also includes glyceraldehyde. Such “sugars” may include substances that can be broken down to form sugars such as plant syrups, such as sugar cane syrups, corn syrups, starch derived sugar syrups, hydrogenated wood pulp derived sugars, and the like. Higher fructose, higher glucose and higher maltose syrups are economical and desirable, especially their Gardner colors are satisfactory. Sugar materials that are reactants include, in this first variant, adducts with amines such as methylamine. These varieties were obtained using the film Hewlett Packard 5890 Series 2 at the column inlet using DB1 15 m 0.25 m film thickness ID 250 m g.c. It was determined (measured) by analysis (gas chromatography or "g.l.c.").

A particular advantage of the "additional" method is that "additional" can be produced in the presence of water. Therefore, raw materials, such as corn syrup, can be used as a sugar raw material. However, sugar solutions can be prepared from granulated, powdered sugars by dissolving sugars in a solvent, preferably an aqueous solvent. The concentration of sugars in solvents such as water is typically from about 40% to about 90%, preferably from about 50% to about 70% (typically 71% is the upper limit). It is very important that the color of the starting sugar stock for the production of all N-alkylaminopolyols can be up to about 1 in the Gardner color range, preferably about Gardner 0 +, more preferably water white. The impact on the catalyst and reaction yields of the typical coloring materials present in the starting sugar feed is negligible. These chromophores also contribute to the final color of the N-alkylamino polyols. If such a color is present, it can be removed by a method such as "carbon bleaching" in which the coloring material is adsorbed. It is desirable to prevent the sugar material from being handled and degraded without excessive heating and / or under non-oxidizing conditions.

Of course, to prepare N-alkylamino polyols using sugars having a low Gardner color (e.g., 0 or <1, ie, water white syrup), it is preferable that N-alkylamino polyols having a low Gardner color be prepared. It helps to ensure that it will. Unless otherwise stated, using a low (0-1) Gardner color sugar (preferably white solid or water white solution) and using the reaction series disclosed herein gives the result of obtaining a low Gardner color N-alkylamino polyol Seen to be.

Catalysts A variety of hydrogenation catalysts can be used for the R-1 reaction. Such catalysts include nickel (preferably treated as described below), platinum, palladium, iron, cobalt, tungsten, various hydrogenation alloys, and the like. Preferred catalysts for use in the hydrogenation step are nickel catalysts, Raney nickel, nickel, for example, other nickel catalysts attached to a substrate material such as silica or alumina. Preference is given to catalysts which are easy to remove (eg by filtration). Highly preferred catalysts here include "United Catalyst G49B", "United Catalyst G96", "UCI C46" granular nickel catalysts (sales: United Catalyst, Louisville, KY) and RAneys such as RA4200 and RA3100. Nickel catalysts (WR Grace & Co., Baltimore, MD).

Obtaining a good color also requires optimizing and maintaining the activity of the desired nickel catalyst, including any of the conventional Raney nickel or "supported" nickel catalysts known in the art. It is very suitable to use conventional nickel sold under the trademarks RANEY NICKEL 4200 and 3200 (Grace Chemicals). UCI (United Catalyst, Inc.) G-96B and G-49B and G-49C are also suitable. In the context of nickel catalysts, it is believed that removing the oxides of nickel from the catalyst prevents or prevents the dissolution of nickel ions into the reaction environment, resulting in the formation of reaction products with the desired low nickel content. Moreover, it has been found that the pretreated, preferably post-treated nickel catalyst, can be reused in subsequent multistage reactions to obtain a substantial total cost savings. In general, commercially available nickel catalysts are typically contaminated, for example by oxides, organic materials, excessively edible materials and / or alumina particulates of nickel, in particular after shipment and storage.

The nickel catalyst used in the present method is preferably devoid of catalytic activity which suppresses the amount of nickel oxide, organic material, edible material, alumina fine particles and the like. Therefore, the catalyst is washed one or more times with a solvent to remove organics and / or water-soluble substances, preferably by lowering the pH and / or by treating the catalyst with a strong reducing agent such as hydrogen gas under pressure and / or temperature conditions. It is desirable to destroy or remove it. Once the catalyst is a "washed" catalyst, the catalyst is preferably maintained under an unreactive atmosphere such as nitrogen gas or more preferably a reducing gas such as hydrogen. Exposure to atmospheric pressure is desirable for only a short time and the temperature should be low. The activity of the catalyst can be substantially increased by their reduction or removal, even in the presence of very small amounts of these impurities. The resulting catalyst also provides amines and amides with good color.

When the nickel catalyst is contacted with N-alkyl polyhydroxy amines or adducts, the hydrogen pressure should be maintained to minimize catalyst solubility. Similarly, high hydrogen pressures, such as from about 100 psig to about 3500 psig, preferably from about 50 psig to about 1500 psig, and from about 20 ° C. to about 135 ° C., preferably from about 40 ° C. to about 85 ° C. The activity is regenerated by reducing the level of nickel ions dissolved in N-alkyl polyhydroxyalkyl amines and depositing nickel backing on the catalyst.

The combination of hydrogen gas and pressure / temperature conditions reduces its solubility and, in fact, reverses the reaction to deposit nickel and regenerate the catalyst. Reductions in the content of soluble nickel in N-alkyl polyhydroxy amine products of less than about 10 ppm, preferably less than about 5 ppm, more preferably less than about 2 ppm will effectively regenerate the catalyst.

When the catalyst is separated from the N-alkyl polyhydroxy amine, the temperature is less than about 135 ° C., preferably less than about 85 ° C., and separation, typically filtration, should be carried out under hydrogen pressure.

Regeneration of the catalyst can be carried out using an initial activation step.

An "substantially nickel free", N-alkylamino polyol reactant contains up to about 20 ppm nickel, preferably about 5 ppm nickel (Ni ⁺⁺ ). Nickel is measured with a conventional atomic absorption spectrometer using a diluted sample (5/1 dilution to minimize interference).

The formation of adducts in the solvent-R-1 process is conveniently carried out in water and / or organic solvents, in particular polar, more preferably hydroxy solvents. Typical examples of organic solvents useful for the formation of amine-sugar adducts are methanol (preferred), ethanol, 1-propanol, isopropanol, butanol, ethylene glycol, 1,2-propylene glycol (preferred), 1,3-propylene glycol , Glycerol and the like are included. The amine itself may typically act as a solvent, in an amine: sugar ratio of about 4: 1 to about 30: 1.

The hydrogenation reaction of the R-1 reaction can also be carried out in the presence of an organic or aqueous solvent which dissolves the adduct. Hydrogenation solvents are polar, in particular hydroxy solvents, ie solvents of the same type as used in the production of adducts. When substantially an organic solvent is used, after the adduct production step, the unreacted amine is removed with water. However, when an aqueous solvent is used, the amine and solvent are not removed until the catalyst removal step.

Water is the preferred solvent for the hydrogenation reaction. Methanol is the preferred organic solvent used in the hydrogenation reaction.

General R-1 Reaction Conditions—R-1 reaction conditions are as follows.

Step (a)-Formation of Additives-Step (a) of this process is carried out in a process using an organic hydroxy solvent, at a temperature of from about 0 ° C. to about 80 ° C., preferably from about 10 ° C. to about 60 ° C., aqueous solvent. When is used, it is carried out at a temperature of less than about 70 ℃, preferably less than about 50 ℃, more preferably less than about 30 ℃, preferably from about 15 ℃ to about 25 ℃.

The reaction time used to form the adduct will be from a few minutes to about 20 hours depending on the reaction temperature selected and / or the ratio of amine to sugar. Generally, with respect to an organic solvent, the small reaction temperature in the range of 0 degreeC-80 degreeC requires many reaction time, and vice versa. For organic solvents in general, good yields, ie at least about 90%, preferably at least about 95%, are obtained in 1-10 hours with respect to the organic solvent, over the preferred reaction temperature of 10 ° C.-60 ° C. For low reaction temperature ranges, 0-70 ° C., preferably 0-30 ° C., which gives a good color, in particular good color in water, the reaction time may be as high as 10 hours, but typically high amines at about 4 hours or less. Equilibrium is practically at the rate of per unit. The temperature and reaction time are chosen to give an adduct of which the Gardner color is preferably about 1 or less. Good adduct color is necessary for good reaction and maintenance of color and catalytic activity in any subsequent hydrogenation reaction. Below about a Gardner color of about 1, the resulting N-alkyl polyhydroxy amines, and thus the resulting amides, have a good color. This chromosome can be removed, for example, by carbon bleach as used for sugar solutions.

The adduct also has a very low level of glucose. The glucose level as a percentage relative to the adduct is less than about 1%, preferably less than about l / 2%. Glucose interferes with the hydrogenation step to form N-alkyl polyhydroxy amines. Excessive amines can also reduce glucose levels and minimize the production of sorbitol during hydrogenation.

In general, since the reaction is exothermic, the temperature will rise during adduct formation. Thus, in a batch process, maintaining a temperature below about 30 ° C. includes providing cooling of the reactants and / or reaction mixtures. Temperatures above about 50 ° C. require a reaction time of less than about 10 minutes to avoid excessive color formation. Such little time is usually not viable except for the continuous reaction. In this continuous reaction, back-mixing, for example using plug flow conditions, should be minimized to avoid excessive exposure of the adduct to high temperatures. Ideally, the adduct reacts rapidly with hydrogen to form the corresponding N-alkyl polyhydroxy amines to minimize degradation. However, a temperature of about 30 ° C. or less, preferably about 20 ° C. or less, makes it possible to handle and / or store the adduct for at least several hours, which facilitates the use of a batch method. At 0 ° C., the adduct is stable for 24 hours.

When preheating the adduct, for example in a hydrogenation process, the surface temperature should be maintained below about 100 ° C, preferably below about 70 ° C.

Reactant concentrations may vary. When using amine at least partially as a solvent, a molar ratio of amine: sugar of about 7: 1 or less is preferably used, although this ratio may be used up to about 30: 1. Generally preferred adduct formation is an excessive amine, such as a molar ratio of greater than 1.1, preferably greater than about 1.1: 1. Such as at molar ratios of amine: sugars greater than about 1.3: 1. Typical reactant concentrations in water and / or hydroxy solvents range from 10-80%, typically 40-50% (weight). The adduct formation can be carried out at atmospheric pressure or under pressure.

Step (b) Reaction with Hydrogen—When hydrogen pressure is less than about 500 psig, step (b) should be carried out to avoid prolonged exposure of the adduct to the catalyst, the hydrogen pressure being at least about 1000, preferably about Should be at least 1500 psig. Maintaining a time of about 1 hour or less, preferably about 30 minutes or less reduces the amount of catalytic metal, such as nickel, which is converted to water soluble ions. These ions are undesirable for a variety of reasons including color formation, incompatibility with other materials, safety, and the like.

Step (b) can be carried out in a slurry process or in a fixed bed. In the organic hydroxy solvent method, step (b) is preferably carried out at a temperature of about 20 ° C to about 120 ° C, preferably about 50 ° C to about 100 ° C. In the aqueous solvent process, step (b) is preferably carried out in two steps. The first step is carried out at a temperature low enough to inhibit the production of the corresponding reducing sugars such as sorbitol in the case of glucose, and other unwanted byproducts. Typically this temperature is from about 20 ° C to about 70 ° C, more preferably from about 40 ° C to about 65 ° C, more preferably from about 50 ° C to about 60 ° C. In the second step, after the reduction (hydrogenation) of the adduct to N-alkylpolyhydroxy amine is at least about 80%, preferably at least about 90%, more preferably at least about 95%, the temperature is about 75 ° C. And above, preferably about 80 ° C. or higher, about 135 ° C. or lower, preferably 130 ° C. or lower, to minimize any other material that may form residual adducts and chromosomes, and the adduct is about 95 ° C. At least%, preferably at least about 98%, more preferably at least about 99.9%, to the corresponding N-alkyl amino polyols. This second step is essential for the preparation of N-alkyl polyhydroxy amines having good and stable color under heating. The thermal stability of the N-alkylamino polyols is improved by using excessive amines in this preparation step and by using higher temperatures than the heat treatment step.

During step (b) it is highly desirable to avoid localized excessive heating, for example on the surface of the heating element or heat exchanger. This surface or "epidermal" temperature is at most about 180 ° C, preferably at most 100 ° C, more preferably at most about 70 ° C, and at most about 100 ° C during the second step.

The reaction with hydrogen is preferably carried out with limited initial water, even when water (eg 1: 1 weight or less water: alcohol) may be present when the solvent is an organic hydroxy solvent. Optional removal of water from the adduct prepared in step (a) can be carried out by the use of a desiccant or by simply dropping water and solvent from the adduct and then dissolving the adduct again in a fresh, water free solvent. Can be. The hydrogenation reaction is, for example, when using an organic solvent, for example, at a temperature of 50 -1000 psi, 20 ° C-120 ° C, or at a temperature of 100-500 psi, 50 ° C-90 ° C, 0.1-35 hours, generally 0.5 8 hours, typically 1 to 3 hours.

When the solvent comprises water, the hydrogenation reaction is carried out in two stages as described above.

The adduct / solvent solution used during the hydrogenation reaction is typically 10-80%, typically 40-50% (weight) solute levels.

The choice of hydrogen reaction conditions depends on the pressure device available in the formulator, and it is appreciated that the reaction conditions can change without being separated from this reaction. However, as mentioned above, where both adducts and catalysts, particularly preferred nickel catalysts, are present, the hydrogen pressure should be at least about 500, preferably at least 1000, more preferably at least about 1500 psig. Using a lower pressure of about 100 psig or less would be required for a separate step of removing nickel ions or for extended post-treatment to achieve very low nickel content, as described below.

The hydrogenation catalyst level is typically from about 1% to about 100%, preferably from about 2% (preferably about 5%) to about 30% (preferably calculated on the basis of catalyst weight: reducing sugar substituent weight). 20%), more preferably about 5% (preferably 10%) to about 15% (preferably about 20%) solid weight.

Step (c) Finish- The catalyst is separated after the reaction is complete. The catalyst is removed from the product of step (c) which is preferably dried by crystallization or solvent / water dropping or by an effective drying agent. This helps to prevent back to sugar starting material.

When comprising a solvent / water run off, step (c) is preferably used in the sweeped film evaporator.

Steps (a)-(c) of method R-1 are preferably carried out under non-oxidizing conditions (such as H ₂ or inert gas) to give good color. The catalyst removal in the step (c) method is preferably carried out under hydrogen pressure to prevent nickel (catalyst) dissolution at least under inert conditions.

[Glucose addition method]

Another suitable method of preparing polyhydroxyamines is at least about 100 psig, preferably at least about 500 psig, at temperatures below about 80 ° C, preferably below about 70 ° C, most preferably below about 60 ° C. As mentioned above, more preferably, glucose addition (preferably "glucose addition" method) is performed after pre-mixing of the catalyst and the amine in a simplified reaction which can achieve excellent results during the application of glucose at a hydrogen pressure of about 1000 Psig or more. The material and conditions of the rest of the reaction are the same as the addition product process described above.

The preparation of N-alkylaminol polyols by both methods can be carried out in a well stirred pressure vessel suitable for carrying out the hydrogenation reaction. In a convenient way for the "glucose addition" method, a pressure reactor with a separate reservoir is used. The reservoir (which can be pressurized by itself) is connected to the reactor by a suitable pipe or the like. In use, the stirred slurry of nickel catalyst is first "washed" including hydrotreating to remove nickel oxide residues. This is conveniently performed in the reactor (optionally, if the manufacturer can obtain an oxide free nickel catalyst stock, H ₂ pretreatment is unnecessary. However, traces of oxide residues are inevitably present in most manufacturing methods, Therefore H ₂ treatment is required). After removing the excess slurry medium (water), N-alkylamine is introduced into the reactor. Thereafter, the sugar from the reservoir is introduced into the reactor by a high pressure pumping system under hydrogen pressure and the reaction proceeds. By regularly removing samples of the reaction mixture and analyzing the unreacted sugars using gas chromatography (“gc”), or by heating the samples for 30 to 60 minutes at about 100 ° C. in sealed vials for color stability measurements. Record the progress of the reaction. Typically, for the reaction on a scale of about 8 liters (about 2 gallons), depending on the catalyst level and temperature, the initial stage (named 95% of the depleted depletion) takes about 60 minutes. The reaction mixture may be terminated by raising the temperature of the reaction mixture (named 99.9% of the depleted depletion).

[Crystallization of polyhydroxyamine]

The quality, stability and / or purity of the color of the N-alkylamino propyl can be further improved by the method of crystallizing the N-alkylamino polyol from an aqueous solvent or a water / organic solvent mixture. By cooling the aqueous mixture of N-alkylamino polyols to step (b) to 0-10 ° C. or above, preferably by concentrating the aqueous mixture to about 70% solids before cooling, most preferably methanol, Crystallization is carried out by adding about 10 to about 200 parts of an organic solvent such as acetone to the feed aqueous solution, or most preferably the concentrated solution. Very high purity crystals of N-alkylamino polyols form what can be separated from the supernatant by filtration and / or centrifugation. To obtain the highest purity crystals possible, the filter cake, or centrifugal cake, is washed with about 0.25-1.25 parts of a cooled (0-5 ° C.) solvent. The wet cake is reduced in color to the polyhydroxy fatty acid amide. Crystallization methods yield surprisingly improved amide products.

[Formation of Polyhydroxy Fatty Acid Amides]

Fatty acids, fatty acid anhydrides and fatty acid esters, especially N-alkylamino polyols having a Gardner color of less than 1 (absorption of less than 0.1 at 440 nm) and fatty acid esters having a transmittance of at least 98% at 460 nm, more preferably from about 0.05% Polyhydroxy fatty acids comprising an amide-forming reaction comprising a fatty acid group reaction such as an ester prepared by the above method in an organic hydroxy solvent distilled in the presence of about 2% alkali metal oxide, for example in the presence of a base catalyst N-alkylamino polyol compounds prepared by the above reactions and having the required Gardner color can be used in all procedures of the amide surfactant preparation. In the detergent former, polyhydroxy fatty acid amide reaction products and reaction solvents such as 1,2-propane diol, (propylene glycol), glycerol, or alcohols (eg in liquid detergents) can be incorporated and / or pumped directly into the final detergent formulation. As such, the formation of such surfactants with high purity and low color is particularly advantageous when using organic hydroxy solvents. This is an economic advantage in that the final solvent removal step is unnecessary, especially when anhydrous glycol or ethanol is used.

In the amide-forming reaction, which is a "R-2" reaction, a polyhydroxyamine product by the above R-1 reaction in which water is continuously removed can be used. A typical R-2 amide-forming reaction is illustrated below:

R ² C00Me + R ³ N (H) CH ₂ (CHOH) ₄ CH ₂ 0H -----------------------------〉

Base catalysts such as methoxide

R ² C (0) N (R ³ ) CH ₂ (CH0H) ₄ CH ₂ 0H + MeOH

Wherein R ² is C ₁₀ -C ₂₀ alkyl and R ³ is each C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyalkyl, or hydroxyalkyl.

Thus, this method optionally comprises the above-mentioned R-1 method, and a fatty acid ester having a transmittance of 98% or more at 460 nm in an organic hydroxy solvent (preferably methanol) and a polyhydride having a color of less than Gardner 1 The hydroxyamine is reacted to form a polyhydroxy fatty acid amide surfactant in the presence of a base catalyst (at about 40 ° C. to about 135 ° C. for less than about 3 hours, more preferably at about 40 ° C. to about 100 ° C., more preferably Preferably at about 50 ° C. to about 80 ° C. for less than about 2 hours); And optionally, the solvent is removed. The resulting amide product is treated with an ion exchange resin, preferably a mixture of acid and base resin, or, optionally, a reducing bleach to give a product that is "water white".

In a more preferred embodiment, the amide surfactant is first treated with an acid ion exchange resin to convert the soap to a fatty acid and remove residual amines that do not change to amides. The amide surfactant is then treated with a base ion exchange resin to remove fatty acids. All resins remove some of the color bodies already formed.

R-2, or a combination of R-1 and R-2 reactions, can be used to prepare polyhydroxy fatty acid amide surfactants of formula (II).

R ² -C (0) -N (R ¹ ) -Z

Wherein each R ¹ is H, C ₁ -C ₄ hydrocarbyl, C ₁ -C ₄ alkoxyalkyl, or hydroxyalkyl such as 2-hydroxyethyl, 2-hydroxypropyl, etc., preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl) or methoxyalkyl; And each R ² is a C ₅ -C ₃₁ hydrocarbyl moiety, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably C ₉ -C ₁₇ alkyl or alkenyl, most preferably C _11- C ₁₇ alkyl or alkenyl, or mixtures thereof, and Z is a polyhydroxyhydrocarbyl moiety having three or more hydroxyl and linear hydroxycarbyl chains directly linked to the chain, or alkoxylation (preferably ethoxylated) Oxidized or propoxylated) derivatives. Z is preferably derived from a reducing sugar in a reduction amination reaction: more preferably Z is a glycidyl moiety. Z is -CH _2- (CHOH) n-CH ₂ OH, -CH (CH ₂ 0H)-(CHOH) n-CH ₂ 0H, -CH _2- (CHOH) ₂ (CHOR ') (CHOH) -CH ₂ Is selected from the group consisting of 0H, n is an integer of 3 or more and 5 or less, and R 'is H or a cyclic monosaccharide or polysaccharide, and thus an alkoxylated derivative. Most preferred is glycidyl, wherein n is 4, in particular -CH _2- (CHOH) ₄ -CH ₂ O. Preferred are mixtures of the Z moieties.

In formula (II), R ¹ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxyethyl, N-1- Methoxypropyl, or N-2-hydroxypropyl.

R ² -CO-N <is, for example, cocamide, steramid, oleamide, lauramid, myristamide, capricamide, palmitamide, thalowamid and the like.

Z is 1-deoxyglycityl, 2-deoxyfuructidyl, 1-deoxymaltidyl, 1-deoxylactidyl, 1-deoxygalactidyl, 1-deoxymannitidyl, 1-deoxymalto Triotidyl.

The following reaction solutions, catalysts and solvents are usefully used in the R-2 reaction, and are listed as examples and not by way of limitation. These materials are all well known and commonly available from a variety of commercial raw materials.

Reactants-Various fatty esters can be used in the R-2 reaction, including mono-, di- and tri-esters (ie triglycerides). Methyl ester, ethyl ester, etc. can all be used. The polyhydroxyamine reaction solution is composed of N-substituents such as -CH _3- , C ₂ H _5- , C ₃ H _7- , HOCH ₂ CH ₂ -and N-alkyl and N-hydroxyalkyl polyhydroxyamines. And a reaction solution usable from the R-1 reaction. (Polyhydroxyamines usable from the R-1 reaction preferably contain a residual amount of hydrogenation catalyst to metal, even if a small amount of ppm (eg 10-20 ppm) is present.) Not contaminated by existence). Mixtures of esters and mixtures of polyhydroxyamine reaction solutions can also be used.

Catalysts-The catalysts used in the R-2 reaction are basic substances such as alkoxides (preferably), hydroxides (less preferred since hydrolysis reactions may occur), carbonates and the like. Preferred alkoxide catalysts include alkali metal C ₁ -C ₄ alkoxides such as sodium methoxide, potassium ethoxide and the like. The catalyst can be prepared separately from the reaction mixture or can be produced by itself in an alkali metal such as sodium. What is produced by itself is, for example, sodium metal in a methanol solvent, preferably no other reaction solution is present until the catalyst production is complete. The catalyst is typically used at levels of about 5-8 mole% of the ester reactants.

Solvents-Organic hydroxy solvents used in the R-2 reaction include, for example, methanol, ethanol, propalol, isopropanol, butanol, glycerol, 1,2-propylene glycol, 1,3-propylene glycol and the like. Methanol is the preferred alcohol solvent and 1,2-propylene glycol is the preferred diol solvent. Mixtures of solvents may also be used.

General R-2 Reaction Conditions—It is also an optional purpose to produce the desired materials while minimizing the formation of the following cyclic byproducts, such as ether amides and color bodies.

The reaction temperature is less than about 135 ° C., typically in the range of about 40 ° C. to 100 ° C., preferably at 50 ° C. to 80 ° C., to meet this purpose, in particular the reaction time reaching 0.5-2 hours, or 6 hours Until. Higher temperatures are possible in a continuous manner with shorter reaction times.

[Purification of Polyhydroxy Fatty Acid Amide]

The polyhydroxy fatty acid amides produced by this process are very pure and have good color. However, in non-colored or clean, pure materials, less colored surfactants are required. Thus, the polyhydroxy fatty acid amide surfactants are preferably post-treated by ion exchange resins, mixtures of ion exchange resins, or combinations of ion exchange resins, and / or reducing bleaches such as NaBH ₄ , or hydrogenation of the catalyst.

If the treatment is carried out carefully, treatment with ion exchange resins can be very effective. Since the secondary contaminants present are both cationic and / or naturally occurring anionics such as soaps and / or fatty acids such as amines, treatment with both anionic and cationic (basic and acidic) ion exchange resins It is preferable. Particularly effective treatments are polyhydroxy fatty acid amide surfactants first treated with acidic ion exchange resins to remove amines, and the fatty acid soaps transformed into fatty acids followed by basic ion exchange resins to remove fatty acids.

Another particularly effective workup is the hydrogenation of a polyhydroxy fatty acid amide surfactant solution against catalytic hydrogenation of nickel, palladium, copper chromate and the like. Surprisingly, hydrogenation is effective in removing the color body and the color body precursor without adverse effects on the surfactant structure.

Hydrogenation is typically carried out in a batch reactor. The catalyst of nickel or palladium is reacted under conditions that are slurried in a polyhydroxy fatty acid amide surfactant solution and exhibit the desired improvement. Typical reaction conditions include a hydrogen pressure of about 150 to about 1000, preferably about 300 to about 500 psi; Temperature about 50 to about 120, preferably about 50 to 65 ° C., temperature until soap formation; And reaction time about 1 to about 4 hours, preferably about 1 to 2 hours.

The color of the surfactant is measured by% transmission at 420 nm, blinded by a 50/50 weight mixture of methanol / distilled water. The surfactant is diluted to 50% by weight with a blind solution and measured by spectrophotometer. Typical colors for commercial products vary from transmittance of about 55% to about 70%, measured according to the above. In clean products, the minimum transmission should be at least about 70%.

The catalyst for exhibiting 70% transmission depends on the type of catalyst used and the desired level of color enhancement. Nickel catalysts for indicating a range from about 2% to about 10%, preferably from about 2% to about 5%, are expressed as the weight of the catalyst relative to the surfactant in solution. This level of catalyst increases from about 40%-48%, about 70% with 2% catalyst and about 80%-85% with 10% catalyst. Post hydrogenation with a palladium catalyst yields better color with less catalyst. Starting with a color having a transmittance of 60%, the range of use of the palladium catalyst with a resultant transmittance of about 85% to about 90% is from about 0.005% to about 0.15%. By comparison, the permeation rate of about 42% at 360 psi hydrogen at about 120 ° C. increases to 75% with nickel catalyst and 93% with palladium catalyst.

Another selective reduction bleaching process uses reducing materials such as NaBH ₄ , LiAlH ₄ . The pH should be about 10 to 10.9, preferably 10.1 to 10.6, more preferably about 10.4. This pH range is well bleached at an excellent rate without overproduction of fatty acid soaps by hydrolysis of amides.

The following examples are intended to illustrate the actuality of the R-2 reaction using N-polyhydroxyamine prepared by the above R-1 reaction. Preference is given to using a concentration range in which the concentrations of the reaction liquid and the solvent are "70% concentrated" (relative to the reaction liquid). This 70% concentrated mixture gives excellent results in that the desired polyhydroxy fatty acid amide product can quickly obtain high yields. In fact, it can be seen that the reaction is completed in less than 1 hour. The concentration of the reaction mixture at 70% concentration facilitates manipulation. However, although better results can be obtained at 80% and 90% concentrations, it can be seen from the chromatography data that undesirable cyclic by-products are formed at these high concentrations. At high concentrations, the reaction system becomes more difficult to operate, even in the early stages of the reaction, and requires more efficient agitation (due to its initial concentration). If the reaction proceeds to a significant extent, the viscosity of the reaction system decreases and the mixing becomes easy.

All percentages, ratios, and ratios here are values for weight unless otherwise defined. All limits and values herein are approximate unless otherwise noted.

Example 1

[Standard reaction]

About 214 g of C ₁₂ fatty acid methyl ester (Procter & Gamble methyl ester CE1295) as solvent; About 195 g of N-methyl-D-glucamine, dry powder, about 10.8 g of 25% sodium methylate; And a reaction mixture consisting of about 37.7 g of propylene glycol. The reaction vessel was a 1 liter, four neck, equipotential bottom flask reactor, one 300 mm coil condenser, one 250 ml round bottom flask; Several adapters; One stirrer with variable speed motor, one mantle connected to Thermo-Watch ™ for temperature control; And a vacuum water aspirator for vacuum.

Methyl ester is added to the reactor and heated to about 60 ° C. with stirring. Propylene glycol and N-methyl glucamine (powder) are added with sufficient stirring to keep the solids suspended. Raise the temperature to about 80 ° C., create a vacuum of about 100 mmHg abs. And remove water if more than about 0.1% moisture is present. Raise to pressure nitrogen and add sodium methylate. The temperature is set to about 80 ° C. and the time is set to zero. The pressure is reduced approximately from about 500 to 350, 200, 100 mmHg about every 30 minutes. The pressure is raised back to nitrogen and the sample is taken for GC analysis.

As a result of this standard reaction, a cyclic material of about 200-600 ppm is obtained, which is considered undesirable. In one standard reaction, the cyclic level is 250 ppm, the conversion rate is 91%, and when the reaction temperature is lowered to about 70 ° C., the cyclic level is lowered to about 80 ppm, the conversion rate is lowered to about 88%, , If the reaction time is reduced to about 1 hour, the cyclic material is reduced to about 50 ppm, the conversion rate is lowered to about 89%, and if the catalyst level is cut in half, the cyclic material is reduced to about 90 ppm, and the conversion rate is Increases to about 93%, removes methanol within 30 minutes, the cyclic material decreases to less than about 50 ppm, the conversion rate rises to about 90%, and reducing the vacuum to a maximum of about 200 mmHg, the conversion rate is about While decreasing to 87%, the cyclic material is reduced to about 40 ppm.

Reducing the time and vacuuming to remove methanol has the most significant effect on reducing ring formation.

Color enhancement can be achieved by using reactants with better colors. Both methyl esters and polyhydroxy amines have a Gardner color of less than about 1, with amines being the most important. Using excess amine in the R-1 reaction, for example, an excess of and / or higher heat treatment temperatures of about 100% gives an improved amine color. The use of the crystallization step further improves the color.

The amide is preferably treated with an ion exchange resin, or more preferably an anion and a cation exchange resin to remove the color body. This treatment is accomplished below.

Example II

The overall process at 80% reactant concentration level for amide synthesis is as follows.

About 84.87 g C ₁₂ fatty acid methyl ester (Procter & Gamble methyl ester CE1270), about 75 g of N-methyl polyhydroxyamine of Example 1, about 1.04 g of sodium methoxide and a total of about 39.96 g of methyl alcohol (ca A reaction mixture consisting of 20% by weight of the reaction mixture). The reaction vessel includes a standard reflux mechanism equipped with a drying tube, a condenser and a mechanical stirring blade. N-methylglucamine / methanol is heated with stirring under nitrogen (reflux). After the solution has reached the desired temperature, ester and sodium methoxide catalyst are added. The reaction mixture is kept at reflux for about 6 hours. The reaction should be complete in about 1.5 hours. After removal of the methanol, the recovered product is about 105.57 g. Chromatography shows only the presence of small amounts of unwanted ester-amide byproducts and no detectable cyclization byproducts.

The above description is generally directed to solvent aids for preparing fatty acid amide derivatives using N-methyl polyhydroxyamines such as N-methylglucamine, as well as fatty methyl esters, but without departing from the spirit and scope of the present invention. It is understood that changes are available. Thus, reducing sugars such as fructose, galactose, mannose, maltose and lactose, and sugar sources such as high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup, etc. Carmine substitute).

Surprisingly, various fats and oils (triglycerides) can be used here instead of the above fatty esters and, in completeness, are not clearly improved. For example, fats and oils such as soybean oil, cottonseed oil, sunflower oil, iron oil, pork oil, safflower oil, corn oil, canola oil, peanut oil, fish oil, rapeseed oil, and the like (or their cured ( Hydrolyzed) form can be used as a source of triglyceride esters for use in the present process. If triglycerides are used, the reaction proceeds to completion and there are few by-products to be removed. In particular, greater than about 95% completion is possible. Preferred triglycerides are palm phosphorus oil, coconut oil, palm oil and iron oil.

[refine]

The surfactant produced by the above process is surprisingly pure. Such, in order to produce a very clean product, it requires very large purity. Therefore, it is necessary to treat the surfactant product with at least one treatment selected from reducing bleaching and ion exchange treatment.

Reducing bleaching is known as a method of reducing / removing color bodies and / or color body precursors which are later converted into color bodies by the action of light, oxygen, interaction with other substances and the like. However, in order to treat N-alkyl polyhydroxy amine amide surfactants, it is necessary to guard against the formation of soap as shown below.

The use of hydrogen and hydrogenation catalysts can also provide good reducing bleaching without excessive soap formation, but such techniques are usually more complex and require special equipment. Preferred hydrogenation catalysts are shown below.

It will be appreciated that the preparation of cleaning surfactants from such new sources is an important advantage of the present process. This process is particularly useful especially when producing long chains (eg C ₁₈ ) and unsaturated fatty acid polyhydroxy amides because relatively mild reaction temperatures and conditions form minimal byproducts in the desired product. The preformed portion of the polyhydroxy fatty acid amide surfactant can be used to assist in initiation of the R-2 amide formation reaction when triglycerides or long chain methyl esters are used as reactants.

Example III

Purification of N-methyl glucamine proceeds as follows.

About 2500 g of an aqueous solution containing about 45% by weight of general grade N-methyl glucamine are charged to a rotary evaporator, which is about 957 g of concentrate corresponding to a solid concentration in about 75% of the evaporator residue. Until it is collected, it is heated to about 71 ° C. under a Hg vacuum of 27.5. The residue is mixed with about 660 g of anhydrous methanol and quenched to about 1-2 ° C. using an N-methyl glucamine ice bath, so that the N-methyl glucamine crystals give a white slurry. About 1100 g portion of the slurry is charged to a Waring blender that is mixed for about 3-4 minutes prior to filtration using a Buchner funnel. After the sample is filtered off and dried, it is washed twice with about 165 g of aliquots of cooled (about 5 ° C.) methanol and once with about 330 g of cooled methanol. The final cake yields about 438 g of purified N-methyl glucamine at about 16% volatiles for a yield of about 83% solids in the first feed.

The table below describes the color and thermal stability improvements produced by this procedure. Purified crystals are dissolved in distilled water to yield the same solid concentration as the original feed. The color is measured on the sample as% transmission using a Milton Roy Spectronic 21D spectrometer at about 420 nm and about 21 cm cells. The sample is also tested for thermal stability by raising the material to about 180 ° C. in an oil bath under an inert atmosphere for about 1 hour.

The treated sample is rediluted to about 50% concentration to replenish the water lost during the heat treatment and show the subsequent color.

Example IV-A

(Preparation of Amides with Uncrystallized Amine)

An aqueous solution of general grade N-methyl glucamine (about 332.62 g) containing about 54% by weight solids is charged to a standard 1 liter reaction flask apparatus containing a mechanical stirring blade, condenser and receiver. Over about 1 hour 20 minutes, the solution is gradually heated to about 132 ° C. and the pressure is reduced to about 66 cm Hg vacuum to remove the collected and condensed water from the receiver.

About 201.71 g of Procter & Gamble CE-1295 methyl ester and about 37.20 g of propylene glycol are added to the dried N-methyl glucamine. After stirring, about 15.01 g of sodium methoxide solution (about 25% by weight in methanol) and about 14 g of methanol are added to the reactor and the time is recorded. The mixture is cooled to about 85 ° C. when methanol is distilled off at atmospheric pressure. After about 30 minutes, no more methanol is distilled distinctly and vacuum is slowly applied to the reaction vessel to remove residual methanol and complete the reaction. The reaction is complete when the vacuum reaches about 66 mm Hg without excessive foaming. After collapse of the vacuum with nitrogen, about 126.86 g of water and about 74.60 g of ethanol are added to the mixture. The resulting glucose amide solution is dark yellow and has a transmittance of about 54.9% at about 420 nm.

Example IV-B

(Amid Crystallization to Crystallized Amine)

A reaction mixture consisting of about 121.0 g of purified N-methyl glucamine filter cake (about 16% volatile) from Example III, about 112.1 9 of Procter & Gamble CE-1295 methyl ester and about 19.7 g of propylene glycol 1 liter of reaction vessel equipped with a mechanical stirring blade, a condenser and a receiver is filled. The mixture is heated to about 80 ° C. with stirring and kept under slight vacuum for about 30 minutes to remove residual moisture and methanol from the filter cake.

After collapse of the vacuum with nitrogen, about 8.4 g of about 25% sodium methoxide solution is charged to the reactor and the time is recorded. Methanol is distilled off and collected in the receiver. After about 1 hour, vacuum is slowly removed to remove residual methanol and the reaction is complete. After about 2 hours 30 minutes, the desired vacuum is achieved and no more methanol is distilled off. The vacuum is collapsed with nitrogen and about 65.1 g of distilled water and about 39.5 g of ethanol are added to the mixture. The resulting glucose amide solution is very pale yellow with a transmittance of about 88.9% at about 420 nm.

Example V

After consumption by polyhydroxy amide elution, the regeneration of the strongly basic anion exchange resin is carried out as follows.

Ethanolic HCl solution is prepared by adding about 27.4 g of concentrated (salt = about 36.5 weight%) HCl to about 972.6 g 3 A ethanol.

The diluted caustic solution is prepared by dissolving about 15.3 g of NaOH pellets (salt = about 98%) in about 1484.7 g of distilled water.

Approximately 450 ml of spent Amberlite IRA-410 resin is charged into a 500 ml graduated dispense cylinder and washed with about 1 liter of warm distilled water to remove residual amide. The resin is acidified by washing with about 1 liter of about 5% ethanol HCl solution (prepared according to above) and then with about 1 liter of ethanol to complete the removal of fatty acids. The resin is then washed with about 1 liter of warm distilled water to rehydrate the resin.

The resin is then regenerated by slowly eluting about 11/2 liter of an aqueous solution of about 5% NaOH through the resin. The resin is then washed with distilled water until the pH is about 8.

After consumption by polyhydroxy amide elution, the regeneration of the strong acid cation exchange resin proceeds as follows:

Ethanolic HCl solution is prepared by adding about 27.4 g of concentrated (about 36.5 weight%) HCl to about 972.6 g of 3 A ethanol.

Approximately 450 ml of consumed Amberlite IR-120 Plus strong acid cationic resin is charged to 500 ml graduation dispense cylinder, wrapped with about 50 ° C. heating tape and washed with about 1 liter of warm distilled water to remove residual amide product. The resin is acidified by eluting about 1 liter of ethanol HCl and then washed with warm distilled water to rehydrate the resin.

Regeneration is completed by slowly eluting an additional 1 liter of about 5% aqueous HCl through the resin. The resin is then washed with distilled water until the pH is about 5.

Example VI

About 200 ml of recycled Amberlite IR-120 Plus of Example VII is filled into a about 250 ml graduated cylinder wrapped with a heating tape set to about 50 ° C. About 2000 g of glucose amide prepared from N-methyl glucamine crystallized according to Example IV-B is eluted through the resin and collected in about 200 g of allicoat.

Then, about 1800 g of eluate from the cation column is eluted through about 200 ml of regenerated Amberlite IR-410 strong anion resin from Example VII. This column temperature is maintained at about 50 ° C. with the aid of an electric heating tape. The eluate is collected in 16, about 100 g of alicoat.

Prior to the resin treatment, the analysis of glucose amides showed the following approximate quality and composition.

Transmission at about 360 nm = 74.1%

N-methyl glucamine = 2.8%

Fatty acid / methyl ester = 4.9%

Glucose Amides = 55.6%

Ester amide = 0.2%

After the resin treatment, the quality and composition of the color of the product is greatly improved.

Transmission at 360 nm = 93.3%

N-methyl glucamine = 0.1%

Fatty acid / methyl ester = 0.6%

Glucose Amides = 55.5%

Ester Amide = 0.1%

EXAMPLE VII

After consumption by polyhydroxy amide elution, a second method of regeneration of the strongly basic anion exchange resin is carried out as follows:

Ethanolic HCl solution is prepared by adding about 27.4 g of concentrated (about 36.5 weight%) HCl to about 972.6 g of 3A ethanol.

A dilute solution of about 7 mole ethoxylated lauryl alcohol is prepared by dissolving about 9 g of ethoxylate in about 9 g of ethanol and about 1482 g of warm distilled water.

About 450 ml of the spent resin is filled into a 500 ml graduation dispense cylinder, wrapped with a heating tape and maintained at about 50 ° C. The resin is washed with about 1 liter of warm distilled water to remove residual amide. About 1 liter of warm, about 5% aqueous HCl is eluted through the resin to acidify. The column is fixed at about 50 ° C. for about 2 hours and the fatty acids migrate to the surface of the resin. The column is backwashed with about 11/2 liter of warm ethoxylate solution to remove fatty acids from the column.

The resin is then regenerated by slowly eluting about 11/2 liter of 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 recycled in the same manner as in Example VII.

Glucose amide prepared by the method of Example IV-A, which has amber color and transmittance of about 32.1% at 360 nm, was passed through these ion exchange resins, and the color was pale yellow with a transmittance of about 82.2% at about 360 nm. Is improved.

EXAMPLE VII

N-methyl glucamine, which has good color stability and continues to produce high quality glucose amide, is prepared by the following method.

About 2 gallons of high pressure vessel example Charge about 360g of Grace 4200 Raney nickel catalyst, about 920g of 50% methyl amine and about 1000g of water as 50% suspension in water. The reactor is pressurized with hydrogen to about 1500 Psig. The reactor contents are heated to about 50 ° C with stirring. It is charged with about 2600 g of Clear Sweat ^™ 99DE corn syrup and the contents are reacted at about 50 ° C. for about 2 hours. When hydrogen is consumed by the reaction, fresh hydrogen is added to maintain pressure. At about 2 hours the sample is removed from the reactor and the composition is roughly measured.

N-methyl glucamine = 95.0%

n-glucosylamine = 1.0%

Glucose = 1.0%

Sorbitol = 0.9%

This material is pale yellow and results in a continuous reaction to glucose amide following the procedure of Example IV-A resulting in a pure black product.

While the hydrogen pressure is maintained at about 1500 psig, the temperature of the reaction mixture remaining in the high pressure vessel is raised from about 50 ° C to about 100 ° C over about 60 minutes. After reaching about 100 ° C., the reactor is rapidly cooled under hydrogen pressure by introducing cooling water into the reactor coil. If the mixture is cooled to about 30-50 ° C., the material is withdrawn from the reactor. Its composition is approximately as follows:

N-methyl glucamine = 97.3%

n-glucosylamine not detected

Glucose not detected

Sorbitol = 0.8%

Glucose amide is prepared according to the procedure of Example IV-A using this colorless material, resulting in a pale yellow product.

EXAMPLE VII

Amide and Base Treated Esters Made from Crystallized NMG

Approximately 49.1 kg of Procter% Gamble CE-1295 methyl ester is charged into a 72 liter distillation flask equipped with a condenser and receiver. About 900 g of sodium methoxide solution (about 25% by weight in methanol) is added to the ester. At an absolute pressure of less than about 10 mmHg, the ester is heated to about 140 ° C. The distillate is concentrated and collected in the receiver. Discard the first approximately 618 g collected in the receiver and collect the remaining distillate as "colorless", low-direction methyl laurate.

About 175.0 g of n-methyl glucamine crystals purified according to Example III were dissolved in water to prepare about 375.0 g of an aqueous solution. This solution is filled into a standard 1 liter reaction flask apparatus containing a mechanical stirring blade, a condenser, and a receiver. Over about 2 hours 40 minutes, the solution is gradually heated to about 130 ° C. and the pressure is reduced to about 26 inches of Hg vacuum to remove condensed and collected water in the receiver.

To the dehydrated n-methyl glucamine is added about 195.9 g of distilled methyl laurate and about 36.5 g of propylene glycol. After stirring, about 14.5 g of sodium methoxide solution (about 25% by weight in methanol) is added to the reactor and the time is recorded. When the methanol is distilled under atmospheric pressure, the mixture is cooled to about 85 ° C. After about 30 minutes, no more methane is distilled distinctly and the reaction vessel is slowly vacuumed to remove residual methanol and complete the reaction. If the vacuum reaches about 25 inches of Hg without excessive bubble formation, the reaction is complete. After collapse of the vacuum with nitrogen, about 123.0 g of water and about 72.3 g of ethanol are added to the mixture. The resulting glucose amine solution is "colorless" and has a transmittance of 95% at 420 nm.

EXAMPLE VII

Amides Prepared Using Triglycerides

Triglyceride reactants include CRISCO® oil, palm oil, sunflower oil, canola oil, rapeseed oil, coconut oil palm stearin, and corresponding hydrogenated oils. The catalyst is a monohydric alcohol, or an alkali metal salt of polyhydroxyalcohol, for example sodium methoxide. The reaction medium is a nonionic surfactant, for example NEODOL® 10-8 or 23-3, or GEVAPOL 26-L-5.

The reaction is carried out in fusion. For triglycerides, N-methylglucamine, nonionic surfactants and triglycerides in a molar ratio of about 2.3: 1 to 2.9: 1 are fused together at about 120-140 ° C. under vacuum for about 30 minutes. For N-methyl glucamine, about 7.5 mole% sodium methoxide is added to the reaction mixture. The reaction mixture becomes homogeneous after a few seconds. The reaction mixture is immediately cooled to about 85 ° C. The reaction mixture is kept in vacuo for about 1-2 hours and complete at this point.

As an alternative, N-methylglucamine is mixed with nonionic surfactant, triglycerides and catalyst at room temperature. The mixture is alternatively heated to 85-90 ° C. under vacuum or nitrogen. The reaction mixture is cleared after 1 to 1.5 hours. The reaction mixture is maintained at about 85 ° C. for about 2-3 hours.

More particularly, about 127.45 g of N-methylglucamine powder is added to a 500 ml 3 neck, round bottom flask with internal thermometer, vacuum line, nitrogen line and mechanical stirrer. N-methylglucamine melts at about 130-140 ° C. and is dried under reduced pressure. Cured palm kernel oil (about 156.41 g) is added to a 500 ml three neck round bottom flask with internal thermometer and vacuum line. The cured palm kernel oil is melted at about 130-140 ° C. and dried under reduced pressure. Dry cured palm kernel oil and about 31.54 g propylene glycol are added to N-methylglucamine with mixing. About 1.76 g sodium methoxide as a 25% mixture with methanol is added to this mixture while mixing and methanol is removed by vacuum. The mixture becomes homogeneous after about 1.5 minutes and cooling is carried out at this time. The mixture is cooled to 90 ° C. for about 7 minutes and held at this temperature for about 85 minutes. The mixture is poured out and analyzed by gas chromatography.

Removal of water from the reactants minimizes the formation of fatty acids. Preferably the water level is less than about 0.1%.

[Example XI]

Treatment of amides and borohydrides

About 200 g of glucose amide are added to a 1 L, three neck round bottom reaction flask with thermometer on top load balance. The reactor is transferred to a heated mantle and connected to a mechanical stirrer.

The temperature is raised and maintained at about 38 ° C. for the duration of the treatment. About 1.23 g of commercially available sodium borohydride and about 0.20 g of powdered sodium borohydride are added to the reactor.

There is about 0.49 g of sodium hydroxide in borohydride, which raises the pH from about 8.7 to about 10.4. The starting color of the amide is about 54% transmission at 420 nanometers and about 76% after about 2 hours of treatment. The final pH of the solution is as low as about 8 with 31% hydrochloric acid.

pH 10.4 precludes increased production of soap, but pH above about 10 requires borohydride stability. Untreated N-methylglucamine amide typically has a soap content of about 3.09. The pH / soap content of borohydride treated N-methylglucamine varies approximately as follows: 10.1 / 3.14; 10.3 / 3.16; 10.6 / 3.17; And 11.O / 3.41. In the end, the pH should be less than about 10.9 during the treatment.

[Example II]

The polyhydroxy fatty acid amide surfactant solution, as in Example II before purification, with less than about 70% permeation, is treated with hydrogen in a high pressure stirred reactor and heated by an internal coil connected to a steam / water mixing device. . The surfactant solution contains approximately: 60% surfactant, 22% water, 12% ethanol and 6% propylene glycol. Approximately 1000 g of solution is slurried with about 1.2 g of palladium catalyst (5% palladium on carbon) wet to about 50% humidity. The reactor is sealed and the stirrer starts at about 500 rpm. The reactor is repeated (five times) slowly pressurized to about 200 psi and then slowly counted out. The reactor is then pressurized to about 400 psi and the stirrer is increased to about 1200 rpm. The temperature is raised to about 66 ° C. and the reaction is run for about 2 hours and the product is filtered under hydrogen pressure to remove the catalyst. % Transmission is about 80% or more.

Claims (13)

Useful methods for the preparation of amides of N-alkylamino polyols comprising: (1) N-alkylamino polyols having a Gardner color of less than 1, crystallizing N-alkylamino polyols from an aqueous solution or a water / organic solvent mixture Purity and improved by the method of recovering the N-alkylamino polyol, the crystallization cooling the aqueous mixture of N-alkylamino polyol to 0-10 ° C. and by filtration, centrifugation, or by filtration and centrifugation. Separate very pure crystals of N-alkylaminopolyol from the supernatant, concentrate the aqueous mixture of N-alkylamino polyols to at least 70% solids as compared to before cooling, then add 10-200 parts of organic solvent to the concentrated solution, Improved purity is achieved by washing the resulting filter cake or centrifugal cake with 0.25-1.25 parts of cooled 0-5 ° C. solvent. Reacting an N-alkylamino polyol having a raw material of a fatty acid acyl group selected from the group consisting of fatty acids, fatty acid anhydrides, fatty acid esters and mixtures thereof having a transmittance of more than 98% at 460 nm, wherein the reaction is less than 3 hours. While, at 40 ° C. to 135 ° C., methanol, ethanol, propanol, isopropanol, butanol, glycerol, 1,2 in the presence of a base catalyst at which the level of the catalyst for the fatty acid ester is at a level of 5-8 mol% of the fatty acid ester. Preparation of amides of N-alkylamino polyols carried out under non-oxidizing conditions, including reactions carried out in an organic hydroxy solvent selected from the group consisting of -propylene glycol, 1,3-propylene glycol and mixtures thereof fair; (2) A method for removing an impurity selected from the group consisting of amines, fatty acids, and mixtures thereof present in the step (1) from an aqueous cleaning surfactant solution, comprising treating the surfactant solution with an ion exchange resin. Process: and (4) A process for regenerating a strongly basic ion exchange resin containing a fatty acyl anion group, comprising acidifying the resin to produce a fatty acid corresponding to the fatty acid acyl anion group, and removing the fatty acid by dissolving it in an organic solvent. The soap present according to claim 1, wherein the step (1) comprises treating the resulting N-alkylpolyhydroxy amine amide with an ion exchange resin and then treating the N-alkyl polyhydroxy amine amide with an acidic ion exchange resin first. Converting to fatty acids, removing any residual amines that may be present, and then removing the fatty acids by treatment with a basic ion exchange resin. The process according to claim 1 or 2, wherein the step (1) comprises treating the N-alkyl polyhydroxy amine amide with a reducing bleach. The process according to claim 1 or 2, wherein (1) the process comprises maintaining the pressure in a vacuum of less than 200 mmHg and removing the solvent from the reaction product for less than 1 hour. The process according to claim 1, wherein the process (2) comprises impurities containing fatty acid soap, and the solution is first treated with an acidic ion exchange resin to remove amines, and the fatty acid soap is converted to a fatty acid, followed by a basic ion exchange resin. Removing the fatty acids by means of. The method according to claim 1, wherein the fatty acid acyl group of the step (4) contains 6 to 30 carbon atoms. The method according to claim 1 or 6, wherein the solvent of step (4) is ethanol. The fatty acid according to claim 1, which is selected from the group consisting of (1) N-alkylamino polyols having a Gardner color of less than 1, and fatty acids, fatty acid anhydrides, fatty acid esters and mixtures thereof having a transmittance of more than 98% at 460 nm. Reacting the raw material of the acyl group, (2) removing impurities selected from the group consisting of amines, fatty acids, and mixtures thereof from an aqueous solution of amides of N-alkyl amino polyols, which step treats the solution with an ion exchange resin, In the case of a strongly basic ion exchange resin containing a fatty acyl anion group, the strong basic ion exchange resin is acidified to form a fatty acid corresponding to the fatty acid acyl anion, which is dissolved in an organic solvent to remove the fatty acid. Including regenerating; And in addition (3) non-oxidizing, comprising removing a chromophore, chromophore precursor, or mixture thereof from the amide of the N-alkylamino polyol, comprising treating the amide of the N-alkylaminopolyol with a reducing bleach. Process for the preparation of amides of N-alkylamino polyols carried out under conditions. Methods useful for the preparation of amides of N-alkylamino polyols comprising the following steps; (1) N-alkylamino polyols having a Gardner color of less than 1, with improved purity by a method of crystallizing N-alkylamino polyols from aqueous solutions or water / organic solvent mixtures and recovering N-alkylamino polyols, The crystallization cools the aqueous mixture of N-alkylamino polyols to 0-10 ° C. and separates very pure crystals of N-alkylaminopolyols from the supernatant by filtration, centrifugation, or filtration and centrifugation, and N-alkyl The aqueous mixture of amino polyols is concentrated to at least 70% solids as compared to before cooling, then 10 to 200 parts of organic solvent is added to the concentrated solution and the resulting filter cake or centrifugal cake is added to 0.25 to 1.25 parts of cooled 0-5 N-alkylamino polyols having improved purity, fatty acids having a transmittance of more than 98% at 460 nm, carried out by washing with a solvent, Reacting raw materials of fatty acid acyl groups selected from the group consisting of dispersing anhydrides, fatty acid esters and mixtures thereof, wherein the reaction is carried out for less than 3 hours at 40 ° C. to 135 ° C., the level of catalyst for fatty acid ester Organic 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 at a level of 5 to 8 mole% A reaction carried out in a hydroxy solvent, comprising: a process for preparing an amide of an N-alkylamino polyol which is carried out under non-oxidizing conditions, including this reaction; And (3) A method for removing the chromophore, chromophore precursor, or mixture thereof present in step (1) from the N-alkyl polyhydroxy amineamide, wherein the N-alkyl polyhydroxy amine amide is treated with a reducing bleach. , Performing the treatment at a pH of 10 to 10.9. 10. The soap according to claim 9, wherein the step (1) comprises treating the resulting N-alkylpolyhydroxy amine amide with an ion exchange resin and then treating the N-alkyl polyhydroxy amine amide with an acidic ion exchange resin first. Converting to fatty acids, removing any residual amines that may be present, and then removing the fatty acids by treatment with a basic ion exchange resin. The process according to claim 9 or 10, wherein (1) the process comprises treating the N-alkyl polyhydroxy amine amide with a reducing bleach. The process according to claim 9 or 10, wherein (1) the process comprises maintaining the pressure in a vacuum of less than 200 mmHg and removing the solvent from the reaction product for less than 1 hour. The process according to claim 9, wherein the process (3) comprises performing the treatment in the presence of a hydrogenation catalyst selected from the group consisting of nickel and palladium catalysts, wherein the reducing bleach is hydrogen.