FIELD OF THE INVENTION

The present invention relates generally to N-acyl amino acid surfactants and derivatives and, in particular embodiments, N-acyl amino acid surfactant compositions with low amounts of impurities.

BACKGROUND OF THE INVENTION

Surfactants are the single most important cleaning ingredient in cleaning products. Environmental regulations, consumer habits, and consumer practices have forced new developments in the surfactant industry to produce lower cost, higher-performing, and environmentally friendly products.

Surfactants are key ingredients playing important roles in a variety of applications and consumer products such as in detergents, hard surface cleaners, fabric softeners, body wash, face wash, shampoo conditioners, conditioning shampoos, and other surfactant-based compositions. Many catalogs and patents describe surfactant options that can be too expensive to use. The high cost is many times due to the starting materials used to make such surfactants, inefficient reaction schemes and/or complex processes required for their manufacture to meet specific quality atributes. Accordingly, new methods are needed to produce surfactant compositions at low cost containing minimal impurities or additives.

N-acyl amino acid surfactants can be commercially manufactured from the corresponding fatty acid chlorides and amino acids using Schotten-Baumann chemistry' as shown in equation I. equation 1

This amidation reaction is typically carried out in water, but the use of mixed water-solvent systems has been reported. Typically, the sodium N-acyl amino acid surfactant formed is obtained in the form of an aqueous composition containing 20-30% active with invariably high levels of undesirable inorganic salt (Nad). The latter can be removed via additional post-reaction steps that can add significant cost and complexity. This surfactant making method is expensive and requires the manufacture of fatty acid chlorides which uses chlorinating agents such as phosphorous trichloride, (PCb), phosphorous pentachloride (PCl ₅ ), thionyi chloride (SOC1 ₂ ), oxalyl chloride (COCl)2 or phosgene (poisonous gas). These chlorinating agents are quite reactive, can be toxic, and might require very special handling and metallurgy. Also, depending on the specific chemistry and process used, separating the fatty acid chlorides away from byproducts and catalysts used has been difficult to solve. Thus, the products may contain undesired impurities that can be carried through to the synthesis of the corresponding surfactant.

One attempt to overcome these deficiencies is the synthesis of N-acyi glycinates and N- acyl alaninates by reacting corresponding amino acids with the fatty- ⁷ acid itself. The process generates highly colored (yellow) surfactant compositions containing relatively high levels of acylated di- and tri-peptide by-products with significant levels of unreacted fatty acid. Further, 100 to 200% mole excess of fatty acid is required for tins process.

Fatty alkyl esters have also been used as starting materials. For example, methyl laurate can be reacted with the sodium salt of an amino acid and sodium rnethoxide in methanol in a pressurized reactor, with reaction pressures varied from 5-50 psig depending on the reaction temperature. Conversion to N-aeyl sarcosinate from this reaction can be only 22%, while N-acyl alamnate conversion can be 67%. The N-acyi ammo acid surfactant formed can be isolated by adding more methanol to the crude reaction mixture, then filtering it off and washing solid obtained with more methanol and finally drying isolated surfactant in the oven. The filtrate can be concentrated and analyzed to determine proportions of methyl laurate, and/or sodium salt of amino acid, and can be reused in the following batch. Hence, a further disadvantage of this approach is that it requires several process steps to isolate the reaction product.

In yet another conventional reaction, N~acyl amino acid surfactant is prepared using a polyol at 50-70 wt. % of the combined mass of the amino acid salt plus the methyl ester. However, the polyols used, glycerol and/or propylene glycol, remain in the final product mixture. Di-peptide impurities are found in the surfactant composition and the level varies depending on the level of polyol used in the reaction.

In summary, N-acyl amino acid surfactants made using these processes tend to contain high levels of undesirable by-products, such as salt (NaC1), di- and tri-peptide derivatives, or solvents such as methanol, glycerol and propylene glycol. Thus, there is a need for N-acyl amino acid surfactant compositions that are made under atmospheric conditions, are produced with low proportion of by-products and low levels of solvents or additives. SUMMARY OF THE INVENTION

The present disclosure atempts to solve one more of the needs by providing a surfactant composition comprising greater than 80%, by weight, of an N-acyl amino acid surfactant of formula (I): wherein R is an C ₅ -C ₂₁ alkyl substituent, Ri represents IT, or C ₁ to C ₄ alkyl radical, R ₂ represents IT, C ₁ to (h alkyl radical, or C ₁ to C ₄ hydroxyaikyl, R ₃ represents the functional moiety COOM. M is a cationic group selected from the group consisting of alkali metal salts and hydrogen. The composition is substantially free of NaCl and solvents such as medianol and glycerol. In a particularly preferred embodiment, the present disclosure also relates to surfactant compositions that are a solid and in still other embodiments an aqueous liquid composition.

The present disclosure further relates to a process for preparation of an N-acyl amino acid surfactant which comprises combining an amino acid, a waterless base a fatty' alkyl ester of formula (HI): wherein R is selected from an C ₅ -C ₂₁ alkyl substituent and R ^" is a C ₁ or higher alkyl substituent, preferably methyl, to form a mixture comprising an amino acid salt of formula (II) wherein Ri represents H, or C: to Cr alkyl radical, R ₂ represents H, C ₁ to C ₄ alkyl radical or C: to C ₄ hydroxyalkyl, R ₃ represents COOM, M is a cationic group selected from alkali metal salts. The temperature of the mixture is increased up to about 180°C or less, preferably up to about 160°C or less, or more preferably up to about 150°C to form a reaction mixture. Alkyl alcohol is continuously removed from the reaction mixture, and the reaction mixture is allowed to become substantially clear.

In another aspect, the invention is directed to a consumer product cleaning or personal care composition comprising about 0.001 wt.% to about 99.999 wt.%, preferably about 0.1 wt % to about 80 wt.% of N-acyl aianinate surfactant, as described herein, based on the total weight of the composition, and 0.001 wt.%to about 99.999 wt.% of one or more additional cleaning components, or one or more additional personal care components.

DETAILED DESCRIPTION OF THE INVENTION

Features and benefits of the present invention will become apparent from the following description, which includes examples intended to give a broad representation of the invention. Various modifications will be apparent to those skilled in the art from tins description and from practice of the invention. The scope is not intended to be limited to the particular forms disclosed and the invention covers all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.

As used herein, the articles including “the,” “a” and “an” when used in a claim or in the specification, are understood to mean one or more of what is claimed or described.

As used herein, the terms “include,” “includes” and “including” are meant to be nonlimiting.

The term “substantially free of’ or “substantially free from” as used herein refers to either the complete absence of an ingredient or a minimal amount thereof merely as impurity or unintended byproduct of another ingredient. A composition that is “substantially free” of/from a component means that the composition comprises less than about 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of the component.

As used herein, the term “ ^' solid” includes granular, powder, flakes, noodles, needles, extrudates, ribbons, beads and pellets product forms and comprise less than about 0.5%, 0.2.5%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of the water.

As used herein, “personal cleansing composition” includes personal cleansing products such as shampoos, conditioners, conditioning shampoos, shower gels, liquid hand cleansers, facial cleansers, and other surfactant-based liquid compositions.

It should he understood that every' maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly writen herein. Every minimum numerical limitation given throughout this specification will include every _' higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly writen herein. In this description, all concentrations are on a weight basis of the composition, unless otherwise specified.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”

N-acyl amino acid surfactant

The N-acyl amino acid surfactants disclosed herein have the following general formula

(I): where R is an C ₅ -C ₂₁ alkyl substituent, Ri represents H, or C ₁ to C ₄ alkyl radical, R ₂ represents H, C ₁ to C ₄ alkyl radical, or C ₁ to C ₄ hydroxy alkyl, R ₃ represents CQQM. M is a cationic group selected from the group consisting of alkali metal salts and hydrogen. Preferably, R is a C7- 17 alkyl substituent. The alkyl substituent may be branched or unbranched and preferably is unbranched.

The N-acyl amino acid surfactants described herein are typically not single compounds as suggested by their general formula (I), but rather, as one skilled in the art would readily appreciate, they comprise a mixture of several homologs having varied chain lengths and molecular weight. The N-acyl amino acid surfactants described herein may be either saturated or unsaturated.

The N-acyl amino acid surfactant composition of the present invention comprises at least 50% by weight of sodium N-acyl amino acid surfactant. The composition preferably comprises from 80-95% by weight of said N-acyl amino acid surfactant.

The N-acyl amino acid surfactant composition of the present invention further comprises fatty acid. The fatty acid may be present as free fatty acid or in the form of fatty' acid soap. The amount in the composition may range from 1 to about 10% by weight, preferably from 2 to 7% by weight, and more preferably from 3-5% by weight, specifically reciting all values within these ranges and any ranges created thereby. Beneficially, the N-acyl amino acid surfactant composition of the present invention may be substantially free of impurities including water, salt (NaCl), polyol solvents, acylated di- and tripeptide by-products, and methanol. The composition of the disclosure may comprise less than 5%, 2%, 1%, 0.1%, substantially free, and in some particularly preferred, free of one or any combination of these impurities.

The present disclosure further encompasses concentrated compositions, often referred to as pastes, and also solids, such as powders and tablets. These concentrated compositions may be combined with various adjunct ingredients (for example, water) to make a variety of detergent products, including personal cleansing compositions and laundry detergents.

Typically, inorganic salt (NaCl) is added to cleansing formulations made with sulfated surfactants to thicken the product. It has been surprisingly found that adding inorganic salt to the formulas that are substantially free of sulfated surfactants and/or using sulfate-free surfactants containing high inorganic salt in the presence of cationic conditioning polymer can cause product instability due to formation of a gel-like surfactant-polymer complex in the composition. Thus, it is desirable to avoid or minimize adding NaCl to the formula and/or use low inorganic salt. (NaCl) containing raw materials. Commercially available sulfate-free surfactants such as sodium cocoyi aianinate, and other amino acid-based surfactants, typically come with high levels of inorganic salt such as 5% or higher. Use of these high salt (such as, NaCl) containing raw materials in sidfate- free surfactant-based cleaning formulations can cause formation of undesired gel-like surfactant- polymer complex in the product before use. The surfactant composition of the invention described herein can enable tire formulation of stable cleansing products substantially free of sulfated surfactants.

Process of Making N-acyl amino acid surfactants

The process described herein allows for the preparation of N-acyl amino acid surfactants having low levels of impurities. The conventional Schotten-Baumann acid chloride route to N- aeyl amino acid surfactants - generates NaCl and other impurities, thereby yielding an undesirable output. Further, other reactions for making N-acyl amino acid surfactants use a low boiling point solvent and are carried out in closed reactors under pressure, and not under atmospheric conditions. High pressure reaction conditions are inherently more dangerous, time consuming, complicated and costly and are, therefore, not desirable. Others have used high boiling solvents such as polyols, glycerol and propylene glycol, to carry out reaction at atmospheric conditions, but the difficult-to- remove solvent stays with the surfactant. A suitable method for preparing an N-acyl amino acid surfactants as disclosed herein includes the steps of: i) neutralizing an amino acid with a waterless base to fonn an amino acid salt of formula (II): where R ₁ represents H, or C ₁ to C ₄ alkyl radical, R ₂ . represents H, C ₁ to C ₄ alkyl radical or C ₁ to C ₄ hydroxyalkyl, R ₃ represents COOM. M is a cationic group selected from alkali metal salts. The waterless base may comprise a C ₁ -C ₄ alkoxide, preferably sodium or potassium methoxide and may be used in an amount within the range of 1.00 to 1.50 moles per mole of amino acid, preferably 1.02 to 1.20 moles per mole of the amino acid and more preferably 1.05 to 1.10 moles per mole of the amino acid, specifically reciting all values within these ranges and any ranges created thereby.

^" The method for preparing an N-acyl amino acid surfactant further includes contacting the alanine salt of formula (11) with a fatty alkyl ester of formula (III): where R is selected from an C ₅ -C ₂₁ alkyl substituent, and R’ is a Ci or higher alkyl substituent, preferably methyl. It is worth nothing that the amino acid may be combined with the waterless base and the fatty alkyl ester in any order to form a mixture which comprises the salt of formula (P) above.

The method of preparing the N-acyl ammo acid surfactant further comprises the steps of increasing the temperature of the mixture to 180°C, preferably 160°C, more preferably 150°C, to form a reaction mixture; continuously removing alkyl alcohol from the reaction mixture and allowing the reaction mixture to become substantially clear. For example, the temperature of the mixture can be from about 65 °C to about I80°C or preferably from about 90°C to about 150°C, specifically reciting all values within these ranges and any ranges created thereby.

According to the present disclosure, the amino acid is a naturally occurring a-amino acid, the unnatural amino acid (opposite 'D' stereochemistry), or the racemic mixture. Suitable amino acids for use with the process of the present disclosure are selected from the group consisting of: alanine, sareosine, glycine, serine, and proline. It is worth noting that combinations of the foregoing amino acids may be utilized. For example, a combination of alanine and glycine may be utilized.

Suitable waterless bases for use are those selected from the group consisting of alkali metals, such as sodium, lithium and potassium: alloys of two or more alkali metals, such as sodium- lithium and sodium -potassium alloys; alkali metal hydrides, such as sodium, lithium and potassium hydride; and alkali metal alkoxides, especially those containing from about one to about four carbon atoms such as sodium methoxide, potassium methoxide, lithium methoxide sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium n-propoxide, potassium n-propoxide, sodium isopropoxide, potassium isopropoxide, sodium butoxide, potassium butoxide, sodium isobutoxide, potassium isobutoxide, sodium sec-butoxide, potassium sec-butoxide, and potassium tert- butoxide. Alkoxides are available in solid form or as solutions m the alcohol from which the alkoxide derives.

The relative molar amounts wherein the alkoxide is added to step i) in an amount within the range of 1.00 to 1.50 moles, preferably 1.02 to 1.20 moles, and more preferably 1.05 to 1.10 per mole of the ammo acid, specifically reciting all values within these ranges and any ranges created thereby. The alkoxide not consumed in the neutralization catalyzes the reaction between amino acid salt and the fatty alkyl ester. Thus, in the process described herein the preferred amount of alkoxide catalyst ranges from 2 to 20 mole percent or, more preferably from 5 to 10 mole percent, specifically reciting all values within these ranges and any ranges created thereby.

As used herein, the terms “fatty alkyl ester(s)" and “fatty acid esters” are intended to include any compound wherein the alcohol portion is easily removed, preferably esters of volatile alcohols, e.g Ci -4 alcohols (preferably methyl). Volatile alcohols are highly desirable. Methyl esters are the most highly preferred ester reactants. Suitable ester reactants can be prepared by the reaction of diazoalkanes and fatty acids or derived by alcoholysis from the fatty acids naturally occurring in fats and oils. Non-limiting examples are methyl octanoate (caprylate), methyl decanoate (caprate), methyl dodeeanoate (laurate), methyl tetradeeanoate (myristate), methyl hexadecanoate (palmitate), methyl octadecanoate (stearate), methyl oieate, ethyl dodeeanoate (laurate), ethyl tetradeeanoate (myristate), isopropyl dodeeanoate (laurate), isopropyl tetradeeanoate (myristate), and mixtures thereoff. Suitable fatty acid esters can be derived from either synthetic or natural, saturated or unsaturated fatty acids. Non-limiting examples of saturated fatty acids include caprylic, capric, lauric, myristic, palmitic, and stearic. Mixtures of fatty acids derived from coconut oil, cottonseed oil, palm kernel oil, soybean oil, cotton seed oil, rapeseed oil, safflower oil, canola oil (low erueic acid), and com oil and mixtures thereoff. Most preferred is coconut oil. It is preferred that the fatly alkyl esters he highly purified to remove color/odor materials, oxidation products, and their precursors. The free fatty acid level should be less than about 0.1%, preferably less than about 0.05%, by weight of the esters. In addition, the fatty acid alkyl esters should have the lowest level of moisture possible, since any water present will react with the aikoxide catalyst, inhibit the amidation reaction and can lead to elevated levels of soap.

The molar ratio wherein the fatty alkyl ester is added to step ii) in an amount within the range of 0.90 to 1.50 moles per mole of amino acid, preferably from 0.95 to 1.20 moles per mole of amino acid, or more preferably from 1.00 to 1.05 moles per mole of amino acid, specifically reciting all values within these ranges and any ranges created thereby. As shown in the examples, high active surfactant compositions with low' levels of impurities are possible without further processing steps wdien the amino acid salt and the fatty alkyl ester are used in about equimolar amounts. Using an excess of fatty alkyl ester would result in a surfactant composition contaminated with unreacted faty alkyl ester, thus requiring further processing for its removal. It is even less desirable to use the amino acid in excess since: (i) it is more expensive than the fatty alkyl ester, (ii) it does not have surface active properties and (iii) it would be difficult and costly to recover the unreacted ammo acid salt from the surfactant mixture.

Surprisingly the reaction between the alanine salt of formula (II) and faty alky ester of formula (ill) can be performed at atmospheric or even under negative pressure while continuously distilling off alkyl alcohol (e.g. methanol) from the reaction mixture. The temperature conditions for the amidation reaction may range from about 65°C to about 180°C or preferably from about 90°C to about 150°C, specifically reciting all values within these ranges and any ranges created thereby. Reaction progress can be monitored by tracking the amount of alkyl alcohol collected and/or by quantitative Ή NMR, or other analytical techniques. The final N-acyl amino acid surfactant reaction mixture, made under these relatively mild conditions, is fluid at the amidation reaction temperature. The high active surfactant melt can be flaked, grinded, prilled, pelletized, and/or made into beads, noodles, needles, and ribbons by known methods to those skilled in the art.

The reaction may utilize an inert gas headspace to help reduce the level of oxygen available during the reaction. The reduced level of oxygen helps to reduce the amount of oxidation of the constituents of the reaction. Oxidation of the constituents can cause discoloration. A suitable example of an inert gas that may be utilized is ni trogen.

Additionally, the benefit of performing the reaction described herein at atmospheric or even negative pressure is that the resultant surfactant can be (if desired) substantially free of any solvents. Additionally, the alkyl alcohol, e.g. methanol, vapors can he condensed and recovered outside of the reactor. This collection of alkyl alcohol vapors can be re-used to make more methyl esters. The resultant surfactant can have less than about 5.0 wt% of fatty acid methyl ester, preferably less than about 3.0 wt% or most preferably less than about 2.0 wt%, specifically reciting all values within these ranges and any ranges created thereby.

One of the advantages of the process of the invention it that the resultant N-acyl amino acid surfactant of formula (I) can be made to be substantially free of solvents, without using excesses of reactants, in high purity and without additional purifications steps.

In order to make a pumpable surfactant composition (pumpable at 50°C or below), the active surfactant melt without any further purification may be diluted into water in an amount of from 20 to 70 wt. percent of the melt, and preferably from about 25 to about 50 wt. percent of the melt. Alternatively, the water may be added to the high active surfactant melt at temperatures preferably below 120°C, more preferably under 100°C under good mixing. The amount of water needed will depend on target surfactant active level, target viscosity and the solubility behavior of the surfactant. Examples 4 and 7 demonstrate making an aqueous, fluid surfactant composition by either directly adding water to the high active surfactant melt or by discharging surfactant from the reactor into another vessel with water and appropriate mixing equipment. The solid form of the surfactant --- powder, flakes, pellets, beads, needles, noodles --- may also be dissolved in water to make a pumpable surfactant composition for formulators to easily incorporate in cleaning formulations.

The process of the present disclosure minimizes the level of acyiated di- and tri-peptide byproducts and soap formed by using low catalyst loading, excluding water from the amidation reaction and by gradually increasing reaction temperature from 90°C to about 150°C. Example 5 show's how higher level of undesirable soap, and oilier impurities are generated at higher temperatures and higher catalyst loading.

The process of the invention can be carried out as batch, semicontinuous, or in a continuous mode using suitable reactor(s) configurations. A conventional stirred-tank batch reactor equipped with a means for heating the reaction, a vapor column and condenser tor collecting volatile alkyl alcohol, an efficient stirrer capable of stirring the reaction product mixture, a means for blanketing the reactor contents with nitrogen, and optionally a vacuum system capable of achieving a vacuum of less than 20 mm of Hg may be used to prepare the N-acyl amino acid surfactant composition disclosed herein. Other reactors useful in the present invention is appropriately an apparatus with which liquid and solid mixtures of liquid and solid substances can be mixed using shear forces. In a static housing, the movement of the reaction mixture are brought about by internal mechanical stirring or mixing devices. The reaction apparatus can be a kneader or mixer equipped with sigma blades, masticator blades, or plough type agitator. Additional useful apparatuses include horizontal or vertical forced mixers equipped with mixing tools, for example sigma blades, masticator blades, plough type agitator, or throwing paddles, in combination with a cutting rotor.

Suitable horizontal forced mixers are those equipped with mixing tools or combinations of mixing tools such as, for example, sigma blades, masticator blades, or plough type agitator, in combination with a cutting rotor installed in the drum; more preferably horizontal forced mixers operating at a Froude number between 0.1 and 6, preferably between 0.25 and 5 and more preferably between 0.4 and 4, and equipped with mixing tools, or combinations of mixing tools, such as, for example sigma blades, masticator blades and plough type agitator in combination with a cutting rotor installed in in the dram. Without wishing to be bound by theory, in the treatment of mixing processes, the Froude number, Fr, plays a major role. This dimensionless quantity is indicative of the relationship between the forces of inertia and gravity acting on a moving particle. The following equation is applicable here:

Fr = v ² /rg where: v ^:::: peripheral speed [m/s] r = radius of mixing drum [m] g = acceleration of gravity [m/s ² ] v ^::: p x D x n /60 where:

D = diameter of mixing dram [m]

N = rotation rate of shaft [rpm]

The N-acyl amino acid surfactant composition and process for making described herein has a number of advantages over known commercial manufacturing processes and include:

1) High active surfactant composition substantially free of solvents and halide salts, like sodium chloride. 2} High conversion and yields can be achieved while avoiding laborious purification steps and concomitant product loss.

3} Fewer chemical engineering unit operations that can result in significant reduction in energy consumption.

4) Free of toxic and hazardous reagents, as described herein, and therefore the issue of handling these materials does not arise.

5) lire resultant surfactant is substantially free of sol vents that would need to be otherwise removed through additional post-reaction processing steps because they limit and/or impact the application and/or formulability of the surfactant.

Applications and Uses

In another aspect, the present disclosure is directed to a consumer product cleaning or personal care composition comprising about 0.001 wt.% to about 99.999 wt.%, preferably about 0.1 wt % to about 80 wt.% of tire N-acyl amino acid surfactants, e.g. alaninate, as described herein, based on the total weight of the composition, and 0.001 wt.% to about 99.999 wt.% of one or more additional cleaning components, or one or more additional personal care components. In various embodiments, the at least one cleaning component is selected from the group consisting of a surfactant, an enzyme, a builder, an alkalinity system, an organic polymeric compound, a hueing dye, a bleaching compound, an aikanolamine, a soil suspension agent, an anti-redeposition agent, a corrosion inhibitor, and a mixture thereof, in some cases, the composition is selected from the group consisting of a granular detergent, a bar-form detergent, a liquid laundry detergent, a liquid hand dishwashing composition, a hard surface cleaner, a tablet, a disinfectant, an industrial cleaner, a highly compact liquid, a powder, and a decontaminant. In a class of cases, the composition is enclosed within a sachet or a multi compartment pouch comprising both solid and liquid compartments.

In some embodiments, the at least one personal care component is selected from the group consisting of an oil, and emollient, a moisturizer, a carrier, an extract, a vitamin, a mineral, an antiaging compound, a surfactant, a solvent, a polymer, a preservative, an antimicrobial, a wax, a particle, a colorant, a dye, a fragrance, and mixtures thereof. In various cases, the composition is a shampoo, a hair conditioner, a hair treatment, a facial soap, a body wash, a body soap, a foam bath, a make-up rernover, a skin care product, an acne control product, a deodorant, an antiperspirant, a shaving aid, a cosmetic, a depilatory', a fragrance, and a mixture thereof. In a class of cases, tire composition is delivered in a form selected from the group consisting of a wipe, a cloth, a bar, a liquid, a powder, a creme, a lotion, a spray, an aerosol, a foam, a mousse, a seram, a capsule, a gel, an emulsion, a doe foot, a roll-on applicator, a stick, a sponge, an ointment, a paste, an emulsion spray, a tonic, a cosmetic, and mixtures thereof. In various embodiments, the composition further comprises a product selected from the group consisting of a device, an appliance, an applicator, an implement, a comb, a brush, a Substrate, and mixtures thereof. In some embodiments, the composition is dispensed from an article selected from the group consisting of a bottle, a jar, a tube, a sachet, a pouch, a container, a tottle, a vial, an ampoule, a compact, a wipe, and mixtures thereof.

EXAMPLES

Examples 1, 2, and 3 demonstrate the syntiiesis/preparation/manufacture of sodium N-acyi aianinate in greater than 85%, by weight, substantially free of solvent and sodium chloride (NaCl).

Analysis of the reactions conducted by a NMR method.

In a scintillation vial reaction product and (internal standard, IS) were weighed out in a precision balance (0.1 mg readability). D ₂ O (deuterium oxide) was added to the vial to fully dissolve sample and internal standard. The quantitative ¾ NMR spectra were recorded at 600 MHz using standard 'H pulse sequence, pulse width of 12.00, 60 sec delay, and a 2.59 sec acquisition time. NMR data was processed using MestReNova 10.0.2. The integration of the peak at 54.15 ppm for the rnethine (-CH-) group was used to calculate the wt. % of N-aeyl aianinate surfactant. The integration of tire triplet at 52.16 ppm for the methylene (-CH ₂ -) adjacent to the carboxyl group was used to calculate the wt. % of fatty acid soap. The integration of the peak at 53.30 ppm for the methine (-CH-) group was used to calculate the wt. % of unreacted alanine sodium salt. The integration of a singlet at 53.65 ppm for the methyl (CH ₃ -) was used to calculate the wt. % of any residual fatty alkyl methyl ester. The integrations were compared to the integration region of die IS and used for the calculations. The wt. % of each species was calculated using the following equation:

Wt. % (y) ^::: weight percent of ^" y” species in the sample A = NMR integration n = number of protons MW = molecular weight P ^::: purity of the internal s tandard

EXAMPLE 1

A glass reactor vessel was used to carry out a series of experiments. It was fitted with a stirring rod with Teflon blade, a Dean-Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. The reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-alanine (108,0 g, 1.20 mol) and 25 wt. % sodium methoxide solution (286.57 g, 1 .32 mol). The contents of reactor were heated to 65-68°C under nitrogen and stirring. At this point CE1270 (265.86 g, 1.20) - a product of P&G Chemicals, methyl laurate/methyi myristate mixture - was added to the reactor (10-15 min) from the addition funnel while maintaining good mixing, and die temperature set to 90°C. Methanol evaporated was collected in the Dean-Stark. The temperature of the reaction was increased gradually to 12Q°C, after it reached 90°C. The initial two-phase reaction became one-phase during this time, and the reaction was considered complete when methanol stopped condensing, 2.5 h. The molten, fluid product was poured out of the reactor and cooled to ambient temperature. The composition of the clear, glassy product analyzed by quantitative 'H NMR (qNMR) was 89.1% sodium lauroyl/myristoyl alaninate, 5.9% fatty acid soap, 3.3% sodium alaninate, 1.0% methanol, and no residual methyl ester. HPLC-MS analysis showed less than 0.1% of di- and/or tri -alaninate by-products.

EXAMPLE 2

A glass reactor vessel was fitted with a stirring rod with Teflon blade, a Dean-Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. The reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-alanine (108.0 g, 1.20 mol) and 25 wt. % sodium methoxide solution (280.0 g, 1.30 mol). The contents of reactor were heated to 65-68°C under nitrogen and stirring. At this point methyl laurate (257.81 g, 1.20 mol) was added to the reactor (~ 30 min) from the addition funnel while maintaining good mixing, and the temperature set to 90°C. Methanol evaporated was collected in the Dean-Stark. The temperature of the reaction was increased gradually to 120°C, after it reached 90°C. The initial two-phase reaction became one-phase during this time. The reaction was considered complete when methanol stopped condensing, 4 h from the start of methyl ester addition. The molten, fluid product was poured out of the reactor and cooled to ambient temperature. The composition of the clear, glassy product analyzed by quantitative ¹ H NMR (qNMR) was 87.2% sodium lauroyl alaninate, 5.7% sodium laurate, 3.2% sodium alaninate, 1.1% methanol, and 0.6% methyl laurate. HPLC-MS analysis showed less than 0.1 % of di- and/or tri-alaninate by-products.

EXAMPLE 3

A glass reactor vessel was fitted with a stirring rod with Teflon blade, a Dean- Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. The reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-alanine (45.0 g, 0.50 mol) and 25 wt. % sodium methoxide solution (129.8 g, 0.60 mol), lire contents of reactor were heated to 65-68°C under nitrogen and stirring. At this point cocoyl methyl ester (119. g, 0.525 mol) was added to the reactor (10 min) from the addition funnel while maintaining good mixing, and the temperature set to 100°C. Methanol e vaporated was collected in the Dean-Stark. The temperature of the reaction was increased gradually to 120°C, after it reached 100°C. The initial two-phase reaction became one-phase during this time. The reaction was considered complete when methanol stopped condensing. The molten, light-yellow, fluid product w as poured out of the reactor and cooled to ambient temperature. The composition of the clear, glassy product analyzed by quantitative ¹ H NMR (qNMR) was 86,0% sodium cocoyl alaninate, 6.4% soap, 1.4% sodium alaninate, HPLC- MS analysis showed less than 0.1% of di- and/or tri-alaninate by-products.

EXAMPLE 4

This example demonstrates the synthesis/preparation/manufacture of an aqueous solution of sodium N-acyi alaninate substantially free of sodium chloride (NaCl). A 2 liter glass reactor w'as fitted with a stirring rod with Teflon blade, a Dean-Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. The reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-alanine (100.9 g, 1.12 mol) and 25 wt. % sodium methoxide solution (2.79.3 g, 1.29 mol). The contents of reactor were heated to 65-68°C under nitrogen and stirring. At this point methyl laurate (240.60 g, 1.12) was added to the reactor (10-15 min) from the addition funnel while maintaining good mixing, and the temperature set to 110°C. Methanol evaporated w'as collected in the Dean-Stark. The temperature of the reaction was increased gradually to 120°C, after it reached 110°C. Methanol was no longer condensing after about 2 hrs. Heat turned off, and the hot, molten, fluid product was cooled down to about 110°C. Deionized water (650.8 g) was added into the reactor with good mixing until product dissolved to form a clear, slightly yellow solution. The resultant solution at 60°C was gently mixed until cooled to ambient temperature. The pH of the solution was adjusted from 13 to 10 with an appropriate acid solution. Analysis by quantitative ¹ H NMR showed it contained 22.9% sodium lauroyl alaninate, 1.5% fatty acid soap, 0.8% sodium alaninate, less than 0.5% of methanol, and no residual methyl laurate.

EXAMPLE 5

This example demonstrates how higher level of undesirable soap, and other impurities are generated at higher temperatures and higher catalyst loading. A glass reactor vessel was fitted with a stirring rod with Teflon blade, a Dean-Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. The reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-alanine ( 18.0 g, 0.20 mol) and 25 wt. % sodium methoxide solution (51.9 g, 0.24 mol). The contents of reactor were heated to 65-68°C under nitrogen and stirring. At this point methyl laurate (47.4 g, 0.21 mol) w'as added to the reactor from the addition funnel while maintaining good mixing, and the temperature set to 150°C. Methanol evaporated was collected in the Dean-Stark. The reaction became clear and bubbly after reaching 150°C in about 20 min. Reaction temperature was increased to 170°C. Reaction was terminated 30 min after, no more methanol was condensing. The clear, glassy product analyzed by quantitative ¾ NMR (qNMR) contained 71.0% sodium lauroyl alaninate, 11.8% sodium laurate, and 3.3% sodium alaninate. HPLC-MS showed the presence of a di-alaninate and N-methyl alaninate by-products in about 3.4% combined.

EXAMPLE 6

In a horizontal forced mixer which has been equipped with plough type agitator, a distillation column and an inert gas inlet, sodium methoxide solution (1368.3 g, 6.4 mol) and solid L-alanine (532.8 g, 6.0 mol) were mixed at a temperature of 22-35°C under nitrogen until a monophase liquid mixture formed. Coco fatty acid methyl ester (1283.8 g, 6.0 mol) was then added to the reactor, the temperature of the reaction mixture was gradually increased to 131°C, and the mixer was operated at a Froude number between 0.4 and 1 depending on the rheology of the composition. The alcohol from the base and alcohol formed during the reaction were removed by distillation from the forced mixer. Pie reaction was considered complete when methanol no longer was collecting. The molten product was discharged from the reactor and quickly cooled down to ambient temperature; 12.55 ,8 g of light-yellow solid was obtained. Quantitative Ή NMR (qNMR) analysis of the solid after grinding it gave the following composition: 88.7% sodium cocoyi alaninate, 4.2% soap, 2.7% sodium alaninate, 0.3% methanol, and 1.1% fatty acid methyl ester.

The resultant surfactant of the reaction described herein can be directly discharged into another vessel containing a solvent, e.g. water, to make a surfactant solution. Alternatively, the resulting surfactant can be discharged in solid form.

EXAMPLE 7

In a horizontal forced mixer which has been equipped with plough type agitator, a distillation column and an inert gas inlet, sodium methoxide solution (1391.4 g, 6.5 mol) and solid L-alanine (543.8 g, 6.1 mol) were mixed at a temperature of 22-31°C under nitrogen until a monophase liquid mixture formed. Coco faty acid methyl ester (1293.1 g, 6.1 mol) was then added to the reactor, the temperature of the reaction mixture was increased gradually to 146°C, and the mixer was operated at a Froude number between 0.4 and 1.2 depending on the rheology of the composition. The alcohol from the base and alcohol formed during the reaction were removed by distillation from the forced mixer. The reaction was considered complete when methanol no longer w'as collecting. The molten product was directly discharged from the reactor into another vessel containing deionized water and equipped with an overhead mixer and impeller to make a surfactant solution. Quantitative Ή NMR (qNMR) analysis of the surfactant solution obtained gave the following composition: 29.0% sodium cocoyi alaninate, 1.9% soap, 2.2% sodium alaninate, and 1.4% fatty acid methyl ester.

EXAMPLE 8 in a horizontal forced mixer which has been equipped with plough type agitator, a distillation column and an inert gas inlet, sodium methoxide solution (1527.1 g, 7.2 mol) and solid L-alanine (597. Ig, 6.7 mol) were mixed at a temperature of 22-32°C under nitrogen until a monophase liquid mixture formed. Coco faty acid methyl ester (1428.6 g, 6.7 mol) was then added to the reactor, the temperature of the reaction mixture was increased gradually to 147°C, and the mixer was operated at a Froude number of 0.8. The alcohol from the base and alcohol formed during the reaction were removed by distillation from the forced mixer. The reaction was considered complete when methanol no longer was collecting. The molten product was directly discharged unto a cooled surface while spreading the fluid product into thin layers of various thicknesses. Quantitative 'H NMR (qNMR) analysis of the surfactant solution obtained gave the following composition: 89.9% sodium cocoyi alaninate, 4.6% soap, 4.2% sodium alaninate, and 2.4%) fatty acid methyl ester.

EXAMPLE 9

In a 130-liter horizontal forced mixer equipped with plough type agitator, a distillation column with condensate receiver and an inert gas inlet, sodium methoxide solution (38.2 kg) and solid L- alanine 14.6 kg) were loaded and mixed at a Froude number of 0.8 and at a temperature of 22- 32°C under nitrogen for 20 minutes. Coco faty acid methyl ester (35.0 kg) was then added to the reactor, the temperature of the reaction mixture was increased gradually to 140°C. The alcohol from the base and alcohol formed during the reaction were removed by distillation from the forced mixer. The reaction was considered complete when methanol no longer was collecting. The molten product was cooled to ambient temperature, and the solid product broken into particles of various sizes. Quantitative ¹ H NMR (qNMR) analysis of the surfactant solution obtained gave the following composition: 94.8% sodium cocoyi alaninate, 3.4% soap, 1.8% sodium alaninate, and 0.1% fatty acid methyl ester.

COMPARATIVE EXAMPLE 10

A 300 mL stainless-steel Parr reactor was charged with L-alanine (18.0 g, 0.20 mol), 25 wt. % sodium methoxide solution (49.5 g, 0.23 mol), methyl !aurate (42.9 g , 0.20 mol), and additional methanol (9.7 g, ~ 40 wt. % based on the amount of charged starting materials). The reactor was sealed, stirrer set to 200 rpm, and heated to 85°C for 4 h. The reactor was cooled down to about 40-45°C and the pressure carefully released. The warm, reaction mixture contents poured into a glass baking sheet to evaporate solvent. The dry crude reaction product analyzed by quantitative 1H NMR and HPLC-HRMS: 27-29% sodium lauroyl alaninate, 25% methyl laurate, 10% sodium laurate soap, and significant levels of unreacted sodium alaninate.

COMPARATIVE EXAMPLE 11

A 300 mL stainless-steel Parr reactor was charged methyl laurate (47.4 g , 0.21 mol), and a methanolic solution of sodium alaninate separately made by mixing L-alanine (18.0 g, 0.20 mol), 25 wt. % sodium methoxide solution (51 .8 g, 0.24 mol). The reactor was sealed, stirrer set to 200 rpm, and heated to 90°C for 4 h 10 min. The reactor was cooled down to about 40-45°C and the pressure carefully released. The warm, reaction mixture contents poured into a glass baking sheet to evaporate solvent. A dry sample of the crude reaction product was analyzed by quantitative 1H NMR: 44,3% sodium lauroyl alaninate, 19,1% methyl laurate, 14.2% sodium laurate soap, and significant levels of unreacted sodium alaninate.

Examples 12 through 15 demonstrate the scope to synthesize/preparc/manufacture other sodium N-acyl ammo acid surfactants in greater than 85%, by weight, substantially free of solvent and sodium chloride (NaCl) via this process,

EXAMPLES 12 & 13

The experiments were executed using starting materials and conditions identical to Example 1, except L -alanine was replaced by sarcosine and glycine, respectively.

Table 1 ^a reaction product contained 1.5% of residual fatty acid methyl ester, ^b reaction product was no longer fluid and mixing property at the end of the reaction. ^c reaction product contained 1 ,7% of residual fatty acid methyl ester. ^d reaction product dissolved in water, Lovibond automated spectro-colorimeter (PFX-i series), 100- mm cell path.

EXAMPLE 14: Sodium Lauroyl Serinate

A glass reactor vessel was fitted with a stirring rod with Teflon blade, a Dean- Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. The reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-serine (20.2 g, 0.19 mol) and 25 wt. % sodium methoxide solution (45.2 g, 0.21 mol). The contents of reactor were heated under nitrogen and stirring until the L-serine had reacted forming a clear solution. At this point methyl laurate (40.7 g, 0.19 mol) was added to the reactor from the addition funnel while maintaining good mixing, and the temperature set to 100°C, Methanol evaporated was collected in the Dean- Stark. The reaction was considered complete when methanol stopped condensing. The composition of the reaction product analyzed by quantitative ₁ HNMR (qNMR) was 89.2% sodium lauroyl serinate, 3.2% soap, 1.6% sodium serinate, 0.9% methyl laurate and < 0.5% methanol.

EXAMPLE 15: Sodium Lauroyl Prolinate

A glass reactor vessel was fitted with a stirring rod with Teflon blade, a Dean-Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. Tire reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-proline (20.1 g, 0.17 mol) and 25 wt. % sodium methoxide solution (41.40 g, 0.19 mol). The contents of reactor were heated to 65-68°C under nitrogen and stirring. At this point methyl laurate (37.2 g, 0.17 mol) was added to the reactor from the addition funnel while maintaining good mixing, and the temperature set to 100°C. Methanol evaporated was collected in the Dean -Stark. The temperature of the reaction was increased gradually to 128°C, after it reached 100°C. The initial two-phase reaction became one- phase during this time. The reaction was considered complete when methanol stopped condensing. The molten, light-yellow, fluid product was poured out of the reactor and cooled to ambient temperature. The composition of the clear, glassy product analyzed by quantitative 1H NMR (qNMR) was 88.4% sodium lauroyl prolinate, 1.7% sodium prolinate. Soap level unknown, peaks overlapping with prolinate surfactant ring peaks. Methyl laurate not detected.

EXAMPLE 16

This example demonstrates the synthesis/preparation/manufacture of a fluid surfactant blend of consisting of sodium N-acyl alaninate / N-acyl glycinate in greater than 85%, by weight, substantially free of solvent and sodium chloride (NaCl).

A glass reactor vessel was fitted with a stirring rod with Teflon blade, a Dean-Stark trap equipped with a condenser, a nitrogen inlet, an addition funnel, and a thermocouple connected to a temperature control device. The reactor was heated by a heating mantle plugged into the temperature control device. The reactor was charged with L-aianine (89.1 g, 1.00 mol), glycine (26.3 g, 0.35 mol) and 25 wt. % sodium methoxide solution (320.0 g, 1,49 mol). The contents of reactor were heated to 68°C under nitrogen and stirring. At this point CE1270 (299.0 g, 1 ,35 mol) a product of P&G Chemicals, methyl laurate/methyl myristate mixture - was added to the reactor (~45 mm) from the addition funnel while maintaining good mixing, and the temperature set to 90°C. Methanol evaporated was collected in the Dean-Stark. The temperature of the reaction was increased gradually to I25°C, after it reached 90°C. The initial two-phase reaction became one- phase during this time. The reaction was considered complete when methanol stopped condensing, 3.5 h from the start of methyl ester addition. The molten, light-yellow, fluid product was poured out of the reactor and cooled to ambient temperature. The composition of the glassy product analyzed by quantitative ¹ H NMR (qNMR) was 67.2% sodium lauroyi/myristoyl alaninate, 24.2% sodium lauroyi/myristoyl glycinate, 5.1%) sodium soap, 2.4% sodium alaninate, 1.3% methanol and 0.1% methyl ester.

Examples 17-22

Examples 17-22 in Table 2 below show the ingredient lists for personal care products, e.g. shampoo, body wash and the like.

Table 2

1. Sodium Cocoyl Alaninate made according to the present disclosure.

2. Chemccinate DSLS from Lubrizol

3. Jordapon Cl Prill from BASF

4. Mackam DAB UL8 from Solvay

5. Amphosol HCA-HP from Stepan

6. Dehyton AB 30 from BASF

7. UCARE Polymer JR-30M from Dow

8. UCARE Polymer LR-30M from Dow

9. UCARE Polymer KG-30M from Dow

10. Flocare C 106 MSS available from SNF

11. Jaguar C500 from Solvay

12. jaguar Excel from Solvay

13. Versene 220 from Dow

14. Sodium benzoate from Emerald Kalama Chemical

15. Sodium salicylate from JQC (Huayin) Pharmaceutical

16. Kathon CG from Dow

17. Citric acid from ADM

Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodimen ts of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.