WO2008103136A1

WO2008103136A1 - Shea butter alkanolamides

Info

Publication number: WO2008103136A1
Application number: PCT/US2007/004582
Authority: WO
Inventors: Steven Rogers; Anthony O'lenick
Original assignee: Rutherford Chemicals LLC
Current assignee: Rutherford Chemicals LLC
Priority date: 2007-02-23
Filing date: 2007-02-23
Publication date: 2008-08-28
Anticipated expiration: 2009-08-23

Abstract

Novel alkanolamides prepared by the reaction of an alkanolamine and shea butter, preferably mild-processed shea butter (MPSB). Materials of the present invention are useful as cosmetic and personal care ingredients; they thicken shampoos and body washes, stabilize foam, and deliver to the hair and skin highly desirable unsaponifiables present in shea butter, including natural antioxidants.

Description

Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001

Shea Butter Alkanolamides Cross-Reference to Related Applications

[0001] Not applicable.

Statement Regarding Federally-Sponsored Research or Development

[0002] Not applicable.

Field of the Invention

[0003] The present invention relates to novel alkanolamides prepared by the reaction of an alkanolamine and shea butter, preferably mild-processed shea butter (MPSB). Materials of the present invention are useful as cosmetic and personal care ingredients; they thicken shampoos and body washes, stabilize foam, and deliver to the hair and skin highly desirable active ingredients present in shea butter, including natural antioxidants. Background of the Invention

[0004] Alkanolamides perform a variety of functions including viscosity enhancement, foam stabilization, emulsifϊcation and detergency. Specific applications include as humectants and hair detanglers. Chemically, alkanolamides are the reaction product of an alkanolamine and a fatty material. Fatty materials are a class of compounds which include fatty carboxylic acids, fatty methyl esters and fatty glycerides. Sources of fatty materials include coconut, peanut, soybean, and rapeseed oils, fractionated and non- fractionated fatty methyl esters and fatty acids of carbon chains of varying lengths. [0005] Variations in carbon chain lengths of the fatty sources can change the properties of alkanolamides. For example, a finished product having as an ingredient Cs to Cio fatty acids exhibit foam stability, but contribute little as thickeners. Ci₂ to Cj₄ fatty acids are particularly useful as foam boosters; they also show good viscosity building properties. Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001

Blending alkanolamides of differing carbon chain lengths can help optimize performance of the finished products in which they are incorporated. Lauric-myristic diethanolamides, for example, are common ingredients in formulations of high foaming products such as dishwashing detergent, bubble bath and hair shampoo. They also impart emolliency and conditioning effects to skin and hair, making them among the most commonly used alkanolamides in the personal care industry.

10006] Higher molecular weight, unsaturated fatty alkanolamides reduce foam and produce good viscosity build. Illustrative are oleic and linoleic alkanolamides which are excellent viscosity builders at low concentrations. This property makes them particularly useful in surfactant-containing formulations that otherwise are difficult to thicken. Higher molecular weight unsaturated products, however, are known to be oxidatively unstable and can interfere with fragrance in finished products.

[0007] Shea butter is a butter extracted from the kernel of Butrospermum parkii. This plant, also referred to as Vitellaria paradoxa, is native to Africa. The term butter describes a material that is a solid at room temperature, but melts at about 40⁰C. Chemically, shea butter is a triglyceride conforming to the following structure

R₃-C(O)-O-CH₂

wherein R_a, R_b and R_c each have one of the following compositions:

R Group Common Name Range (%) Tvoical (%)

C_{1 1}H₂₃ Lauryl 0.1 - 2.0 0.2

C₁₃H₂₇ Myristyl 0.5 - 2.0 1.0

C₁₅H3₁ Cetyl 2.0 - 6.0 4.0

C₁₇H₃5 Stearyl 25.0 - 50.0 35.0

C₁₇H₃₃ Oleyl 40.0 - 60.0 59.0 Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001

C17H31 Linoleyl 0.5 - 1.0 0.8

[0008] The average composition of R_b is different than R_n and R₀, the latter two being similar. The Rb moiety contains predominantly the unsaturated Ci₈ group (oleyl) while R_a and R₀ contain predominantly the saturated C is group (stearyl). Differences between internal (Rb) and terminal (R₃, R₀) substitution are seen in natural products but not in synthetic molecules produced in the laboratory.

[0009] The high levels of stearyl and oleyl groups make shea butter and its alkanolamide derivatives of particular interest in the personal care industry. While other raw materials used in personal care products have these species, the compounds of the present invention have significantly high concentrations of unsaponifiables, which posses highly desired antioxidant, ultra-violet radiation protection, and free-radical scavenging properties. MPSB of the present invention typically contains from about 5% to about 15% by weight of unsaponifiables. In contrast, other butters commonly used in personal care products have less than 2% unsaponifiables. For example, coca butter (from Theobroma cacao) averages 0.4% unsaponifiables and Illipe butter (from Shorea stenoptera) averages 1.1%. |0010] As described in greater detail below, the novel shea butter alkanolamide compounds of the present invention are produced by reacting shea butter, preferably MPSB, with an alkanolamine, preferably under specific mild processing conditions. By "mild processed" is meant processes that do not remove or otherwise diminish the amount or potency of active ingredients, particularly highly desired unsaponifiables. In one aspect of the present invention, mild processing is employed both at the time of harvesting and initial extraction (creating mild-processed shea butter) and during Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001 subsequent preparation of derivatives. These mild processes result in materials containing unexpectedly high amounts unsaponifiables, notably antioxidants. [0011] Prior art alkanolamides do not possess the antioxidant and free-radical scavenging properties of compounds of the present invention. For example, U.S. Patent 5,741,916 discloses the use of meadowfoam seed oil to make alkanolamides. The materials described in the '916 Patent do not possess the desirable unsaponifiable fractions which are present in the alkanolamides of the present invention. [0012] The shea butter alkanolamides of the present invention thus deliver unexpectedly high amounts of unsaponifiables to the skin and hair in a heretofore unachievable manner. They not only thicken but also act as antioxidants and free radical scavengers. Summary of the Invention

[0013] The present invention relates to a novel class of alkanolamides made by reacting shea butter with alkanolamines and a process for using them in personal care applications. In a preferred aspect of the present invention, mild processing is employed both at the time of harvesting and initial extraction (creating mild-processed shea butter) and during subsequent preparation of alkanolamide derivatives. In so doing, materials containing unexpectedly high amounts of active ingredients, particularly highly desired unsaponifiables, are produced. Detailed Description of the Invention

[0014] The compounds of the present invention are alkanolamides produced by reacting shea butter with an alkanolamine. Preferably, the shea butter is mild-processed and is reacted with an alkanolamine under mild processing conditions. The novel Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001 alkanolamides of the present invention are rich in unsaponifϊables, including antioxidants and free-radical scavengers.

[0015] Shea butter alkanolamide derivatives of the present invention conform to the following structure:

R¹

Wherein

(i) R¹ is derived from shea butter and comprises . from about 0.1 to about 2.0 % by weight C] ^₂₃; from about 0.5 to about 2.0% by weight Ci₃H₂₇; from about 2.0 to about 6.0% by weight C₁₅H₃₁; from about 25 to about 50% by weight Ci₇H₃₅; and from about 40.0 to about 60.0 % by weight Ci₇H₃₃; (ii) R² is selected from the group consisting Of-CH-CH₂OH,

-CH₂CH(CH₃)OH and -CH₂CH₂OCH₂CH₂OH; and (iii) R³ is selected from the group consisting of -H, -CH₂CH₂OH. [0016] Shea Butter

[0017[ Shea butter can be prepared by standard extraction techniques known to those of skill in the art. For example, U.S. Patent No. 6,552,208, the disclosure of which is incorporated herein by reference, describes several methods for processing shea butter. Suitable extraction vehicles may include, but are not limited to, ethanol, methanol, ethyl acetate, acetone, chloroform and water, or any other solvent and water. [0018] In a preferred aspect of the present invention, shea butter is mild-processed; it is extracted using a hydrocarbon-free solvent system and its alkanolamide derivatives are Rogers; O'Lenick, Jr. Shea Butter AIkanolamides Atty. Docket VER-PCT-001 made under mild processing conditions. At the time of harvesting and initial extraction ground-up kernels are boiled in water under mild conditions as described in the examples below. The oil phase is then separated from the water phase by decanting. This process provides a yellow solid wax rich in unsaponifiables. By wax is meant a material obtained by boiling in water under ambient conditions, decanted and filtered. [0019] The mild processing of the present invention may be contrasted with separation using solvents and high temperature treatment with high pressure steam. While the latter processes result in what some may describe as a "more pure" triglyceride, unsaponifiables, and the benefits derived therefrom, are lost. Vacuum distillation which strips off the desirable components is also to be avoided in processing MPSB of the present invention. By processing shea butter under mild conditions, materials comprising from about 5% to about 15% by weight of unsaponifiables can be produced. [0020] Sterols comprise about 20% of the unsaponifiables in shea butter. More particularly, the sterols comprise: cholesterol (from about 1 % to about 3%); alpha- spinasterol (from about 1% to about 4%); delta-7-stigmasterol (from about 40% to about 44%); delta-7-avenasterol (from about 38% to about 41%). The remaining constituents of the unsaponifiables (about 80%) include other highly desirable active compounds including tocopherol, karitin, cinamic acid esters, alpha and beta amyrin and phenolics. [0021] Phenolic compounds are natural products composed of one or more aromatic benzene rings with one or more hydroxyl group. They are a class of natural products that possess antioxidant and free radical scavenging properties. Among the phenolics in the unsaponifiables of mild-processed shea butter include gallic acid, gallocatchin, catechin, Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001 epigallocatechin gallate, epicatechin, gallocatechin gallate, gallocatechin gallate and quercetin.

[0022] AIkanolamines

[0023] Alkanolamides of the present invention are made by the amidation reaction of shea butter (or, preferably, MPSB) with an alkanolamine conforming to the following structure:

N-R²

Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001 wherein

(i) R² is selected from the group consisting Of-CH₂CH₂OH,

-CH₂CH(CH₃)OH and -CH₂CH₂OCH₂CH₂OH; and (ii) R³ is selected from the group consisting of -H, -CH₂CH₂OH. [0024] Alkanolamines suitable for use in the present invention are commercially available from a variety of suppliers, including Dow Chemical (Midland, Michigan). Illustrative examples of suitable alkanolamines are listed below:

Example R* R^ Chemical Name

1 -CH₂CH₂OH -H Monoethanolamine

2 -CH₂CH₂OH -CH₂CH₂OH Diethanolamine

3 -CH₂CH₂O-CH₂CH₂OH -H Diglycolamine

4 -CH₂CH(CH₃)OH -H Monoisopropanol amine

[0025] In a preferred embodiment, the amidation is conducted at a temperature of from about 80⁰C to about 90⁰C in the presence of an anhydrous alkaline catalyst. [0026] Another aspect of the present invention is a process for delivering antioxidants to the skin or hair by topically applying a finished product comprising an effective amount of an alkanolamide made by the amidation reaction of shea butter (or, preferably, MPSB) and an alkanolamine conforming to the following structure:

N-R²

R³ wherein

(i) R² is selected from the group consisting Of-CH₂CH₂OH,

-CH₂CH(CH₃)OH and -CH₂CH₂OCH₂CH₂OH; and (ii) R³ is selected from the group consisting of -H, -CH₂CH₂OH. [0027] In a preferred embodiment, the amidation is conducted at a temperature of from Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001 about 80⁰C to about 90°C in the presence of an anhydrous alkaline catalyst. By processing in this temperature range, alkanolamides of the present invention and glycerin remain in the product. Tn contrast, when methyl esters or fatty acids are used in preparing alkanolamides, methanol or water, respectively, are distilled off, resulting in the loss of desirable unsaponifϊables. The lower processing temperatures are also more compatible with, and maintain the potency of, antioxidants present in the unsaponifϊables.

[0028] In a preferred embodiment, the effective concentration of alkanolamide ranges from about 0.5% to about 15.0% by weight.

[0029] In a preferred embodiment R² is -CH₂CH₂OH, and R³ is -H.

[0030] In a preferred embodiment R² is -CH₂CH₂OH, and R³ is -CH₂CH₂OH.

[0031] In a preferred embodiment R² is -CH₂CH₂O-CH₂CH₂OH, and R³ is -H.

[0032] In a preferred embodiment R² is -CH₂CH(CH₃)OH, and R³ is -H.

[0033] The following examples are further illustrative of the present invention. The components and specific ingredients are presented as being typical, and various modifications can be derived in view of the foregoing disclosure within the scope of the invention. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius unless otherwise specified.

[0034] Examples

[0035] Mild-processed shea butter is made according to the following procedure:

500.0 grams of nuts from the shea butter tree are cracked into small pieces and placed into a one-liter vat of water. The water is then heated to 100⁰C. As the temperature increases, an oil phase develops on the surface of the water. The temperature is held for about 2 hours, after which the oil is decanted and passed through filter paper. The Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001 resulting oil is mild-processed shea butter according to the present invention and may be used in making alkanolamides. It is rich in unsaponifiables, from about 7% to about 15% by weight.

[0036] Examples 5 — 8 are illustrative of the MPSB alkanolamides of the present invention. To the specified number of grams of alkanolamine (Examples 1-4) is added the specified number of grams of MPSB. This mass is heated to from about 80⁰C to about 90⁰C. Thereafter, about 0.4% by weight of solid sodium methylate powder is added. The mass is held within the specified temperature range for a period of from about four to about six hours. Nothing is distilled off during this time. The amine value drops during this period and, after several hours, stabilizes. Once the amine value stabilizes, the reaction is held an additional hour and the reaction mass is cooled to ambient temperature. Important to the preparation of MPSB alkanolamides of the present invention is the low processing temperatures. This requires neither distillation of water or processing at high temperatures (e.g., from about 18O⁰C to about 19O⁰C). [0037] Examples 5 - 8 (Mild-Processed Shea Butter Alkanolamides)

Alkanolamine Alkanolamine MPSB

Example Example Grams Grams

5 Example 1 295.0 1450.0

6 Example 2 525.0 1450.0

7 Example 3 510.0 1450.0

8 Example 4 370.0 1450.0

[0038] While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth hereinabove but Rogers; O'Leπick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001 rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

Claims

Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001Claims

1. An alkanolamide derived from shea butter conforming to the structure:

R¹ -C(O)-N-R²

wherein A.

(i) R¹ is derived from shea butter and comprises from about 0.1 to about 2.0 % by weight CπH₂₃; from about 0.5 to about 2.0% by weight C_BH₂₇; from about 2.0 to about 6.0% by weight C₁₅H₃₁; from about 25 to about 50% by weight C17H₃₅; and from about 40.0 to about 60.0 % by weight Ci₇H₃*; (ii) R² is selected from the group consisting Of-CH₂CH₂OH,

-CH₂CH(CH₃)OH and -CH₂CH₂OCH₂CH₂OH; and (iii) R³ is selected from the group consisting of -H and -CH₂CH₂OH.

2. An alkanolamide of claim 1 wherein R¹ is -CH₂CH₂OH, and R² is — H.

3. An alkanolamide of claim 1 wherein R¹ Js -CH₂CH₂OH, and R² is -CH₂CH₂OH.

4. An alkanolamide of claim 1 wherein R¹ is -CH₂CH₂O-CH₂CH₂OH, and R² is -H.

5. An alkanolamide of claim 1 wherein R¹ is -CH₂CH(CH₃)OH, and R² is -H.

6. An alkanolamide made by the amidation reaction of

(a) an alkanolamine conforming to the following structure: N-R²

R³ wherein Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001

(i) R² is selected from the group consisting Of-CH₂CH₂OH,

-CH₂CH(CH₃)OH BnCi -CH₂CH₂OCH₂CH₂OH; and (ii) R³ is selected from the group consisting of -H , -CH₂CH₂OH; and (b) a shea butter comprising from about 0.1 to about 2.0 % by weight C11H₂₃; from about 0.5 to about 2.0% by weight Ci₃H₂₇; from about 2.0 to about 6.0% by weight C15H₃₁; from about 25 to about 50% by weight Ci₇H_3S; and from about 40.0 to about 60.0 % by weight C_nH₃₃;

7. An alkanolamide of claim 6 wherein R² is -CH₂CH₂OH, and R³ is -H.

8. An alkanolamide of claim 6 wherein R² is -CH₂CH₂OH, and R³ is -CH₂CH₂OH.

9. An alkanolamide of claim 6 wherein R² is -CH₂CH₂O-CH₂CH₂OH, and R³ is -H.

10. An alkanolamide of claim 6 wherein R² is -CH₂CH(CH₃)OH, and R³ is -H.

11. An alkanolamide of claim 6 wherein the amidation is conducted at a temperature of from about 8O⁰C to about 9O⁰C in the presence of an anhydrous alkaline catalyst.

12. An alkanolamide of claim 11 wherein R² is -CH₂CH₂OH, and R³ is -H.

13. An alkanolamide of claim 11 wherein R² is -CH₂CH₂OH, and R³ is -CH₂CH₂OH.

14. An alkanolamide of claim 1 1 wherein R² is -CH₂CH₂O-CH₂CH₂OH, and R³ is -H.

15. An alkanolamide of claim 11 wherein R² is -CH₂CH(CH₃)OH, and R³ is -H.

16. A process for treating hair and skin with an effective concentration of an alkanolamide made by the amidation reaction of shea butter and an alkanolamine conforming to the following structure:

N-R² Rogers; O'Lenick, Jr. Shea Butter Alkanolamides Atty. Docket VER-PCT-001

R³ wherein

(i) R² is selected, from the group consisting Of-CH₂CH₂OH,

-CH₂CH(CH₃)OH and -CH₂CH₂OCH₂CH₂OH; and (ii) R³ is selected from the group consisting of -H , -CH₂CH₂OH.

17. A process of claim 16 wherein R² is -CH₂CH₂OH, and R³ is -H.

18. A process of claim 16 wherein R² is -CH₂CH₂OH, and R³ is -CH₂CH₂OH.

19. A process of claim 16 wherein R² is -CH₂CH₂O-CH₂CH₂OH, and R³ is -H.

20. A process of claim 16 wherein R² is -CH₂CH(CH₃)OH, and R³ is -H.

21. A process of claim 16 wherein the amidation is conducted at a temperature of from about 80⁰C to about 9O⁰C in the presence of an anhydrous alkaline catalyst.

22. A process of claim 21 wherein R² is -CH₂CH₂OH, and R³ is -H.

23. A process of claim 21 wherein R² is -CH₂CH₂OH, and R³ is -CH₂CH₂OH.

24. A process of claim 21 wherein R² is -CH₂CH₂O-CH₂CH₂OI-I, and R³ is -H.

25. A process of claim 21 wherein R² is -CH₂CH(CH₃)OH, and R³ is -H.

26. A process of claim 16 wherein the effective concentration of the alkanolamide ranges from about 0.5% to about 15.0% by weight.

27. A process of claim 26 wherein R² is -CH₂CH₂OH, and R³ is -H.

28. A process of claim 26 wherein R² is -CH₂CH₂OH, and R³ is -CH₂CH₂OH.

29. A process of claim 26 wherein R² is -CH₂CH₂O-CH₂CH₂OH, and R³ is -H.

30. A process of claim 26 wherein R² is -CH₂CH(CH₃)OH, and R³ is -H.

31. An alkanolamide of claim 1 where the shea butter is mild-processed.

32. A process of claim 16 where the shea butter is mild-processed.