CN118401226A - Natural oil-based vaseline and preparation method thereof - Google Patents

Abstract

The present disclosure relates to a composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the esters of ester-containing fatty acids are C8-C22 branched or straight chain fatty acid esters, and wherein the composition has a drop melting point between 30 ℃ and 70 ℃ and/or a combined mono-and diglyceride content between 0.5% and 10%.

Description

Natural oil-based vaseline and preparation method thereof

Cross Reference to Related Applications

This patent application claims the benefit of U.S. provisional application Ser. No. 63/367,339, filed on 30 months 6, 2022, and U.S. provisional application Ser. No. 63/264,211, filed on 17 months 11, 2021, each of which is incorporated herein by reference in its entirety.

Technical Field

The present application relates to natural oil-based petrolatum compositions, methods of making, and uses thereof in personal care products.

Background

Petrolatum is a byproduct of petroleum refining. In the case of melting points close to body temperature, petrolatum softens after application and forms a occlusive film around the applied area, creating an effective barrier against the natural moisture evaporation of the skin and foreign particles or microorganisms that may cause infection. Petrolatum is odorless and colorless, and it has an inherently long shelf life, however, it is not readily biodegradable. Petrolatum is not a single entity, but rather comprises a complex mixture of organic compounds having various structures. This diversity of components gives petrolatum unique rheological properties over a wide range of temperatures. For example, petrolatum does not have a distinct melting point as conventionally thought of as an organic compound, but rather melts over a range of temperatures and condenses over about the same temperature range. These properties make petrolatum a useful and popular ingredient in skin care products and cosmetics. It is often used as an ingredient in a wide variety of personal care products such as skin creams, lotions, hair care products and cosmetics. The main benefit is the occlusive nature of petrolatum, where it can create a barrier to protect or maintain hydration of the skin. Thus, it is commonly used to protect the skin, hair, and lips, or to assist in healing of damaged skin or lips. It is most commonly under the trade nameAre known.

Petrolatum has no known health problems when properly refined. However, in the case of incomplete refining, petrolatum can potentially be contaminated with polycyclic aromatic hydrocarbons or PAHs. PAH is a byproduct of the combustion of organic materials, which is typically stored in fat after exposure due to its lipophilicity.

Many efforts have been made to develop bio-based petrolatum substitutes. Most of these efforts have involved producing blends of higher melting waxes, hydrogenated oils, or other natural oils. By blending, it is possible to produce products having a feel similar to petrolatum, however these products have common disadvantages. Because they are simple blends, the rheology of the material does not match that of petrolatum throughout the application temperature range. These materials may have a multimodal melting curve in which the lower melting point component melts first, while the higher melting point component remains intact until the temperature reaches a higher point. In other words, these alternative products do not have a smooth melting curve or a smooth change in rheology over a range of temperatures. In contrast, they have a biphasic or multiphasic melting curve, so they do not mimic the properties of petrolatum at various temperatures. In addition, these blends can have a much higher Iodine Value (IV), which indicates the presence of significantly higher unsaturation in the natural oil. Such unsaturation is undesirable because it can lead to significantly lower oxidative stability over time. Finally, these alternative products may also have relatively high hydroxyl numbers. These high hydroxyl number products can be difficult to formulate into personal care applications because the hydrophilicity of the hydroxide groups can create additional surfactant effects that interfere with the product formulation.

Thus, it would be advantageous to have an improved natural-based material that more closely mimics the texture, appearance, morphology, rheology, stability, formulation, and surfactant properties of petrolatum. It would be environmentally and economically desirable if such materials were more readily or completely biodegradable and were derived from renewable raw materials such as natural oils.

Disclosure of Invention

The compositions disclosed herein more closely simulate petroleum-based petrolatum than blends of ingredients of the prior art by containing mixtures of components having different molecular weights and rheological properties. Producing such products by blending would be extremely time consuming and expensive.

The present disclosure relates to a composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the esters of ester-containing fatty acids are C8-C22 branched or straight chain fatty acid esters, and wherein the composition has a drop melting point between 30 ℃ and 70 ℃ as measured by AOCS standard procedure Cc 18-80.

The present disclosure provides a composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the ester of an ester-containing fatty acid is a C8-C22 branched or straight chain fatty acid ester, and wherein the composition has less than 10% of combined mono-and diglycerides.

The present disclosure provides a composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the ester of an ester-containing fatty acid is a C8-C22 branched or straight chain fatty acid ester, and wherein the composition has: a) Contains less than 10% of the combined mono-and diglycerides, and b) has a drop melting point between 30 ℃ and 70 ℃ as measured by AOCS standard procedure Cc 18-80.

The present disclosure also provides a method of preparing a natural oil-based petrolatum composition. The process involves (i) mixing a C8-C22 fatty acid with a triglyceride component containing one or more hydroxyl-containing fatty acid chains and optionally a hydrogenated natural oil, (ii) heating the mixture (optionally in the presence of an acid catalyst), and (iii) exposing the heated mixture to a pressure below ambient pressure to produce a product, wherein one or more of the hydroxyl-containing fatty acid chains are esterified with a C8-C22 fatty acid, and wherein the composition: a) Contains less than 10% of the combined mono-and diglycerides, and/or b) has a drop melting point between 30 ℃ and 70 ℃ as measured by AOCS standard procedure Cc 18-80, and (iii) separates the natural-based petrolatum composition.

The low IV of the natural oil-based petrolatum disclosed herein results in improved oxidative stability and, correspondingly, improved shelf life and quality. The lower hydroxyl number enhances the ability of the natural oil-based petrolatum disclosed herein to be more efficiently used in personal care formulations. In addition, surprisingly, the structures of the natural oil-based petrolatum disclosed herein are biodegradable.

The natural oil-based petrolatum compositions described herein are useful in industrial applications and personal care products. In particular, in the case of personal care products, it is desirable for petrolatum substitutes to have properties that can improve ease of manufacture while providing a pleasing look and feel.

Advantages are achieved by aspects of the present disclosure, some of which are unexpected. For example, the various compositions described herein advantageously spread evenly and uniformly over the skin. They have a much more consistent rheology over a range of temperatures and more closely mimic the properties of petroleum-based petrolatum. The natural oil-based petrolatum compositions disclosed herein have a occlusive effect and are capable of coating the skin and protecting the skin from moisture loss.

The compositions of the present disclosure also have improved manufacturing properties and may be incorporated into personal care products such as shampoos, conditioners, creams, lotions, sunscreens, hair care, hair styling, body washes, and the like.

The compositions of the present disclosure also have significant advantages over the prior art. In some applications, it may be advantageous for the composition to have a low hydroxyl number in order to be incorporated into the finished product. Limiting the amount of MAG and DAG present in the composition affects the hydroxyl number and is easy to formulate into finished products.

In a separate aspect, specific manufacturing process conditions limit the production of MAG, DAG and related free fatty acids. Limiting the production of free fatty acids, particularly when castor oil or hydrogenated castor oil is used in the reaction, limits the production of hydroxystearic acid oligomers as reaction byproducts. Any significant formation of these compounds can lead to undesirable rheology, production of the corresponding MAG and DAG, and resistance to biodegradation.

As another advantage, the various compositions described herein are based on natural oils and thus have the advantage of containing biodegradable, renewable and environmentally friendly components. For example, the natural oil-based petrolatum compositions of the present disclosure may be prepared from natural oils and still provide the advantages described above.

Detailed Description

Reference will now be made in detail to certain aspects of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it should be understood that the illustrated subject matter is not intended to limit the claims to the disclosed subject matter. An aspect described in connection with a particular embodiment is not necessarily limited to that embodiment and may be practiced with any other embodiment.

Throughout this document, values expressed in a range format should be construed in a flexible manner to include not only the values explicitly recited as the limits of the range, but also to include all the individual values or sub-ranges encompassed within that range as if each value and sub-range is explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also individual values (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%,1.1% to 2.2%,3.3% to 4.4%) within the indicated range. Unless otherwise indicated, the statement "about X to Y" has the same meaning as "about X to about Y". Also, unless otherwise indicated, the statement "about X, Y or about Z" has the same meaning as "about X, about Y, or about Z".

As used herein, the singular forms "a," "an," and "the" include plural referents in the context of describing elements (especially in the context of the following claims) unless the context clearly dictates otherwise. For example, reference to "a substituent" encompasses a single substituent as well as two or more substituents, and the like. It is to be understood that any term in the singular may include its plural counterparts, and vice versa, unless the context clearly dictates otherwise or otherwise.

The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. At least one of "a and B" is stated to have the same meaning as "A, B, or a and B".

Also, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description and not of limitation. Any use of chapter titles is intended to aid reading files and should not be construed as limiting; information related to chapter titles may appear inside or outside the particular chapter. Any publications, patents, and patent documents cited in this document are incorporated by reference in their entirety to the extent allowed by law, as if individually incorporated by reference. If usage between this document and those documents so incorporated by reference is inconsistent, the usage in the incorporated references should be considered as supplementary to the usage of this document; for irreconcilable inconsistencies, the usage in this document controls.

As used herein, the following terms have the following meanings unless explicitly stated to the contrary.

As used herein, the terms "e.g.", "such as" or "comprising" are intended to introduce examples that further clarify more general subject matter. Unless otherwise indicated, these examples are provided solely as an aid in understanding the application described in this disclosure; and are not intended to be limiting in any way.

In the methods described herein, acts may be performed in any order without departing from the principles of the present disclosure, except when time or order of operation is explicitly recited. Furthermore, unless an explicit declaration language states that specified actions are performed separately, they may be performed concurrently. For example, the claimed actions of doing X and the claimed actions of doing Y may be performed simultaneously in a single operation, and the resulting process would fall within the literal scope of the claimed process.

As used herein, the term "about" may allow for some degree of variability in a value or range, for example, within plus or minus 10%, within 5%, or within 1% of a specified limit of a specified value or range, and include the exact specified value or range.

The term "some" as used herein may allow for a degree of variability. This means that a subset of a group has a particular quality or aspect. This is intended to mean that more than one member of the group has a particular quality or aspect, but is not intended to mean that all members of the group have such a particular quality or aspect.

As used herein, the term "substantially" refers to a majority or a majority, as at least about or greater than about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.

As used herein, the term "natural oil" may refer to oils derived from plant or animal sources. The term "natural oil" includes natural oil derivatives unless otherwise indicated. Examples of natural oils include, but are not limited to, vegetable oils, algae oils, animal fats, tall oils, derivatives of these oils, combinations of any of these oils, and the like. Representative non-limiting examples of vegetable oils include canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil, camelina oil, pennycress oil, algae oil, jojoba oil, and castor oil. Representative non-limiting examples of animal fats include lard, tallow, poultry fat, yellow grease, and fish oil. Tall oil is a byproduct of wood pulp manufacture. In some aspects, the natural oil may be refined, bleached, and/or deodorized. In some aspects, the natural oil is present alone or as a mixture thereof.

As used herein, the term "hydrogenated" or "hydrogenated natural oil" refers to the partial, complete, or substantially complete hydrogenation of a natural oil. Partial or substantially complete hydrogenation of natural oils is well known in the art. The skilled artisan will appreciate that it is difficult and impractical to completely hydrogenate a natural oil because of the high probability of some unsaturation remaining in any hydrogenated oil no matter how long the hydrogenation process has been performed. Efforts to fully hydrogenate the oil will result in economic inefficiency and degradation of the oil. The degree of hydrogenation is generally reflected by the residual iodine value of the reference product. Thus, many of the oils sold or referred to as "fully" hydrogenated have been processed to a reduced extent and still have a small residual iodine value. Many hydrogenated natural oils are commercially available and available from a variety of commercial sources.

As used herein, "natural oil-based" composition means that the composition contains oils and fatty acids derived primarily, substantially or entirely from natural oils and natural oil derivatives. In various aspects, the natural oil based composition may contain an oil that is at least 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, 99.9%, 99.99%, or about 100% natural or hydrogenated natural oil.

"Acylglyceride" refers to a molecule having at least one glycerol moiety with at least one fatty acid residue linked via an ester linkage. For example, the acyl glycerides may include monoacylglycerides, diacylglycerides, triacylglycerides. The class of acylglycerides may be further refined by additional descriptive terminology, and may be modified to specifically exclude or include certain subsets of the acylglycerides. For example, the phrases mono-and diglycerides refer to MAG (monoacylglycerides) and DAG (diacylglycerides), while the phrase non-MAG/non-DAG acylglycerides refers to a class of acylglycerides excluding MAG and DAG.

"Monoacylglycerides" refers to molecules having a glycerol moiety with a single fatty acid residue linked via an ester linkage. The terms "monoacylglycerol", "monoacylglyceride", "monoglyceride" and "MAG" are used interchangeably herein. Monoacylglycerides include 2-acyl glycerides and 1-acyl glycerides.

"Diacylglycerol" refers to a molecule having a glycerol moiety with two fatty acid residues linked via an ester linkage. The terms "diacylglycerol," "diacylglycerol ester," "diglyceride," and "DAG" are used interchangeably herein. Diacylglycerides include 1, 2-diacylglycerides and 1, 3-diacylglycerides.

"Triacylglycerides" refers to molecules having a glycerol moiety linked to three fatty acid residues via an ester linkage. The terms "triacylglycerol", "triglyceride" and "TAG" are used interchangeably herein.

In some aspects, the triglycerides comprise C8-C22 fatty acids. In a further aspect, the triglyceride comprises hydroxyl-containing fatty acids. The hydroxyl-containing fatty acids of triglycerides may also be modified by esterification. The hydroxyl-containing fatty acid can react with the free fatty acid to produce an ester bond, which corresponds to the ester-containing fatty acid.

In some aspects, the triglyceride comprises ester-containing fatty acids. In some aspects, more than 20% of the hydroxyl-containing fatty acids are esterified. In some aspects, more than 30% of the hydroxyl-containing fatty acids are esterified. In some aspects, more than 40% of the hydroxyl-containing fatty acids are esterified. In some aspects, more than 50% of the hydroxyl-containing fatty acids are esterified. In some aspects, more than 20% of the triglyceride fatty acids are substituted with C8-C22 fatty acid esters. In some aspects, more than 30% of the triglyceride fatty acids are substituted with C8-C22 fatty acid esters. In some aspects, more than 40% of the triglyceride fatty acids are substituted with C8-C22 fatty acid esters. In some aspects, more than 50% of the triglyceride fatty acids are substituted with C8-C22 fatty acid esters. In some aspects, between 20% and 90% of the triglyceride fatty acids are substituted with C8-C22 fatty acid esters. In some aspects, between 20% and 70% of the triglyceride fatty acids are substituted with C8-C22 fatty acid esters. In some aspects, between 30% and 50% of the triglyceride fatty acids are substituted with C8-C22 fatty acid esters.

As used herein, the term "fatty acid" may refer to a molecule comprising a hydrocarbon chain and a terminal carboxylic acid group. As used herein, the carboxylic acid group of a fatty acid may be modified or esterified, for example as occurs when incorporating the fatty acid into a glyceride or another molecule (e.g., COOR, where R refers to, for example, a hydrocarbon chain). Alternatively, the carboxylic acid groups may be in the form of free fatty acids or salts (i.e., COO' or COOH). The "tail" or hydrocarbon chain of a fatty acid may also be referred to as a fatty acid chain, fatty acid side chain or fatty chain, whether in its esterified or free form. The hydrocarbon chain of the fatty acid will typically be a saturated or unsaturated aliphatic group. Fatty acids having N carbons will typically have fatty acid side chains containing N-1 carbons.

The application also relates to modified forms of fatty acids, and thus the term fatty acid may be used in situations where the fatty acid has been substituted or otherwise modified as described above. For example, in various aspects, the fatty acid may be substituted with another alkyl chain (as in the case of isostearic acid or hydroxyl, as in the case of ricinoleic acid present in castor oil).

The fatty acids and/or natural oils containing them may be hydrogenated as described herein.

The content of a particular type of fatty acid may be provided herein as a percentage of the total fatty acid content of the oil. Unless explicitly indicated otherwise, such percentages are based on weight percent of total fatty acids, including free fatty acids and esterified fatty acids calculated experimentally by methods well known to the skilled artisan.

A "saturated" fatty acid is a fatty acid that does not contain any carbon-carbon double bonds in the hydrocarbon chain. "unsaturated" fatty acids contain one or more carbon-carbon double bonds. "polyunsaturated" fatty acids contain more than one such carbon-carbon double bond, whereas "monounsaturated" fatty acids contain only one carbon-carbon double bond. The carbon-carbon double bond may take one of two stereoconfigurations, denoted cis and trans. Naturally occurring unsaturated fatty acids are typically in the "cis" form.

Non-limiting examples of fatty acids include C8, C10, C12, C14, C16 (e.g., C16:0, C16:1), C18 (e.g., C18:0, C18:1, C18:2, C18:3, C18:4), C20, and C22 fatty acids. For example, the fatty acids may be caprylic acid (8:0), capric acid (10:0), lauric acid (12:0), myristic acid (14:0), palmitic acid (16:0), stearic acid or isostearic acid (18:0), oleic acid (18:1), linoleic acid (18:2) and linolenic acid (18:3).

The term "C8-C22 fatty acid" means a fatty acid containing 8-22 carbons. The C8-C22 fatty acids may be linear or branched and may be substituted with additional substituent groups such as C1-C3 alkyl groups, hydroxyl groups or ester groups. In some aspects, the C8-C22 fatty acid has a straight chain. In some aspects, the C8-C22 fatty acid is a C16 or C18 fatty acid. In some aspects, the C8-C22 fatty acid comprises stearic acid. In some aspects, the C8-C22 fatty acid comprises greater than 40% or greater than 70% stearic acid. In some aspects, the C8-C22 fatty acid comprises between 40% and 95% stearic acid.

The C8-C22 fatty acid may be a mixture of C8-C22 fatty acids. Stearic acid is commercially available in a variety of purities. It can be sold as 1890, meaning that it contains 90% C18 (stearic acid). The remainder typically comprises other fatty acids, principally C16. Alternatively, stearic acid may be sold as 1845 (or 1655); meaning about 45% stearic acid and 55% palmitic acid. In some aspects, the C8-C22 fatty acids consist essentially of stearic acid and palmitic acid.

In any aspect, the C1-C3 alkyl substituent may be selected from methyl, ethyl, or propyl. In any embodiment, the C1-C3 alkyl substituent may be methyl. In any of the embodiments described herein, the C8-C22 fatty acid substituted with one or more C1-C3 alkyl substituents may be isopalmitic acid, isomyristic acid, isostearic acid, 19-methyl arachidic acid, and isostearic acid.

As used herein, the term "isostearic acid" refers to 16-methylheptadecanoic acid, a chemical of a methyl branched fatty acid, which is heptadecanoic acid substituted at the 16-position with a methyl group. Isostearic acid is a lightly branched liquid fatty acid that can be produced by the reaction of oleic acid with a natural mineral catalyst. Isostearic acid is used in applications requiring liquid fatty acids with stability: thermal stability in the case of lubricants, odor stability for cosmetic formulations and oxidative stability for products with long shelf life requirements. The branched structure of isostearic acid also enhances its dispersing ability and is used in cosmetic and industrial applications to stabilize pigments and mineral particles in oils and solvents. Isostearic acid is well known and commercially available. As used herein, the term isostearic acid refers to a composition that comprises substantially all isostearic acid but is not necessarily 100% pure. The term isostearic acid also specifically includes all potential isomers of isostearic acid in which the methyl substituents occur at different positions on the fatty acid chain.

The fatty acid composition of the oil can be determined by methods well known in the art. The american society of oleochemists (AOCS) claims methods of analysis for various tests performed on vegetable oils. Hydrolyzing the oil components to produce free fatty acids, converting the free fatty acids to methyl esters and analyzing by Gas Liquid Chromatography (GLC) is a well-known standard method for determining oil-like fatty acid compositions. AOCS procedures Ce 1-62 describe the procedure used.

The term "esterification (esterified)" means the creation of an ester linkage, including: 1) Dehydration reaction of alcohol with acid; 2) Transesterification, the alcohol reacts with the ester to form a new ester; or 3) an transesterification reaction, a rearrangement of fatty acids within the triacylglycerol structure.

"Drop point" or dropping point "generally refers to the temperature at which a material, such as a wax, softens and becomes sufficiently fluid to flow as measured under the given standardized test conditions. As used herein, the drop point is determined via AOCS standard procedure Cc 18-80. (official methods and recommended practice of the American Society of oleochemists) (Official Methods and Recommended Practices of THE AMERICAN Oil Chemists' Society, 7 th edition). The drop point is similar to the melting point in that it reflects the thermal properties of the compound, however, the drop point can be used to define a material that does not have a defined melting point. In some aspects, the natural oil-based petrolatum exhibits a drop melting point of about 30 ℃ to about 70 ℃. In some aspects, the natural oil-based petrolatum exhibits a drop melting point of about 35 ℃ to about 50 ℃.

As used herein, the term "polydispersity index" (also referred to as "molecular weight distribution") is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn). Polydisperse data were collected using a gel permeation chromatography instrument equipped with a Waters 510 pump and 410 differential refractometer. Samples were prepared at a concentration of about 2% in THF solvent. A flow rate of 1 ml/min and a temperature of 35℃were used. The column consisted of a Phenogel 5 micron linear/hybrid guard column and a 300mm by 7.8mm Phenogel 5 micron column (styrene-divinylbenzene copolymer) of 50, 100, 1000 and 10000 angstroms. Molecular weights were determined using the following criteria:

As used herein, the term "weight average molecular weight" refers to M _w, which is equal to Σm _i ²n_i/ΣM_in_i, where n _i is the number of molecules of molecular weight M _i. In various examples, the weight average molecular weight can be determined using the tests described herein or by size exclusion chromatography, light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity.

As used herein, the term "number average molecular weight" refers to M _n, which is equal to the total weight of the sample divided by the number of molecules in the sample. M _n may be represented by the formula Σm _in_i/n_i, where n _i is the number of molecules of molecular weight M _i.

In some aspects, the natural oil-based petrolatum exhibits a polydispersity index of greater than 1.3. In some aspects, the natural oil-based petrolatum exhibits a polydispersity index of between 1.3 and 2.0.

As used herein, the term "acid number" (AV) is defined as the weight of KOH (mg) required to neutralize the organic acids present in 1g of the sample, and it is a measure of the free fatty acids present in the composition. AV may be determined by AOCS official method Cd 3 d-63. The acid number of the compositions described herein may be less than 20.0, or less than 10.0, or less than 4.0, or between 0.5 and 20.0, or between 0.5 and 10.0, or between 0.5 and 4.0.

As used herein, the term "hydroxyl number" is expressed in milligrams of potassium hydroxide and corresponds to the number of hydroxyl groups present in 1g of the sample, which is one of the traditional characteristics of oils and fats. The hydroxyl number can be determined by AOCS standard method Cd 13-60. The compositions described herein may have a hydroxyl number of less than 90 or less than 50. In some aspects, the composition may have a hydroxyl number between 10 and 90 or between 30 and 90. In some aspects, the composition may have a hydroxyl number between 50 and 90.

As used herein, the term "iodine value" (commonly abbreviated IV) is the mass of iodine in grams consumed by 100 grams of chemical. Iodine number is often used to determine the amount of unsaturation in fats, oils and waxes. In fatty acids, unsaturation occurs primarily as double bonds that are very reactive to halogen (in this case iodine). Thus, the higher the iodine value, the higher the degree of unsaturation present in the sample. The iodine value of a material can be determined by the standard well known Wijs method (A.O.C.S.Cd 1-25).

Natural oil-based petrolatum composition

The natural oil-based petrolatum compositions described herein have unique compositions that provide more consistent rheology at a variety of temperatures, more closely mimicking petroleum-based petrolatum.

The present disclosure provides a composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the esters of ester-containing fatty acids are C8-C22 branched or straight chain fatty acid esters, and wherein the composition has a drop melting point between 30 ℃ and 70 ℃ as measured by AOCS standard procedure Cc 18-80.

The present disclosure provides a composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the ester of an ester-containing fatty acid is a C8-C22 branched or straight chain fatty acid ester, and wherein the composition contains less than 10% of combined mono-and diglycerides.

The triglyceride component can be prepared by the skilled artisan, for example, by epoxidizing a natural oil containing unsaturated fatty acids and ring-opening the epoxide. Such chemicals are well known in the grease art. Alternatively, the triglyceride component may naturally contain hydroxyl groups. Some natural oils contain hydroxy fatty acids in their natural state. Castor oil is one such example. Typically, castor oil comprises from about 70% to 90% ricinoleic acid fatty acid residues. The triglyceride component may be partially, substantially or fully hydrogenated. High quality castor oil has a hydroxyl number of approximately 160. Fully hardened or hydrogenated castor oil typically has a minimum hydroxyl number of 150.

The procedure of the present disclosure is tailored to minimize the amount of transesterification and transesterification reactions that occur during the reaction. Excessive transesterification reactions may produce hydroxystearic acid oligomers and high molecular weight structures and unwanted MAG and DAG. In some aspects, the composition contains less than 10% combined MAG and DAG. In some aspects, the composition contains less than 10% combined MAG and DAG. In some aspects, the composition contains between 0.5% and 10% combined MAG and DAG. In some aspects, the composition contains between 1% and 8% combined MAG and DAG. The amount of MAG and DAG in the composition can be routinely determined by those skilled in the art. Size exclusion chromatography or GPC as described above can be used to determine the molecular weight and corresponding fractions of mono-, di-or triglycerides in the composition. The skilled artisan will appreciate that a standard curve may be created and used to celebrate a particular chromatographic apparatus.

In some aspects, the triglyceride component is hydrogenated. In some aspects, the triglyceride component comprises hydrogenated castor oil.

In some aspects, the reaction mixture comprises additional natural or hydrogenated natural oil.

In some aspects, the additional natural oil is hydrogenated soybean oil or hydrogenated coconut oil.

The composition may contain a minimum amount of free fatty acids. For example, the composition may comprise less than about 2% by weight free fatty acids. In another embodiment, the composition may comprise less than about 1 wt%, less than about 2.5 wt% free fatty acids, or between 0.1 wt% and 2.5 wt% fatty acids.

The composition may comprise a minimum amount of combined mono-and diglycerides. For example, the composition may comprise less than about 10% by weight of the combined mono-and diglycerides. In another aspect, the composition may comprise less than about 8 wt%, about 6 wt%, less than about 5 wt%, or less than about 3 wt% of the combined mono-and diglycerides. In another aspect, the composition may comprise between about 1% to about 10% by weight; or between about 1% to about 7% by weight; or between about 2% to about 5% by weight; or between about 2% to about 5% by weight of the combined mono-and diglycerides.

The compositions described herein may have an iodine value of less than about 5.0, or less than about 3.0, or between about 0.1 and about 3.

As described herein in any embodiment, the composition may comprise one or more of the following: (i) an acid number of less than about 20.0; (ii) Between about 2% to about 7% by weight of the combined mono-and diglycerides, or (iii) an iodine value of less than about 3.0. In some aspects, the natural oil-based petrolatum composition may have two or all three of the aforementioned characteristics.

Unlike waxes or hard fats, the natural oil-based petrolatum formulation described herein may be a semi-solid material that can retain its own shape, but flex under pressure, more resembling a fat or shortening. The resistance to flexing under pressure can be determined by using a cone penetration test. Penetration can be measured by using standard methods ASTM D217-2.

Natural oil-based petrolatum exhibits a combination of rheological properties that provide spreading and viscosity comparable to petroleum-based petrolatum. In any of the embodiments disclosed herein, the natural oil-based petrolatum exhibits one or more rheological properties selected from the group consisting of: a drop melting point of about 35 ℃ to about 70 ℃, a cone penetration of greater than 20 or from about 20 to about 100 or from about 60 to about 90 (Dmm (1/10 mm)) at 25 ℃, a dynamic viscosity of about 5mm ²/s to about 35mm ²/s at 100 ℃, a congealing point of about 25 ℃ to about 45 ℃, or a combination thereof.

Method for preparing natural oil-based petrolatum compositions (also referred to herein simply as compositions)

The present disclosure also provides a method of preparing a natural oil-based petrolatum composition. The method involves mixing fatty acids with a triglyceride component containing one or more hydroxyl-containing fatty acid chains and optionally hydrogenated natural oil, heating the mixture to an elevated temperature (optionally in the presence of an acid catalyst), and exposing the heated mixture to a pressure below ambient pressure to produce a product, wherein a plurality of the hydroxyl-containing fatty acid chains in the hydroxyl-containing fatty acid chains are esterified with a C8-C22 branched or linear chain, and wherein the triglyceride component: a) Contains less than 10% of the combined mono-and diglycerides, and/or b) has a drop melting point between 30 ℃ and 70 ℃ as measured by AOCS standard procedure Cc 18-80, and isolating the petrolatum composition.

Depending on the nature sought, the reaction may be monitored in a number of different ways. If the reaction is allowed to proceed, the reaction will reach a certain steady state point at which some form of equilibrium is reached. At this point, the parameters of the product do not change significantly and the continued reaction time promotes degradation, thereby affecting the quality of the product. Alternatively, the reaction may be allowed to proceed to a certain set point, such as an acid number, hydroxyl number, or until a certain drop melting point is reached. This is determined by the operator. In some aspects, the reaction is continued until the reaction mixture reaches an acid number of less than 20.0 or less than 10 or less than 5 or until the reaction mixture reaches an acid number of less than 4.0 to provide a natural oil-based petrolatum composition. In some aspects, the reaction mixture achieves an acid number between 0.5 and 20.0. In some aspects, the reaction mixture achieves an acid number between 0.5 and 10.

The reaction mixture has a composition as described herein and the mixture is treated by methods well known in the art to induce chemical or enzymatic esterification. The procedures of the present disclosure, including the use of vacuum and limited catalyst, are tailored to minimize or control the amount of transesterification and transesterification reactions that occur during the reaction. Excessive transesterification reactions can produce hydroxystearic acid oligomers and high molecular weight structures that reduce biodegradability, and unwanted MAGs and DAGs.

For chemical esterification, the catalyst may be added in an amount of about 0.1 wt% relative to the reaction mixture of the components. Exemplary catalysts may be acids, such methane sulfonic acid, or bases such as sodium hydroxide and calcium hydroxide, or metal catalysts. In some aspects, methanesulfonic acid is a catalyst. Hypophosphorous acid may optionally be added to the reaction mixture to prevent the formation of discoloration. The reaction temperature may then be raised to about 140 ℃ to 250 ℃. Typically, a reaction temperature of approximately 160℃is utilized. The reaction temperature is maintained for a period of time and the reaction vessel is evacuated to a pressure between 20 torr and 50 torr until the desired endpoint or steady state is reached. In some aspects, an acid number of less than 15 or less than 10 or less than 5 is achieved, or a polydispersity index of greater than 1.3 is obtained. A base, for example a mineral base such as sodium hydroxide or calcium hydroxide, may be added in an amount of about 0.2 wt.% to neutralize the catalyst slightly in excess. The reaction mixture may then be cooled to a temperature in the range of about 60 ℃ to 80 ℃. The filter medium may be added to the reaction mixture in an amount of about 2 wt.% or less relative to the reaction mixture, such as, for example, B80 neutral orAcid activated bleaching clay of silica to remove impurities. The final product, i.e., the natural oil-based petrolatum composition, is then filtered to remove the mixture of salts, silica, or clay.

In some aspects, the catalyst is selected from the group consisting of a base, an acid, a metal, or a combination thereof. In some aspects, the catalyst is an acid catalyst or a combination of acid catalysts.

Alternatively, the enzyme catalyst may be added in an amount of 2wt% relative to the reaction mixture in order to perform the enzymatic transesterification reaction. An exemplary enzyme catalyst may be lipase Novozyme 435. When the reaction is in progress, a vacuum of about 50 torr may be used to remove water. The reaction temperature ranging from about 60 ℃ to 80 ℃ is maintained until an acid number of less than 5.0 is reached or a polydispersity index of greater than 1.3 is obtained. The enzyme catalyst may then be filtered off using a suitable filter device to obtain the final product, i.e., the natural oil-based petrolatum composition.

Alternatively, the esterification may be performed without a catalyst. The reaction mixture of C8-C22 branched or straight chain fatty acids and hydrogenated natural oil such as castor oil is pre-melted and heated to a temperature ranging from 60 ℃ to 80 ℃ and then added together into the reaction vessel by nitrogen sparging to prevent oxidation. Vacuum was applied to the reaction vessel to reach a pressure between 20 torr and 50 torr and the temperature was raised to 180 ℃ to 250 ℃. Depending on the equipment chosen for the reaction, lower pressures and/or temperatures may also be utilized. The acid number of the reaction was monitored and the reaction temperature and vacuum were maintained until an acid number of less than 20 (or other endpoint) was reached. The product is isolated after cooling the reaction mixture to 60 ℃ to 80 ℃ and filtering (such as by a bag filter) to remove any particulates.

Topical formulations

The compositions provided herein are useful in the manufacture of topical formulations, such as personal care products or cosmetics. The inventors have unexpectedly found that formulations comprising natural oil-based petrolatum have many desirable characteristics, as further explained below, and can be used to replace all or part of the petroleum-based petrolatum currently used in personal care or cosmetic formulations.

In one aspect, the invention is a topical formulation comprising a natural oil-based petrolatum as described herein. As used herein, the term "topical formulation" refers to a formulation that can be directly applied to a part of the body. For use in personal or household care, the term "formulation" is used herein to refer to a composition of the various ingredients in the various weight ranges, in accordance with the present disclosure.

"Personal care" refers to and includes any cosmetic, hygiene, rinse-off, and topical care product, including, but not limited to, leave-on products (i.e., products that remain on the skin or keratinous substrate after application); rinse-off products (i.e., products that are washed or rinsed from the skin and keratinous substrate during application or within minutes); a shampoo; hair frizzing and hair straightening products; combed or disentangled creams, hair style maintenance and hair conditioning products (concentrated masks or more standard formulations; whether rinse-off or leave-on); lotions and creams for nails, hands, feet, face, scalp and/or body; a hair dye; facial and body cosmetics; a foundation; a facial mask; nail care products; an astringent; a deodorant; antiperspirant agents; an anti-acne agent; an anti-aging agent; a depilatory agent; cologne and perfume; skin protective creams and lotions (such as sunscreens); skin and body cleansers/baths; a facial cleanser; a skin conditioning agent; skin toner; a skin tightening composition; skin tanning and lightening compositions; liquid soap; a bar soap; synthetic detergent bars (synset bar); a bathing product; a shaving product; personal lubricants, and oral hygiene products (such as toothpastes, oral suspensions, and oral care products).

The natural oil-based petrolatum disclosed herein may be used on skin or hair alone, and is particularly useful in reducing or replacing various components in shampoo, body wash and hair care, anti-kink and conditioner formulations.

The texture of such personal care formulations is not limited and may be, but is not limited to, liquids, gels, sprays, emulsions (such as lotions and creams), shampoos, conditioners, comb creams, pomades, foams, tablets, sticks (such as lip care products), cosmetics, suppositories, and the like, any of which may be applied to the skin or hair and are generally designed to remain in contact therewith until removed, such as by rinsing with water or washing with a shampoo or soap or synthetic detergent bar. Other forms may be soft, rigid or squeezable gels. The spray may be a non-pressurized aerosol delivered by a manually pumped finger-driven sprayer, or may be a pressurized aerosol in which a chemical propellant or a gaseous propellant is used, such as a mousse, spray or foam-forming formulation.

Formulations prepared using the natural oil-based petrolatum disclosed herein have a white or pale white color that is generally considered to be aesthetically attractive. In some cases, the formulations of the present disclosure may also be processed to produce colored end products. In such cases, white is beneficial because it will reveal additional pigment without affecting the final color.

Formulations containing the natural oil-based petrolatum of the present disclosure may optionally contain additional ingredients to tailor viscosity to the needs of a particular application. The skilled artisan will readily appreciate the range of additives that may be used for this purpose, including but not limited to the following: sclerotium gum (sclerotium gum), xanthan gum, carrageenan, gellan gum (gellan gum), native starch, modified starch, sodium starch octenyl succinate, aluminum starch succinate, hydroxypropyl starch phosphate (hydroxypropyl starch phosphate), pectin, calcium citrate, salt NaCl, KCl, acrylate polymers, acrylate-based copolymers, carbomers, cellulose, citrus fibers and derivatives, hydroxyethyl cellulose, carboxymethyl cellulose, polyols (such as sorbitol) and mixtures thereof. These additives may be used to increase the texture, viscosity or structure of the formulation. The skilled artisan will appreciate that these ingredients may be present in various concentrations, and may even be the primary element of a particular formulation, depending on the needs of the particular formulation.

Formulations containing the natural oil-based petrolatum of the present disclosure may optionally contain at least one additional ingredient selected from the group consisting of: preservatives, salts, vitamins, emulsifiers, conditioners, nutrients, micronutrients, sugars, proteins, polysaccharides, polyols, glucose, sucrose, glycerol, sorbitol, pH adjusting agents, emollients, dyes, pigments, skin actives, oils, hydrogenated oils, waxes or silicones.

Formulations containing the natural oil-based petrolatum of the present disclosure may have a wide range of pH values. Aspects of the disclosure include formulations having a pH between 3-11, or between 4-8, or between 4-7.

The formulations of the present disclosure may contain any useful amount of the natural oil-based petrolatum of the present disclosure. In the final formulation, the formulation will preferably contain between 1 to 100 wt%, 50 to 99 wt%, 75 to 95 wt%, 20 to 90 wt%, 20 to 80 wt%, 1 to 30 wt%, 2 to 20 wt%, 3 to 5 wt% or 1 to 8 wt% of natural oil-based petrolatum.

In some aspects, the personal product comprising natural oil-based petrolatum is a body wash, facial cleanser, shampoo, conditioner, toilet cream, leave-on conditioner, skin moisturizer, lip moisturizer, or cosmetic.

In another embodiment, the composition is the esterification product of: about 55% to about 85% by weight of fully hydrogenated castor oil, about 15% to about 45% by weight of a C8-C22 branched or straight chain fatty acid.

In another embodiment, the composition is the esterification product of: about 55% to about 85% by weight of fully hydrogenated castor oil, about 15% to about 45% by weight of a C8-C22 branched or straight chain fatty acid, and about 5% to about 15% by weight of a hydrogenated natural oil other than castor oil.

The inventors have expressly contemplated and envisaged any and every combination of two or more features of the natural oil-based petrolatum disclosed herein. Accordingly, the inventors have conceived and accordingly disclosed each combination of the disclosed single points and ranges for a triglyceride component containing a plurality of hydroxyl-containing fatty acid chains and C8-C22 branched or straight chain fatty acids; and each combination of one or more values or ranges of the following parameters: drop melting point, cone penetration, congealing point, hydroxyl number, acid number, iodine number, and polydispersity index.

Examples

Table 1.

Table 2.

* The amounts of HCO, stearic acid and HSO were taken as weight% of the reaction mixture.

Example 1:

the following chemical esterification process was performed to prepare examples 1A and 1B. All components or oils described in table 2 were premelted and heated to 80 ℃ and then added to the reaction vessel under nitrogen sparge. The stirrer was turned on to mix the contents. If used, hypophosphorous acid was added at a dose of 0.2% and methanesulfonic acid was added at a dose of 0.1%. Once all ingredients are added and thoroughly mixed, the temperature is raised to approximately 160 ℃. The acid number was monitored throughout the reaction and once AV <20 or AV varied by less than 1 unit/hour, a vacuum was applied to the reaction vessel to achieve a pressure of approximately 30 torr. The reaction temperature is maintained until an acid value of 5 or less is reached. The reaction system was then cooled to approximately 85 ℃ and calcium hydroxide solution was added to neutralize the catalyst slightly in excess. The mixture was cooled to 70℃and 1% was added to the reaction system Silica and allows it to absorb salts from the catalyst. The product is then filtered to remove salt and clay mixtures as well as other impurities.

Example 2:

The following chemical esterification process was performed to purposely limit the transesterification reactions in the preparation of examples 2A to 2D. All components or oils as described in table 2 were pre-melted and heated to approximately 80 ℃ and then added to the reaction vessel under nitrogen sparge to prevent oxidation of the product during the reaction. The stirrer was turned on to mix the contents. If used, hypophosphorous acid was added at a dose of 0.2%. Once all ingredients are added and thoroughly mixed, the temperature is raised to approximately 180 ℃ and a vacuum is applied to the reaction vessel to achieve a pressure of approximately 20 torr to 30 torr. The acid number was monitored throughout the reaction. The reaction temperature and vacuum were maintained until an acid value of 20 or less was reached. The reaction was then cooled to about 85 ℃ and filtered through a bag filter to remove any particulates.

Examples 3A to 3M were prepared as shown in table 3. They were run for different times at different orders of magnitude and utilized the catalyst-free or acid catalyst systems described in examples 1 and 2. The reaction is allowed to proceed until an equilibrium steady state is reached or the reaction is run until an acid number of less than 18 is reached.

Example 4:

Table 4.

* The amounts of HCO and stearic acid were taken as weight% of the reaction mixture.

Examples 4A to 4F were prepared as shown in table 4. They were run for different times at different orders of magnitude and utilized the catalyst-free or acid catalyst systems described in examples 1 and 2. In addition, the vacuum degree and the vacuum timing are changed. Typically, the reaction is allowed to proceed until a steady state is reached in which equilibrium is achieved or for a period of time. By varying the reaction conditions shown, the skilled artisan can govern the preference of esterification of hydroxy fatty acids over transesterification of triglycerides.

Claims (21)

1. A composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the esters of ester-containing fatty acids are C8-C22 branched or straight chain fatty acid esters, and wherein the composition has a drop melting point between 30 ℃ and 70 ℃ as measured by AOCS standard procedure Cc 18-80.

2. The composition of claim 1, wherein the composition contains between 0.5% and 10% of the combined mono-and diglycerides.

3. The composition of claim 1, wherein some of the individual triglycerides contain more than one ester-containing fatty acid.

4. The composition of claim 1, wherein the mixture of triglycerides contains 20% to 70% ester-containing fatty acids.

5. A composition according to claim 3, wherein the C8-C22 branched or straight chain fatty acid ester comprises stearic acid and palmitic acid.

6. The composition of claim 5, wherein the C8-C22 branched or straight chain fatty acid ester consists essentially of stearic acid and palmitic acid.

7. The composition of claim 1 comprising between 50% and 100% by weight of the triglyceride component.

8. The natural oil-based petrolatum of claim 1 having an acid number between 0.5 and 20.

9. The natural oil-based petrolatum of claim 1 having a hydroxyl number between 10 and 90.

10. The natural oil-based petrolatum of claim 4, wherein the natural oil-based petrolatum has an acid number between 0.5 and 5.

11. The natural oil-based petrolatum of claim 4, wherein the triglyceride component is derived from castor oil or hydrogenated castor oil.

12. A composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides containing one or more ester-containing fatty acids, and wherein the esters of ester-containing fatty acids are C8-C22 branched or straight chain fatty acid esters, and wherein the composition contains between 0.5% and 10% of combined mono-and diglycerides.

13. The composition of claim 12, wherein some of the individual triglycerides contain more than one ester-containing fatty acid.

14. The composition of claim 13, wherein the mixture of triglycerides contains 20% to 70% ester-containing fatty acids.

15. The composition of claim 13, wherein the C8-C22 branched or straight chain fatty acid ester comprises stearic acid and palmitic acid.

16. The composition of claim 15, wherein the C8-C22 branched or straight chain fatty acid ester consists essentially of stearic acid and palmitic acid.

17. The composition of claim 12 comprising between 50% and 100% by weight of the triglyceride component.

18. The natural oil-based petrolatum of claim 12 having an acid number between 0.5 and 20.

19. The natural oil-based petrolatum of claim 12 having a hydroxyl number between 10 and 90.

20. The natural oil-based petrolatum of claim 14, wherein the triglyceride component is derived from castor oil or hydrogenated castor oil.

21. A composition comprising a triglyceride component, wherein: the triglyceride component comprises a mixture of triglycerides, and wherein the mixture of triglycerides comprises individual triglycerides comprising one or more ester-containing fatty acids, and wherein the esters of ester-containing fatty acids are C8-C22 branched or straight chain fatty acid esters, and wherein the composition a) contains between 0.5% and 10% of combined mono-and diglycerides; b) Having a drop melting point between 30 ℃ and 70 ℃ as measured by AOCS standard procedure Cc 18-80;

c) Having a hydroxyl number between 10 and 90; an acid number between 0.5 and 20, and wherein the C8-C22 branched or straight chain fatty acid ester comprises stearic acid and palmitic acid.