CN116723824A

CN116723824A - Natural oil-based vaseline and preparation method thereof

Info

Publication number: CN116723824A
Application number: CN202280012006.3A
Authority: CN
Inventors: E·P·J·M·埃弗雷特; 托德·L·库斯; 蒂莫西·艾伦·墨菲; 周一军
Original assignee: Cargill Inc
Current assignee: Cargill Inc
Priority date: 2021-01-05
Filing date: 2022-01-05
Publication date: 2023-09-08

Abstract

The present disclosure relates to natural oil-based petrolatum compositions and methods of preparing the same. The natural oil-based petrolatum composition comprises the esterification product of a pre-esterification mixture of: about 15 wt.% to about 25 wt.% of a fatty acid dimer, about 15 wt.% to about 25 wt.% of glycerin, and about 55 wt.% to about 70 wt.% of a hydrogenated natural oil, wherein the natural oil-based petrolatum product has an acid number of less than 5.0. The natural oil-based petrolatum composition may be used in personal care products.

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 No. 63/134,015, filed on 5-1-2021, and U.S. provisional application No. 63/156,563, filed on 4-3-2021, each of which is incorporated herein by reference in its entirety.

Technical Field

The present application relates to natural oil-based petrolatum compositions and methods of making the same.

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 waterproof film around the area of application, creating an effective barrier against the evaporation of natural moisture from the skin and foreign particles or microorganisms that may cause infection. Petrolatum is odorless and colorless, and it has an inherently long shelf life. It is not a single entity but rather comprises a complex mixture of organic compounds having a wide variety of molecular weights. This diversity of components gives petrolatum unique rheological properties over a wide range of temperatures. For example, petrolatum does not have a significant melting point as organic compounds traditionally considered. 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 name Are 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 when they are heated. 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 a significantly higher degree of unsaturation in the oil. Such unsaturation is undesirable because it can lead to significantly lower oxidative stability over time. The lower IV of the natural-based petrolatum disclosed herein results in improved oxidative stability and correspondingly improved shelf life and quality.

Thus, it would be advantageous to have an improved natural-based material that more closely mimics the texture, viscosity, stability, and melting curve of petrolatum. It is environmentally and economically desirable if such materials are biodegradable and derived from renewable raw materials, such as natural oils.

Disclosure of Invention

The compositions disclosed herein more closely mimic petroleum-based petrolatum by containing a complex mixture of components having different molecular weights and rheological properties than a simple blend of several ingredients. Producing such products by blending would be extremely time consuming and expensive.

The present disclosure provides a natural oil-based petrolatum composition comprising fatty acid dimers, esterified products of hydrogenated natural oil and glycerin, wherein the natural oil-based petrolatum composition has an Acid Value (AV) of less than about 5.0.

The present disclosure provides a natural oil-based petrolatum composition comprising the esterification product of a pre-esterification mixture comprising from about 15 wt% ("wt%") to about 25 wt% fatty acid dimer based on the total weight of the pre-esterification mixture, from about 15 wt% to about 25 wt% glycerin based on the total weight of the pre-esterification mixture, and from about 55 wt% to about 70 wt% hydrogenated natural oil based on the total weight of the pre-esterification mixture. As described herein in any embodiment, the natural-based petrolatum composition may include one or more of the following: i) An acid number of less than about 5.0; ii) a polydispersity index of greater than about 1.3 or an iodine value of less than about 10.0.

The present disclosure provides a natural oil-based petrolatum composition comprising the esterification product of a pre-esterification mixture comprising from about 15 wt.% to about 25 wt.% fatty acid dimer based on the total weight of the pre-esterification mixture, from about 15 wt.% to about 25 wt.% glycerin based on the total weight of the pre-esterification mixture, and from about 55 wt.% to about 70 wt.% hydrogenated natural oil based on the total weight of the pre-esterification mixture. As described herein in any embodiment, the natural oil-based petrolatum composition may have one or more of the following: i) An acid number of less than about 1.5; ii) a polydispersity index of greater than about 1.3 or an iodine value of less than about 10.0.

The present disclosure also provides a method of preparing a natural oil-based petrolatum composition. The method comprises mixing a hydrogenated natural oil, a fatty acid dimer, and glycerin to form a pre-esterified mixture; and adding a caustic catalyst or enzyme catalyst to the mixture to promote transesterification reactions until the mixture achieves an Acid Value (AV) of less than about 5.0 to obtain a natural oil-based petrolatum composition.

The present disclosure also provides a method of preparing a natural oil-based petrolatum composition. The method comprises mixing a hydrogenated natural oil, a fatty acid dimer, and glycerin to form a pre-esterified mixture; and adding a caustic catalyst or an enzyme catalyst to the mixture to promote the transesterification reaction until the mixture has one or more of: i) An acid number of less than about 1.5; ii) a polydispersity index of greater than about 1.3 or an iodine value of less than about 10.0.

The natural oil-based petrolatum compositions described herein may be used in personal care or cosmetic products. In particular, in the case of personal care products, it is desirable for petrolatum substitutes (i.e., natural oil-based petrolatum) to have properties that can improve ease of manufacture while providing a pleasing look and feel.

The advantages achieved by embodiments 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

The natural oil-based petrolatum compositions of the present disclosure also have improved manufacturing properties.

As another advantage, the various compositions described herein are natural oil-based 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 embodiments 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, a statement of "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 unless the context clearly dictates otherwise, in the context of the described element (especially in the context of the following claims). 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 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 terms "e.g.", "such as" or "comprising" are intended to introduce examples that further clarify more general subject matter. 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 unless otherwise specified.

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.

As used herein, the term "substantially" refers to a majority or majority, as at least 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 following terms have the following meanings unless explicitly stated to the contrary.

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, hemp 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 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, and 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 embodiments, 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.

"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.

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 carbon atom). 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. 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. However, the present application also relates to modified forms of fatty acids, such as dimerized fatty acids, so 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 embodiments, one fatty acid may dimerize with another fatty acid to produce a dimerized fatty acid or a dimer fatty acid. Unless otherwise indicated, the term fatty acid as used herein refers to non-dimerized fatty acids, while the term dimerized fatty acids and the like refer to dimeric forms of fatty acids.

"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, and acyl glyceride polymers. 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 monoacylglycerides and diacylglycerides 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. As another example, acyl glycerides comprising C36 dimerized fatty acid residues refer only to those acyl glycerides having the specified residues.

A "fatty acid residue" is a fatty acid in its acyl or esterified form.

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.

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 (18:0), oleic acid (18:1), linoleic acid (18:2), and linolenic acid (18:3).

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 the fatty acid composition of oil samples. AOCS procedures Ce 1-62 describe the procedure used.

The term "esterification" 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) transesterification, rearrangement of fatty acids within the triacylglycerol structure.

The terms "fatty acid dimer" and "dimerized fatty acid" are used interchangeably herein and generally refer to compounds containing two fatty acid subunits, wherein the individual fatty acid side chains are covalently bonded to each other, e.g., via a bond or linking group. Thus, as described herein, the fatty acid dimer is a covalent fatty dimer. The fatty acid dimer may be a heterodimer or homodimer. As used herein, the carboxylic acid groups of the fatty acid dimer may be modified or esterified, for example as occurs when the fatty acid dimer is incorporated into a glyceride or attached to another molecule. Suitable fatty acid dimers are commercially available, for example, the radio 0960 hydrogenated standard dimer and the radio 0970 distilled dimer acid (Belgium, olean N.V.) and the UNIDYME 18 dimer acid (Kotanium, kraton Corporation, houston, TX), respectively.

As one example, the dimerized fatty acid residue may have the following structure:

in exemplary dimerized fatty acid residues, R ¹ And R is ² Each independently is a substituted or unsubstituted aliphatic group. The aliphatic group may correspond to a saturated fatty acid side chain or an unsaturated fatty acid side chain having one, two, three or more double bonds. The aliphatic group may be, for example, 5 to 25 carbons, 7 to 21 carbons, 12 to 21 carbons, 15 to 19 carbons, or 17 carbons. Optionally R ¹ And R is ² May be substituted, and exemplary substituents include alkyl, alcohol, halide, and oxygen to form epoxide rings. R is R ¹ And R is ² May be a saturated or unsaturated linear aliphatic group having 7, 9, 11, 13, 15, 17, 19 or 21 carbons. When R is ¹ And R is ² In the case of saturated or unsaturated groups of 17 carbons each, the resulting dimer fatty acid residue has 36 carbons. R is R ¹ And R is ² May contain hydrogen, carbon, oxygen and nitrogen atoms; or R is ¹ And R is ² May consist of carbon, hydrogen and oxygen atoms; or R is ¹ And R is ² May consist of carbon and hydrogen atoms.

The linking group Z is a bond, an oxygen atom, or any other suitable linking group. The linking group Z may be attached to R via any position ¹ And R is ² . For example, the linking group Z may be attached to R ¹ And R is ² At positions other than the terminal carbon. As another example, R ¹ And R is ² May be a linear aliphatic group corresponding to a fatty acid side chain, and the linking group Z may be attached at the ω number 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, etc., or alternatively the linking group Z may be attached at the terminal (ω -1) carbon. In another example, the Z groups represent multiple bonds such that R ¹ And R is ² To form a carbocyclic or heterocyclic ring therebetween. When Z is a bond, the dimerized fatty acid residue may have the following structure:

"plurality" means two or more. For example, the polymeric compound having a plurality of glycerol units may have 2 or more glycerol units, 10 or more glycerol units, 100 or more glycerol units, 1,000 or more glycerol units, and the like.

"drop point" generally refers to the temperature at which a material (such as wax) softens and becomes sufficiently fluid to flow as measured under 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.

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 sigma M _i ² n _i /∑M _i n _i Wherein n is _i Is the molecular weight M _i Molecular number of (3). 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.

The term "number average molecular weight" as used herein refers to M _n Which is equal to the total weight of the sample divided by the number of molecules in the sample. M is M _n Can be represented by sigma M _i n _i /n _i Representation, where n _i Is the molecular weight M _i Molecular number of (3).

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 10.0, or less than 5.0, or less than 4.0, or between 0.5 and 5.0, or between 0.5 and 4.0.

As used herein, the term "hydroxyl number" is defined as the hydroxyl number 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.

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 compositions of the present invention comprise the esterification product of a pre-esterification mixture comprising a dimer fatty acid, glycerol, and a hydrogenated natural oil.

Prior to esterification, the pre-esterification mixture may comprise fatty acid dimers in an amount of from about 15% to about 25% by weight; glycerin in an amount of about 15% to about 25% by weight and hydrogenated natural oil in an amount of about 55% to about 70% by weight.

In some embodiments, the fatty acid dimer may be present in the pre-esterification mixture from about 18 wt.% to about 23 wt.% prior to esterification. In some embodiments, prior to esterification, the fatty acid dimer may be present in the pre-esterification mixture at about 15 wt.%, about 16 wt.%, about 17 wt.%, about 18 wt.%, about 19 wt.%, about 20 wt.%, about 21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, or any range comprising and/or between any two of the foregoing values.

In some embodiments, the fatty acid dimer is a radiac 0960 hydrogenated standard dimer and a radiac 0970 distilled dimer acid (belgium euclidean) and UNIDYME 18 dimer acid (koteng of houston, texas).

In some embodiments, the fatty acid dimer may be radio 0970.

In some embodiments, the hydrogenated natural oil may be present in the pre-esterification mixture at about 55 wt.% to about 70 wt.% prior to esterification. In some embodiments, the hydrogenated natural oil may be present in the pre-esterification mixture prior to esterification at about 55 wt.%, about 60 wt.%, about 65 wt.%, about 70 wt.%, or any range that includes and/or is between any two of the foregoing values. In some embodiments, the hydrogenated natural oil may be present in the pre-esterification mixture at about 55 wt.% to about 65 wt.% prior to esterification.

In some embodiments, the hydrogenated natural oil may be hydrogenated soybean oil, palm oil, canola oil, castor oil, coconut oil, or a combination thereof. In some embodiments, the hydrogenated natural oil is hydrogenated soybean oil.

In some embodiments, the hydrogenated natural oil is a blend of two or more hydrogenated natural oils selected from the group consisting of: hydrogenated soybean oil, hydrogenated palm oil, hydrogenated canola oil, hydrogenated castor oil or hydrogenated coconut oil.

In some embodiments, the glycerol may be present in the pre-esterification mixture in an amount of from about 18 wt.% to about 23 wt.% prior to esterification. In some embodiments, prior to esterification, glycerol may be present in the pre-esterification mixture in an amount of about 15 wt.%, about 16 wt.%, about 17 wt.%, about 18 wt.%, about 19 wt.%, about 20 wt.%, about 21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, or any range that includes and/or is between any two of the foregoing values.

After esterification, the natural oil-based petrolatum composition may contain minimal amounts of free fatty acids and glycerin. For example, the composition may comprise less than about 2% by weight free fatty acids and free glycerin. In another embodiment, the composition may comprise less than about 1 wt.%, about 2.5 wt.%, less than about 5 wt.%, or less than about 10 wt.% free fatty acids, free glycerol, and triacylglycerides.

In some embodiments, the acylglyceride polymer having at least two dimer structures is represented by: wherein R3 is hydrogen, glycerol, substituted glycerol or fatty acid, and n is one or more.

The composition may comprise from about 5.0% to about 50% by weight of an acylglyceride polymer having at least two dimer structures. Alternatively, the composition may comprise greater than 10% or about 5.0% to about 50% by weight of the acylglyceride polymer having at least two dimer structures.

The natural oil-based petrolatum composition of the present invention may be further described in terms of average molecular weight distribution, which may be determined by Gel Permeation Chromatography (GPC).

As described herein in any embodiment, the natural-based petrolatum composition may include one or more of the following: i) An acid number of less than about 5.0; ii) a polydispersity index of greater than about 1.3 or an iodine value of less than about 10.0.

As described herein in any embodiment, the acid number may be less than about 5.0mg KOH/g, less than about 1.5mg KOH/g, or from about 0.1mg KOH/g to about 1.5mg KOH/g. For example, in any of the embodiments disclosed herein, the acid number may be from about 0.1mg KOH/g to less than about 5.0mg KOH/g, from about 0.1mg KOH/g to about 3.5mg KOH/g, from about 0.1mg KOH/g to about 1.5mg KOH/g, or any range comprising and/or between any two of the foregoing values.

The compositions described herein may have an iodine value of less than about 10.0, or less than about 5.0, or between about 0.5 and about 4.5. Suitable iodine values, as described herein in any embodiment, may include about 0.5, about 1.0, about 1.5, about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about 8.0, about 8.5, about 9.0, about 9.5, about 10.0, or any range including and/or between any two of the foregoing values. For example, the iodine value may be about 0.5 to about 5.0, about 0.5 to about 4.5, about 1.0 to about 4.5, or about 2.5 to about 4.5.

As described herein in any embodiment, the composition may have a polydispersity index (PDI) of greater than about 1.3. For example, the composition may have a PDI of about 1.3 to about 2.0 or from about 1.3 to about 1.7.

The natural-based petrolatum composition described herein may be a semi-solid material that may retain its own shape, but flex under pressure, resembling a grease 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: drop point of about 30 ℃ to about 60 ℃, cone penetration of greater than 20 or from about 20 to about 100 or from about 40 to about 60 (Dmm (1/10 mm) at 25 ℃, about 5mm at 100 DEG C ² /s to about 35mm ² Dynamic viscosity of/s, congealing point from about 25 ℃ to about 45 ℃, or combinations thereof.

Process for preparing natural oil-based petrolatum compositions

The present disclosure also provides a method of preparing a natural oil-based petrolatum composition. The method involves mixing a hydrogenated natural oil, a fatty acid dimer, and glycerin. The resulting mixture is treated with an esterification catalyst that induces esterification and transesterification. The reaction is allowed to proceed until the reaction mixture reaches an acid number of less than 5.0mg KOH/g or until the reaction mixture reaches an acid number of less than 1.5mg KOH/g to provide a natural oil-based petrolatum composition. In some embodiments, the reaction mixture achieves an acid number of about 0.1mg KOH/g to about 1.5mg KOH/g. In some embodiments, the reaction mixture achieves an acid number between 0.5mg KOH/g and 1.5mg KOH/g.

The natural oil may be a vegetable oil or an animal oil. Examples of natural oils may include, but are not limited to, 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, hemp oil, algae oil, castor oil, lard, tallow, poultry fat, yellow grease, fish oil, or mixtures thereof. As described herein in any embodiment, the natural oil may be a hydrogenated natural oil.

In various embodiments, the fatty acid dimer has the following structure

R ¹ And R is ² Are each independently defined divalent fatty acid chains, such that R ¹ And R is ² May be the same or different. When R is ¹ And R is ² In the same case, dimerized fatty acids represent fatty acid homodimers. When R is ¹ And R is ² Unlike the above, dimerized fatty acids represent fatty acid heterodimers. In various embodiments, R ¹ And R is ² Each of which is independently substituted or unsubstituted C ₇ -C ₂₁ An aliphatic group corresponding to a saturated chain or an unsaturated fatty acid side chain having one, two, three or more double bonds. R is R ¹ And R is ² Can represent a substituted form of the side chain of a naturally occurring fatty acid. For example, R ¹ And R is ² May each independently be a saturated or unsaturated linear aliphatic group having 7, 9, 11, 13, 15, 17, 19 or 21 carbons. When R is ¹ And R is ² In the case of saturated or unsaturated groups of 17 carbons each, the resulting dimer fatty acid has 36 carbons. R is R ¹ And R is ² May contain hydrogen, carbon, oxygen and nitrogen atoms; or R is ¹ And R is ² May consist of carbon, hydrogen and oxygen atoms; or R is ¹ And R is ² May consist of carbon and hydrogen atoms.

The linking group Z is a bond, an oxygen atom or a sulfur atom. The linking group Z may be attached to R via any position ¹ And R is ² . When Z is a bond, the dimerized fatty acid may have the following structure:

non-limiting examples of dimerized fatty acids include those commercially available as the radiac 0960 hydrogenated standard dimer and the radiac 0970 distilled dimer acid (belgium euclidean corporation) and UNIDYME 18 dimer acid (kotanium corporation of houston, texas). The dimerized fatty acids may be derived from natural oils. As another example, T18 dimer acid may be used. As used herein, the radio 0960 distilled dimer acid (belgium euclidean) was analyzed to contain 1.6% monomer, 79.22% dimer, 14.99% trimer, and 4.19% tetramer or higher.

The methods described herein may include the following steps. The reaction mixture of hydrogenated natural oil, glycerol and fatty acid dimer is pre-melted and heated to a temperature ranging from 60 ℃ to 80 ℃ and then added to the reaction vessel along with a nitrogen sweep to prevent oxidation.

The reaction mixture has the composition described herein and the mixture is treated by methods well known in the art to induce chemical or enzymatic transesterification and esterification.

For chemical transesterification, the catalyst may be added in an amount of about 0.1% by weight relative to the reaction mixture. Exemplary catalysts may be potassium hydroxide or calcium hydroxide. The reaction temperature may then be raised to about 200 ℃ to 250 ℃. The reaction temperature is maintained until an acid number of less than 5.0 is achieved or a polydispersity index of greater than 1.3 is obtained. An acid, for example a mineral acid such as phosphoric acid, may be added in an amount of about 0.2% by weight 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 ℃. A filter medium, such as an acid activated bleaching clay, may be added to the reaction mixture in an amount of about 2 wt.% relative to the reaction mixture to remove impurities. The final product, the natural oil-based petrolatum composition, is then filtered to remove the mixture of salts and clay.

Alternatively, the enzyme catalyst may be added in an amount of 2 wt.% relative to the reaction mixture for enzymatic transesterification. 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 achieved 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.

Topical formulations

The emulsions provided herein are useful for making topical formulations, such as personal care products or cosmetics. The inventors have unexpectedly found that formulations comprising a natural oil-based petrolatum as described herein possess a number of desirable properties, 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" means and includes any cosmetic, hygiene, rinse-off, and topical care products, 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; toilet or anti-knotting creams; hair style maintenance and conditioning products (concentrated mask 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 shampoos, body washes and conditioner formulations, or any conditioning formulation.

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 be further 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. Those skilled in the art will readily appreciate the range of additives that may be used for this purpose, including but not limited to the following: sclerotium gum, xanthan gum, carrageenan, 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. Those skilled in the art will appreciate that they 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. Additional texturizers may or may not be used in the formulation comprising the anhydride modified starch disclosed herein and will depend on the needs of the formulation and the purpose of the product being prepared. When the anhydride modified starches disclosed herein are used in shampoo or hair conditioning formulations, it may be desirable to add additional conditioning agents to aid in viscosity.

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 1 wt% to 100 wt%, 50 wt% to 99 wt%, 75 wt% to 95 wt%, 20 wt% to 90 wt%, 20 wt% to 80 wt%, 1 wt% to 30 wt%, 2 wt% to 20 wt%, or 1 wt% to 15 wt% of natural oil-based petrolatum.

In some embodiments, 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 agent.

In another embodiment, the esterification product of the pre-esterification mixture comprises: about 15 wt.% to about 25 wt.% of a fatty acid dimer, about 15 wt.% to about 25 wt.% of glycerol, and about 55 wt.% to about 70 wt.% of a hydrogenated natural oil, wherein the esterification product has an iodine value of less than 50, or less than 25, or less than 10.

In another embodiment, the esterification product of the pre-esterification mixture comprises: about 15 wt% to about 25 wt% fatty acid dimer, about 15 wt% to about 25 wt% glycerol, and about 55 wt% to about 70 wt% hydrogenated natural oil, wherein the esterification product has an iodine value of between 1 and 50, or between 1 and 25, or between 1 and 10.

In another embodiment, the esterification product of the pre-esterification mixture comprises: about 15 wt.% to about 25 wt.% of fatty acid dimer, about 15 wt.% to about 25 wt.% of glycerol, and about 55 wt.% to about 70 wt.% of hydrogenated natural oil, wherein the esterification product has a polydispersity index of greater than 1.3, or greater than 1.5, or between about 1.3 and about 2.0, or between about 1.3 and about 1.7.

In another embodiment, the esterification product of the pre-esterification mixture comprises: about 15 wt.% to about 25 wt.% of fatty acid dimer, about 15 wt.% to about 25 wt.% of glycerol, and about 55 wt.% to about 70 wt.% of hydrogenated natural oil, wherein the esterification product has an acid number of less than 5.0mg KOH/g or between 0.1mg KOH/g and 1.5mg KOH/g or between 0.5mg KOH/g and 1.5mg KOH/g.

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 fatty acid dimer, hydrogenated natural oil, and glycerin ratios; and each combination of one or more values or ranges of the following parameters: drop melting point, cone penetration, dynamic viscosity, set point, hydroxyl number, acid number, iodine number, and polydispersity index.

Examples

TABLE 1.

Example 1：

The following chemical transesterification method was performed to prepare sample C1. Will be described in Table 2All components (including dimers) or oils were premelted and heated to 70 ℃ and then added to the reaction vessel under a nitrogen sweep to prevent oxidation of the product during the reaction. The stirrer was turned on to mix the contents. Caustic catalyst (potassium hydroxide (KOH) or calcium hydroxide (Ca (OH)) was added at a dose of 0.1% ₂ )). Once all ingredients are added and thoroughly mixed, the temperature is raised to 200 ℃ to 250 ℃. The reaction temperature is maintained until an acid value of 10 or less is achieved. 0.2% acid (85% strength phosphoric acid) was added to neutralize the catalyst slightly in excess. The mixture was cooled to 70 ℃, then acid activated bleaching clay B80 was added to the reaction in an amount of 2% and the salt was allowed to be absorbed from the catalyst. The product is then filtered to remove salt and clay mixtures as well as other impurities.

TABLE 2.

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Claims

1. A natural oil-based petrolatum composition comprising the esterification product of a pre-esterification mixture comprising:

about 15 wt% to about 25 wt% of a fatty acid dimer based on the total weight of the pre-esterification mixture;

about 15 wt% to about 25 wt% of glycerol based on the total weight of the pre-esterification mixture; and

about 55 wt% to about 70 wt% hydrogenated natural oil based on the total weight of the pre-esterification mixture;

wherein the natural oil-based petrolatum product has an acid number of less than about 5.0mg KOH/g.

2. The natural oil based petrolatum of claim 1 wherein the acid number is less than about 1.5mgKOH/g.

3. The natural oil-based petrolatum of claim 1, wherein the acid value is from about 0.1mg KOH/g to about 1.5mg KOH/g.

4. The natural oil-based petrolatum of claim 1, wherein the pre-esterified mixture comprises from about 18% to about 23% by weight of the fatty acid dimer.

5. The natural oil-based petrolatum of claim 1, wherein the pre-esterified mixture comprises from about 18% to about 23% by weight of the glycerin.

6. The natural oil-based petrolatum of claim 1, wherein the pre-esterified mixture comprises from about 55% to about 65% by weight of the hydrogenated natural oil.

7. The natural oil-based petrolatum of claim 1, wherein the hydrogenated natural oil comprises hydrogenated soybean oil, hydrogenated palm oil, hydrogenated canola oil, hydrogenated castor oil, hydrogenated coconut oil, or combinations thereof.

8. The natural oil-based petrolatum of claim 7, wherein the hydrogenated natural oil comprises at least two or more hydrogenated soybean oil, hydrogenated palm oil, hydrogenated canola oil, hydrogenated castor oil, hydrogenated coconut oil, or combinations thereof.

9. The natural oil-based petrolatum of claim 1, wherein the natural oil-based petrolatum further has an iodine value of less than about 10.0.

10. The natural oil-based petrolatum of claim 1, wherein the natural oil-based petrolatum further has a polydispersity index of greater than about 1.3.

11. According to claim 1Wherein the natural oil-based petrolatum exhibits one or more rheological properties selected from the group consisting of: drop point of about 30 ℃ to about 60 ℃, cone penetration of from about 20 to about 100 (Dmm (1/10 mm)) at 25 ℃, about 5mm at 100 °c ² /s to about 35mm ² Dynamic viscosity of/s, congealing point from about 25 ℃ to about 45 ℃, or combinations thereof.

12. A personal care product comprising a natural oil-based petrolatum composition, wherein the natural oil-based petrolatum composition comprises the esterification product of a pre-esterification mixture comprising:

13. The personal care product of claim 12, wherein the natural oil-based petrolatum has an acid number of less than about 1.5mg KOH/g.

14. The personal care product of claim 12, wherein the natural oil-based petrolatum has an acid number of from about 0.1mg KOH/g to about 1.5mg KOH/g.

15. The personal care product of claim 12, which is a body wash, facial cleanser, shampoo, conditioner, toilet cream, skin moisturizer, skin lotion, lip moisturizer, or cosmetic agent.

16. A method of making a natural oil-based petrolatum composition, the method comprising:

mixing a hydrogenated natural oil, a fatty acid dimer and glycerol to obtain a pre-esterified mixture;

treating the pre-esterification mixture with an esterification catalyst to obtain a reaction mixture; and

reacting the reaction mixture until the reaction mixture reaches an acid value of less than about 5.0mgKOH/g to obtain the natural oil-based petrolatum composition.