CN116723823A - Natural oil-based vaseline and preparation method thereof - Google Patents

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: from about 0.1% to about 40% by weight of a dimer fatty acid, from about 99.9% to about 60% by weight of one or more components selected from the group consisting of C1-C6 polyols, natural oils, fatty acids, and acylglycerols, wherein the natural-based petrolatum product has a cone penetration value of greater than 10 and a polydispersity index of greater than 1.3. 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. 63/134,019 filed on day 1 and 5 of 2021 and U.S. provisional application No. 63/156,570 filed on day 3 and 4 of 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 unique melting point as organic compounds traditionally thought to be. 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 cases where the refining history is incomplete, 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 rheological properties 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 elegant esterification methods disclosed herein utilizing fatty acid dimers and multiple components allow for the production of natural-based petrolatum mimics. The present disclosure provides a natural oil-based petrolatum composition comprising the esterification product of: about 0.1% to about 40% by weight of a dimer fatty acid; from about 99.9% to about 60% by weight of one or more components selected from the group consisting of C2-C6 polyols, natural oils, hydrogenated natural oils, fatty acids, and acylglycerols, wherein the natural-based petrolatum product has a cone penetration value of greater than 10 and a polydispersity index of greater than 1.3.

The present disclosure also provides a method of preparing a natural oil-based petrolatum composition. The method comprises about 0.1 wt% to about 40 wt% of a fatty acid dimer, about 99.9 wt% to about 60 wt% of one or more components selected from the group consisting of C2-C6 polyols, natural oils, hydrogenated natural oils, fatty acids, and acylglycerols, to form a pre-esterified mixture; and adding a caustic catalyst or enzyme catalyst to the mixture to promote the esterification reaction until the mixture achieves an Acid Value (AV) of less than about 20 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 about 0.1 wt% to about 40 wt% of a fatty acid dimer, about 99.9 wt% to about 60 wt% of one or more components selected from the group consisting of C2-C6 polyols, natural oils, hydrogenated natural oils, fatty acids, and acylglycerols, to form a pre-esterified mixture; and adding a caustic catalyst or an enzyme catalyst to the mixture to promote the esterification reaction until the mixture has one or more of: i) A cone penetration value greater than about 10.0; 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 industrial applications. 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 the ability to coat and protect the skin.

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 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. One aspect described in connection with a particular aspect is not necessarily limited to that aspect and may be practiced with any other aspect.

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 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.

"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 by 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 aspects, one fatty acid may dimerize with another fatty acid to produce dimerized fatty acids. 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 by 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.

"fatty acids" are C8-C22 alkyl chains linked to an acid moiety. The fatty acids may be saturated or unsaturated. The fatty acids may be linear or branched and may contain substituents such as C1-C3 alkyl or hydroxy.

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), isostearic acid, ricinoleic acid, oleic acid (18:1), linoleic acid (18:2), and linolenic acid (18:3). In some aspects, the fatty acid may be isostearic acid or stearic acid.

The fatty acid composition of the oil can be determined by methods well known in the art. The american society of oleochemists (AOCS) claims analytical methods for many 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 term "C2-C6 polyol" means any two to six carbon atom structure containing more than one hydroxyl group. Non-limiting examples of C2-C6 polyols include: ethylene glycol, glycerol, butylene glycol, propylene glycol, hexylene glycol, sugar alcohols, sorbitol and erythritol. In some aspects, the C2-C6 polyol may be glycerol.

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, such as by 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 Can be corresponding to fatLinear aliphatic groups of fatty acid side chains, and linking groups Z may be linked at ω numbers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, etc., or alternatively linking groups Z may be linked at terminal (ω -1) carbons. 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, drop points are determined by 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 "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.

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 300X 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 ² n _i /ΣM _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 Σm _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 20.0, or less than 10.0, 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.

In some aspects, the hydrogenated natural oil is hydrogenated soybean oil, palm oil, canola oil, castor oil, or coconut oil.

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

In some aspects, 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 aspects, the fatty acid dimer may be radio 0970. 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 aspect, 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 and triacylglycerides.

In some aspects, 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 application may be further described in terms of average molecular weight distribution, which may be determined by Gel Permeation Chromatography (GPC).

As described in any aspect herein, the natural-based petrolatum composition may comprise one or more of the following: i) An acid number of less than about 20.0; ii) a polydispersity index of greater than about 1.3; or an iodine value of less than about 10.0.

In any aspect, the acid number as described herein can be from about 5 to about 20.0, or from about 10 to about 20.

The compositions described herein may have an iodine value of less than about 10.0, or less than about 8.0, or between about 4.0 and about 10. In any aspect, suitable iodine values as described herein can 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 in any aspect herein, 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 about 1.3 to 1.7.

Unlike waxes or hard fats, the natural-based petrolatum formulation described herein may be a semi-solid material that may 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. The natural-based petrolatum formulations described herein may have an cone penetration of greater than 10Dmm, or about 10Dmm to about 250Dmm, or from about 50Dmm to about 100Dmm (1/10 mm) at 25 ℃.

The natural-based petrolatum exhibits a combination of rheological properties that provide spreading and viscosity comparable to petroleum-based petrolatum. In any aspect disclosed herein, the natural-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 20Dmm or about 20Dmm to about 250Dmm or about 60Dmm to about 200Dmm (1/10 mm) at 25 ℃, about 5mm at 100 DEG C ² From/s to about 60mm 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 fatty acids, hydrogenated natural oils, fatty acid dimers, 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 5.0 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 4.0. In some aspects, the reaction mixture achieves an acid number between 0.5 and 3.5.

The natural oil may be a vegetable oil or an animal oil. Examples of 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, castor oil, lard, tallow, poultry fat, yellow grease, fish oil, or mixtures thereof.

In various aspects, 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 aspects, 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. One or more reaction mixtures of components selected from the group consisting of C2-C6 polyols, natural oils, hydrogenated natural oils, fatty acids and acylglycerols and fatty acid dimers are premelted and heated to a temperature in the range of 60 ℃ to 80 ℃ and then added to the reaction vessel 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 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 is maintained in the range of about 60 ℃ to 80 ℃ 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.

Alternatively, for acid catalyzed transesterification, it is preferred that the components (excluding dimers and catalyst) are premelted and heated to 110 ℃ and then added to the reaction vessel. The dimer may then be added to the reaction vessel under a nitrogen sweep to help prevent the introduction of oxygen, resulting in an onset temperature of 60 ℃ to 70 ℃. An acid catalyst may be added to promote the reaction. Those skilled in the art will appreciate that a wide variety of catalysts may be used in such reactions. In some aspects, the catalyst may be (methanesulfonic acid (MSA)) and/or HPPA (hypophosphorous acid, 50% in water). The catalyst is generally utilized in an amount of 0.1% to 0.2% based on the mass of the reaction components. The reaction was then stirred and heated to an elevated temperature. The reaction rate will depend on the temperature and thus an elevated temperature may be desired, however, at too high a reaction temperature also undesired by-products may be degraded and produced. In some aspects, the reaction temperature is 140 ℃ to 180 ℃. In other aspects, the reaction temperature is about 160 ℃. The reaction temperature was maintained until an acid value of 2 or less was achieved and the melting point and molecular weight distribution had stabilized. Reduced vacuum pressure may be applied to accelerate or complete the reaction. The reaction mixture may be cooled to about 80 ℃ to 90 ℃ and then base is added to neutralize any residual acid. In some aspects, the base is solid calcium hydroxide. The base may be added in any amount sufficient for neutralization. The reaction product may be isolated or, alternatively, silica gel (such as TRISYL) may be added to the reaction at about 1% to bleach and absorb polar impurities. The product may then be filtered to remove salt and silica mixtures as well as other impurities.

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 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 application 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 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), pectin, calcium citrate, salts (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 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 agent.

The inventors have expressly contemplated and envisaged any and every combination of two or more features of the natural-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, isostearic acid, hydrogenated natural oil, and glycerin ratio; 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 samples from tables 2 to 4. All components (including dimers) and other components as described in tables 2-4 were pre-melted 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.

TABLE 3 Table 3.

TABLE 4 Table 4.

Example 2：

The following chemical transesterification method was performed to prepare samples A3 to A7 in Table 5. The components (excluding dimers) were pre-melted and heated to 110 ℃ before being added to the reaction vessel. The dimer was then added to the reaction vessel under a nitrogen sweep to give an onset temperature of 60 ℃ to 70 ℃. The acid catalyst (methanesulfonic acid (MSA)) and HPPA (hypophosphorous acid, 50% in water) were each added at a dose of 0.1% based on the mass of the reactants. The stirrer was turned on to mix the contents. Once all ingredients were added and thoroughly mixed, the temperature was raised to 160 ℃. The reaction temperature was maintained until an acid value of 2 or less was achieved and the melting point and molecular weight distribution were stable. The mixture was cooled to 85 ℃ and then solid calcium hydroxide was added at 0.16% based on the total mass of the reactants. Silica gel TRISYL was added to the reaction at 1% based on the total mass of the reactants. The product is then filtered to remove salts, silica mixtures, and other impurities.

TABLE 5.

The repetition number may be included in () with any value.

Claims (5)

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

about 0.1% to about 40% by weight of a dimer fatty acid,

About 99.9% to about 60% by weight of one or more components selected from the group consisting of C2-C6 polyols, natural oils, hydrogenated natural oils, fatty acids, and acylglycerols, wherein the natural-based petrolatum product has a cone penetration value of greater than 10 and a polydispersity index of greater than 1.3.

2. The natural oil-based petrolatum of claim 1, having an iodine value of less than 5.0.

3. 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:

about 0.1% to about 40% by weight of a dimer fatty acid,

About 99.9% to about 60% by weight of one or more components selected from the group consisting of C2-C6 polyols, natural oils, hydrogenated natural oils, fatty acids, and acylglycerols, wherein the natural-based petrolatum product has a cone penetration value of greater than 10 and a polydispersity index of greater than 1.3.

4. The personal care product of claim 3, wherein the natural oil-based petrolatum has an iodine value of less than 5.

5. A personal care product which is a body wash, facial cleanser, shampoo, conditioner, toilet cream, skin moisturizer, skin lotion, lip moisturizer or cosmetic agent.