Emulsion blends for coating carbonates

Abstract

Provided herein are compositions and methods for coating nanoparticles. More specifically, the present invention relates to coated carbonates and to a process for the preparation thereof and to the use thereof as an additive in the production of composite materials.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application Nos. 63 / 414,210 (filed on October 7, 2022) and 63 / 542,266 (filed on October 3, 2023), the entire contents of which are hereby incorporated by reference for all purposes. Technical Field

[0003] Provided herein are compositions and methods of making the same, including nanoparticle carbonates containing an organic composition comprising one or more fatty acids. Background Art

[0004] Carbonates can be used as filler materials for resins, but they are usually surface treated to change their polarity and chemical properties. Surface treated carbonates can provide improved characteristics, such as improved dispersibility and adhesion properties. For example, see: U.S. Patent Nos. 6,686,044 and 4,191,670. But these and other properties can be further customized for specific uses or composite materials.

[0005] Thus, there remains a need for compositions and related methods comprising carbonates surface treated with an unsaturated fatty acid or fatty acid mixture. Summary of the invention

[0006] Provided herein are compositions and methods including surface-treated carbonate (eg, calcium carbonate) nanoparticles, wherein the surface treatment includes an unsaturated fatty acid, such as eladic acid, or a fatty acid mixture, such as tall oil fatty acid (TOFA).

[0007] In certain aspects and embodiments, the compositions provided herein are nanoparticle compositions, including surface-treated carbonate (e.g., calcium carbonate) nanoparticles;

[0008] wherein the carbonate nanoparticles are treated with a fatty acid mixture comprising about 40-80% saturated fatty acids or mixtures thereof and about 20-60% unsaturated fatty acids or mixtures thereof;

[0009] The unsaturated fatty acid or mixture thereof comprises at least about 10% of elaidic acid or a salt thereof.

[0010] In certain embodiments, the unsaturated fatty acid or mixture thereof comprises at least about 20% elaidic acid or a salt thereof.

[0011] In certain embodiments, provided herein are filler compositions comprising the nanoparticle compositions disclosed herein.

[0012] In certain embodiments, provided herein are methods of preparing a nanoparticle composition disclosed in the embodiments herein, the methods comprising:

[0013] preparing a surface coating emulsion comprising a fatty acid mixture under alkaline conditions; and

[0014] The calcium carbonate nanoparticles are mixed with a surface coating emulsion.

[0015] These and other objects, aspects and embodiments will become more apparent when read in conjunction with the following detailed description. DETAILED DESCRIPTION

[0016] Description of Exemplary Embodiments

[0017] Provided herein are compositions and methods comprising surface-treated calcium carbonate nanoparticles, wherein the surface treatment comprises an unsaturated fatty acid, such as eladic acid, or a fatty acid mixture, such as tall oil fatty acid (TOFA).

[0018] definition

[0019] When referring to the compounds provided herein, the following terms have the following meanings unless otherwise indicated. Unless otherwise defined, all technical and scientific terms used herein have the meanings commonly understood by those of ordinary skill in the art. If a term herein has multiple definitions, the definition in this section shall prevail unless otherwise indicated.

[0020] Unless otherwise indicated, the terms "a" and "an" as used herein include not only aspects and embodiments having one member, but also aspects and embodiments having multiple members. For example, a composition comprising a saturated fatty acid and an unsaturated fatty acid is understood to give aspects having at least a second saturated fatty acid, at least a second unsaturated fatty acid, or both.

[0021] Unless otherwise indicated, the term "about" used herein to modify a numerical value refers to a determined range around the value. For example, "about X" generally refers to a value between 0.95X and 1.05X. Any reference to "about X" specifically refers to a value of at least 0.95X, 0.96X, 0.97X, 0.98X, 0.99X, 1.00X, 1.01X, 1.02X, 1.03X, 1.04X, and 1.05X. Therefore, "about X" is used to guide claim limitations such as "0.98X" and "X" and provide support for written descriptions.

[0022] When "about" is used at the beginning of a numerical range, it applies to both ends of the range. Thus, "from about 50 nm to 300 nm" is equivalent to "about 50-300 nm". When "about" is used at the beginning of a numerical list, it applies to all members of the list. Thus, "about 50%, 60% or 75%" is equivalent to "about 50%, about 60% or about 75%".

[0023] As used herein, unless otherwise indicated, the terms "nanoparticle" and "nanoparticle" refer to one or more objects having nanoscale dimensions (ie, length, width, and height are all in the range of about 1-500 nm).

[0024] As used herein, the term "or" should generally be interpreted as a Boolean "or" (i.e., not excluding "and"). For example, an embodiment of "a composition comprising A or B" will generally present aspects of a composition comprising A and B. The term "or" should be interpreted as excluding those aspects presented that cannot be combined without contradiction.

[0025] Unless otherwise indicated, the terms "%" or "% composition" as used herein refer to weight / weight percentages (i.e., w / w). For example, a composition containing 67% fatty acids contains 67g of fatty acids per 100g of the total composition, while a mixture containing 40% saturated fatty acids and 60% unsaturated fatty acids contains 40g of unsaturated fatty acid esters for every 60g of saturated fatty acids. Unsaturated fatty acids or mixtures thereof containing at least 10% elaidic acid contain at least 10g of elaidic acid per 100g of unsaturated fatty acids.

[0026] Unless otherwise specified, the term "saturated fatty acid" as used herein refers to fatty acids R a -CO 2 H or a salt thereof, wherein R a is an aliphatic hydrocarbon chain which may be straight (ie, unbranched) or branched, and wherein R a Does not contain carbon-carbon double or triple bonds. Saturated acids or R a The hydrocarbon chain may contain a specified number or range of carbon atoms. For example, palmitic acid is C 16 Saturated fatty acids, while "C 6 -C 30 "Saturated fatty acids" refer to fatty acids that can have from 6 to 30 carbon atoms.

[0027] Unless otherwise specified, the term "unsaturated fatty acid" as used herein refers to fatty acids R b -CO 2 H or a salt thereof, wherein R b is an aliphatic hydrocarbon chain which may be straight (ie, unbranched) or branched, and wherein R b Contains at least one carbon-carbon double or triple bond. An unsaturated acid or R bCan contain the specified number or range of carbon atoms. For example, elaidic acid is a C 18 Unsaturated fatty acids, and "C 12 -C 30 "Unsaturated fatty acids" refer to fatty acids that can have from 12 to 30 carbon atoms.

[0028] Composition

[0029] In certain embodiments, provided herein is a nanoparticle composition comprising surface-treated calcium carbonate nanoparticles.

[0030] In certain embodiments, provided herein is a nanoparticle composition comprising surface-treated calcium carbonate nanoparticles;

[0031] wherein the calcium carbonate nanoparticles are treated with a fatty acid mixture comprising about 40-80% saturated fatty acids or mixtures thereof and about 20-60% unsaturated fatty acids or mixtures thereof;

[0032] The unsaturated fatty acid or mixture thereof comprises at least about 10% of elaidic acid or a salt thereof.

[0033] In certain embodiments, the unsaturated fatty acid or mixture thereof comprises at least about 20% elaidic acid or a salt thereof.

[0034] In certain embodiments, the unsaturated fatty acid or mixture thereof comprises at least about 5% elaidic acid or a salt thereof.

[0035] In certain embodiments, the unsaturated fatty acid is elaidic acid or a salt thereof. In certain embodiments, the unsaturated fatty acid comprises elaidic acid or a salt thereof.

[0036] In certain embodiments, provided herein are nanoparticle compositions disclosed herein, wherein the unsaturated fatty acid or mixture thereof is tall oil fatty acid (TOFA) (e.g. 1483 etc.) or a salt thereof. In certain embodiments, provided herein is a nanoparticle composition disclosed herein, wherein the unsaturated fatty acid or mixture thereof comprises TOFA or a salt thereof.

[0037] In certain embodiments, the unsaturated fatty acid or mixture thereof is a mixture derived from a vegetable oil (e.g., AltaVeg TM FA 140, etc.) or a salt thereof. In certain embodiments, provided herein is a nanoparticle composition disclosed herein, wherein the unsaturated fatty acid or mixture thereof comprises a plant oil-derived mixture or a salt thereof.

[0038] In certain embodiments, the unsaturated fatty acids or mixtures thereof comprise TOFA and a mixture derived from a vegetable oil (e.g., AltaVeg TM In certain embodiments, the unsaturated fatty acid or mixture thereof is a mixture of TOFA and a mixture derived from a vegetable oil or a mixture of a salt thereof.

[0039] In certain embodiments, the tall oil fatty acid (TOFA) comprises about 5-13% saturated fatty acids (e.g., about 5, 6, 7, 8, 9, 10, 11, 12 or 13%, such as 10%) and about 75-95% (e.g., about 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92 or 93%, such as 83%) unsaturated fatty acids.

[0040] In some embodiments, provided herein are nanoparticle compositions disclosed herein wherein the average particle size is about 30 nm (e.g., about 25, 30, 35, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100) to about 200 nm (e.g., about 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, or 275 nm). In some embodiments, the average particle size is about 50-150 nm.

[0041] In some embodiments, provided herein are nanoparticle compositions disclosed herein, wherein the fatty acid mixture is about 40% (e.g., about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50%) to about 64% (e.g., about 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70%) of unsaturated fatty acids or mixtures thereof.

[0042] In some embodiments, provided herein are nanoparticle compositions disclosed herein wherein the fatty acid mixture is about 40-80% (e.g., about 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, or 84%) saturated fat. acid or mixtures thereof (e.g., stearic acid or a mixture of stearic acid and palmitic acid or a salt thereof) and about 60-20% (e.g., about 63, 62, 61, 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20 or 19%) of unsaturated fatty acids or mixtures thereof (e.g., TOFA, such as 1483, or a salt thereof).

[0043] In some embodiments, provided herein are nanoparticle compositions disclosed herein, wherein the fatty acid mixture is about 60% saturated fatty acids or mixtures thereof and about 40% unsaturated fatty acids or mixtures thereof.

[0044] In certain embodiments, the saturated fatty acid is selected from the group consisting of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, lignic acid, hexadecanoic acid, montanic acid, melissic acid, and salts thereof.

[0045] In certain embodiments, provided herein are nanoparticle compositions disclosed herein, wherein the saturated fatty acid or mixture thereof comprises stearic acid or a salt thereof and palmitic acid or a salt thereof.

[0046] In certain embodiments, the unsaturated fatty acid is C 16 -C 22 Unsaturated fatty acids or C 16 -C 22 Mixture of unsaturated fatty acids. In certain embodiments, the unsaturated fatty acid is selected from oleic acid, palmitoleic acid, elaidic acid, α-linolenic acid, linoleic acid (conjugated or non-conjugated), and salts thereof.

[0047] In some embodiments, provided herein are nanoparticle compositions disclosed herein wherein the unsaturated fatty acid or mixture thereof comprises at least about 40% (e.g., at least about 20, 25, 30, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, or 65%) elaidic acid or a salt thereof.

[0048] In some embodiments, provided herein are nanoparticle compositions disclosed herein wherein the unsaturated fatty acid or mixture thereof comprises at least about 20% (for example, at least about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 61, 62, 63, 64, or 65%) of elaidic acid or a salt thereof.

[0049] In some embodiments, provided herein are nanoparticle compositions disclosed herein wherein the unsaturated fatty acid or mixture thereof comprises at least about 10% (for example, at least about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 61, 62, 63, 64, or 65%) of elaidic acid or a salt thereof.

[0050] In some embodiments, provided herein are nanoparticle compositions disclosed herein wherein the unsaturated fatty acid or mixture thereof comprises at least about 5% (for example, at least about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 61, 62, 63, 64, or 65%) of elaidic acid or a salt thereof.

[0051] In certain embodiments, the unsaturated fatty acid is a mixture of fatty acids and their salts comprising oleic acid, elaidic acid, linoleic acid (conjugated or non-conjugated). In certain embodiments, the unsaturated fatty acid is a mixture of fatty acids comprising elaidic acid or its salt.

[0052] In some embodiments, provided herein is a nanoparticle composition disclosed herein, wherein the unsaturated fatty acid or mixture thereof comprises oleic acid or a salt thereof and linoleic acid or a salt thereof.

[0053] In some embodiments, provided herein are nanoparticle compositions disclosed herein, wherein the unsaturated fatty acid or mixture thereof comprises less than about 30% (e.g., less than about 35, 30, 25, 20, 15, 10, 5, or 1%) linolenic acid or a salt thereof.

[0054] In certain embodiments, provided herein are filler compositions comprising the nanoparticle compositions disclosed herein.

[0055] In certain embodiments, provided herein is a method of preparing a nanoparticle composition disclosed in the embodiments herein, the method comprising:

[0056] preparing a surface coating emulsion comprising a fatty acid mixture under alkaline conditions; and

[0057] The calcium carbonate nanoparticles are mixed with a surface coating emulsion.

[0058] In certain embodiments, provided herein is a method for preparing a nanoparticle composition disclosed in the embodiments herein, wherein preparing a surface coating emulsion comprises:

[0059] preparing a mixture having about 5-9% solids; and

[0060] The mixture was stirred at about 80-85 °C.

[0061] In certain embodiments, the mixture is about 4, 5, 6, 7, 8, 9, or 10% solids.

[0062] In some embodiments, provided herein is a method of preparing a nanoparticle composition disclosed in the embodiments herein, wherein the mixture is stirred for at least about 30 minutes (e.g., at least about 30, 35, 40, 45, 50, 55, or 60 minutes).

[0063] In some embodiments, provided herein is a method of preparing a nanoparticle composition disclosed in the embodiments herein, wherein the basic conditions require at least 1.03 equivalents of a strong base (e.g., about 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.15, 1.20, 1.25, 1.3, 1.4, or 1.5 equivalents).

[0064] In certain embodiments, provided herein is a method of preparing a nanoparticle composition disclosed in the embodiments herein, wherein the method of preparing the nanoparticle composition further comprises dehydrating the surface-treated calcium carbonate nanoparticles.

[0065] Preparation of components

[0066] The component compounds and nanoparticle carbonates provided herein can be prepared, isolated or obtained by any method apparent to one skilled in the art.

[0067] Example

[0068] As used herein, the symbols and conventions used in the methods, protocols and examples, regardless of whether or not particular abbreviations are specifically defined thereto, are consistent with those used in contemporary scientific literature.

[0069] Example 1

[0070] Tall Oil Fatty Acid (TOFA) Method Description

[0071] After preparing ultrafine precipitated calcium carbonate (PCC) having a primary particle size of 30-200 nm (more specifically 50-150 nm), the surface of the particles is surface treated with a hydrophobic agent.

[0072] Use 60% stearic acid (e.g. ~41-50% palmitic acid (C 16 ) and ~42-52% stearic acid (C 18 ) with 40% TOFA (e.g. 1483) to prepare the surface coating. The 60 / 40 blend was converted to the fatty acid salt by mixing in enough NaOH or KOH to reach the stoichiometric point, with 3-10% excess NaOH or KOH to ensure complete conversion of the fatty acids to salts. The emulsion was made at 5-9% solids in water at 80-85°C and mixed for at least 30 minutes to ensure proper micelle formation.

[0073] The resulting emulsion is then mixed with ultrafine PCC slurry at 80-85° C. The coated slurry is passed through a mixing pump to induce shear and recirculated back to the storage tank before dewatering.

[0074] Example 2

[0075] Method Description of Elaidic Acid

[0076] The process was carried out according to the procedure of Example 1, except that 40% of elaidic acid was used instead of TOFA to prepare the surface coating.

[0077] Example 3

[0078] Method Description of Elaidic Acid Compositions

[0079] The process was carried out according to the procedure of Example 1 except that 40% of an acid mixture comprising at least 30% elaidic acid was used in place of TOFA to prepare the surface coating.

[0080] Example 4

[0081] Description of the method for preparing vegetable oil-derived compositions

[0082] The process was carried out according to the procedure of Example 1 except that a 40% vegetable oil derived acid blend (AltaVeg TM FA 140) was used to replace TOFA to prepare the surface coating.

[0083] Example 5

[0084] TOFA / Plant-Based Composition Method Description

[0085] The process was carried out according to the procedure of Example 1 except that 20% of the vegetable oil derived acid mixture (AltaVeg TM FA 140) and 20% TOFA ( 1483) was used to replace TOFA to prepare surface coating.

[0086] Example 6

[0087] Comparison of example samples to control samples in the Hegman pull-down

[0088] The exemplary oil compositions and control compositions were tested by Hegman pull-down.

[0089] sample

[0090] The control composition consists of 22m 2 / g of ultrafine precipitated calcium carbonate (PCC) (about 70 nm nanoparticles, Calofort SV), which was coated with 100% of a stearic acid / palmitic acid blend by the procedure of Example 1.

[0091] Example composition MD1619 consists of 22m 2 / g of ultrafine precipitated calcium carbonate (PCC) (about 70 nm nanoparticles, Calofort SV), which was coated with 60% of a stearic acid / palmitic acid blend and 40% of TOFA by the procedure of Example 1.

[0092] Hegman pull-down assay

[0093] For the test composition, PCC (31.0 g) was mixed with diisononyl phthalate (DINP) (46.0 g) and Molecular sieves (3.0 g) were mixed to give a 40% paste.

[0094] The procedure included 5 x 16 seconds mixing time at 3000 rpm. The composition was mixed in a DAC 150.1 FVZ-K Speedmixer from Synergy Devises Limited. Pre-wetting was performed before the first mix, and the sides and bottom were scraped between each mixing cycle.

[0095] The Hegman pull-down was performed according to the standard procedure of ASTM standard D 1210-96. The grinder fineness was 5254.

[0096] result

[0097] The control sample showed poor dispersion when compared to the pull down done on the black matrix. When compared to the mixing time of 5 x 16 seconds at 3000 rpm, the control sample had a Hegman result of "3" (Cleanliness Level A), while the MD1619 sample had a Hegman result of "7.0" (Cleanliness Level A).

[0098] The comparison shows that the MD1619 sample wets much faster than the control sample. This indicates that it is more compatible with DINP. Since the PCC powder wets faster, it has less time to spheroidize and form small agglomerates.

[0099] All publications and patents and applications cited in this specification are incorporated herein by reference, just as each publication or patent application is specifically and individually indicated to be incorporated by reference. Although the claimed subject matter has been described according to various embodiments, it will be understood by those skilled in the art that various adjustments, substitutions, omissions and changes may be made without departing from the essence thereof. Therefore, the scope of the subject matter is limited only by the scope of the appended claims, including their equivalents.

Claims

1. A nanoparticle composition comprising surface-treated calcium carbonate nanoparticles, wherein the calcium carbonate nanoparticles are treated with a fatty acid mixture comprising about 40-80% saturated fatty acids or mixtures thereof and about 20-60% unsaturated fatty acids or mixtures thereof, wherein the unsaturated fatty acids or mixtures thereof comprise at least about 10% elaidic acid or a salt thereof.

2. The nanoparticle composition of claim 1, wherein the unsaturated fatty acid or mixture thereof comprises at least about 20% elaidic acid or a salt thereof.

3. The nanoparticle composition of claim 1 or 2, wherein the unsaturated fatty acid or mixture thereof comprises tall oil fatty acid (TOFA) or a salt thereof.

4. The nanoparticle composition of any one of claims 1 to 3, wherein the unsaturated fatty acid or mixture thereof comprises a plant oil-based mixture or a salt thereof.

5. The nanoparticle composition of any one of claims 1-4, wherein the average particle size is about 30-200 nm.

6. The nanoparticle composition of any one of claims 1-5, wherein the average particle size is about 50-150 nm.

7. The nanoparticle composition of any one of claims 1-6, wherein the fatty acid mixture is about 40-64% saturated fatty acids or mixtures thereof and about 36-60% unsaturated fatty acids or mixtures thereof.

8. The nanoparticle composition of any one of claims 1-7, wherein the fatty acid mixture is about 60% saturated fatty acids or mixtures thereof and about 40% unsaturated fatty acids or mixtures thereof.

9. The nanoparticle composition of any one of claims 1 to 8, wherein the saturated fatty acid or mixture thereof comprises stearic acid or a salt thereof and palmitic acid or a salt thereof.

10. The nanoparticle composition of any one of claims 1-9, wherein the unsaturated fatty acid or mixture thereof comprises at least about 40% elaidic acid or a salt thereof.

11. The nanoparticle composition of any one of claims 1 to 10, wherein the unsaturated fatty acid or mixture thereof comprises oleic acid or a salt thereof and linoleic acid or a salt thereof.

12. A filler composition comprising the nanoparticle composition of any one of claims 1-11.

13. A method for preparing the nanoparticle composition of any one of claims 1 to 11, the method comprising: preparing a surface coating emulsion comprising a fatty acid mixture under alkaline conditions; and The calcium carbonate nanoparticles are mixed with a surface coating emulsion.

14. The method of claim 13, wherein preparing the surface coating emulsion comprises: preparing a mixture having about 5-9% solids; and The mixture was stirred at about 80-85 °C.

15. The method of claim 14, wherein the mixture is stirred for at least 30 minutes.

16. The method of any one of claims 13-15, wherein the basic conditions require at least 1.03 equivalents of a strong base.

17. The method of any one of claims 13-16, wherein the method of preparing the nanoparticle composition further comprises dehydrating the surface-treated calcium carbonate nanoparticles.