METHOD FOR PREPARING A WATER DISPERSION OF LIGNINE NANOPARTICLES

专利摘要:
dispersions of lignin nanoparticles and methods to produce and use them. the present invention relates to a simple, lightweight process for preparing dispersions of lignin nanoparticles. in addition, compositions and methods of preparing lignin nanoparticles - polymer complexes comprising dispersions of derivatized and / or non-derivatized lignin nanoparticles and soluble dispersible polymers and / or water are described. in addition, methods of using at least one of the dispersions of lignin nanoparticles, dispersions of the derivatized lignin nanoparticles, and / or the lignin nanoparticle - polymer complex are described to impart rinse resistance properties, as hydrophilic properties, for substrates, or work as tunable nanoparticle surfactants.
公开号:BR112016012411B1
申请号:R112016012411-1
申请日:2014-12-12
公开日:2021-03-30
发明作者:Leo Z. Liu；John C. Gast；Kyle J. Bottorff
申请人:Solenis Technologies, L.P.；
IPC主号:

专利说明:

[1] The present patent application claims the benefit under 35 U.S. C. 119 (e), from US Provisional Patent Application 61/915, 442. Which is expressly incorporated into the present invention by reference. FIELD
[2] The process (s), procedure (s), method (s), product (s), result (s) and / or concept (s) presently described and / or claimed ( s), (collectively hereinafter referred to as "the inventive concept (s) presently described and / or claimed (s)" generally refers to dispersions of nanoparticles of lignin and / or derivatized from lignin nanoparticle dispersions More particularly, but not by way of limitation, the inventive concept (s) presently described and / or claimed refers to a simple, lightweight process for the preparation of dispersions of lignin nanoparticles The inventive concept (s) presently described and / or claimed also refers in general to compositions and methods of preparing dispersions of lignin nanoparticles - polymer complexes comprising water-soluble and / or water-dispersible polymers and derivatized and / or non-derivatized from lignin nanoparticles.
[3] In addition, the inventive concept (s) presently described and / or claimed (s) of the present invention refers in general to a method of using at least least one of the dispersions of lignin nanoparticles to impart resistant rinse adsorption of the lignin nanoparticles to a substrate. In addition, the inventive concept (s) presently described and / or claimed refers in general to a method of using at least one of the dispersions of lignin nanoparticles and / or dispersion of lignin nanoparticles - polymer complex to impart hydrophilic rinse-resistant properties to surfaces, or function as a nanoparticle surfactant. BACKGROUND
[4] Lignin is a complex chemical compound that is part of the cell walls of secondary plants and some algae. Lignin is most commonly obtained from wood, but it is also derived from secondary sources, such as corn husks, grass, straw, and sources other than wood. As such, lignin is an abundant source of renewable material, only the second cellulose. The main sources of lignin are the various chemical processes for the production of wood pulp that generate by-products of "liquor" containing lignin, hemicellulose and other extracts that remain after the cellulose fibers have been separated from the wood. Several of the most popular chemical pulping processes over the years have been the sulfate process (generally referred to as the "kraft" process), and the sulfite process. However, from around 1940, the kraft process has been the dominant process. As of 2008, the kraft process was responsible for approximately 90% of the cellulose produced by means of chemical processes, generating globally around 1.3 billion tons of "black" liquor per year.
[5] Until recently, the lignin contained in wood pulping liquors, specifically the "black" liquor from the kraft process, was unable to be effectively extracted and liquors were often burned as an alternative fuel source. With the advent of new capabilities for the extraction of lignin from beverage by-products, for example, LignoBoost® technology (Innventia AB) and LignoForce ™ technology (Innovations FP, Point-Clair, PQ) to specifically isolate lignin from the By-product of "black" liquor from the kraft process, an industrial need arose to develop value-added lignin products in order to get the most out of lignin as a raw material.
[6] Previous attempts to use lignin, especially kraft lignin, for value-added products have led to the discovery of a variety of ways that lignin can be derivatized in order to increase the functionality of lignin. For example, Cui et al. (2013), "Lignin polimers: Part 2," BioResources 8 (1), 864-886, incorporated into the present invention by reference in its entirety, describes the blocking of phenolic units of lignin by forming ether to increase the thermal stability of kraft lignin so that lignin can be used in thermoplastic materials.
[7] Lignin derivatives are also described in US Patent 3,956,261, incorporated into the present invention by reference in their entirety, in which esterification of the lignin phenolic groups was used to add functional groups, such as carboxylate ethyl, for lignin for specific industrial purposes. The blocking of phenolic groups by means of esterification can also reduce the intensity of the black color associated with lignin obtained from Kraft and sulfite paste production processes, as described in US Patent 4,454,066 and incorporated into the present invention by means of reference in its entirety. Alternative methods of lignin derivatization also include methylation of lignin using formaldehyde as described in, for example, US 5,972,047 and US 5,989,299, both of which are incorporated into the present invention by reference in their entirety. , and the lignin graft polymerization as described in, for example, US 7,691,982, incorporated into the present invention by reference in its entirety. Additional lignin deprivation methods are also reviewed in John J. Meister, Plastic Engineering, "Modification of Lignin", pages 67 to 144. Vol. 60. Polimer Modification: Principles, Techniques and Applications, Ed. John J. Meister (1. Ed. 2000), incorporated into the present invention by reference in its entirety. Currently, such methods for the derivatization of lignin require intensive processing or the use of organic solvents or hazardous chemicals such as formaldehyde, ethylene oxide, and other alkylene oxides.
[8] In recent years there has also been a growing interest in the field of nanotechnology including some interest in lignin nanoparticles. Although naturally occurring lignin nanoparticles have been detected in the ocean as carriers of dissolved iron, as described in Krachler et al., Global Biogeochemical Cycles 26, GB3024 / 1-GB3024 / 9, (2012), incorporated in the present invention by reference in its entirety, naturally occurring lignin nanoparticles such as these are rare and not economically viable for harvesting for general applications.
[9] Nanoparticles can have physical and chemical properties that are generally attributable to their nanoscale size. Recently, processes for obtaining lignin nanoparticles have emerged including, for example, but not limited to, physical methods based on processes that use both ultrasound and / or mills and / or anti-solvents (ie , solvents in which the product is insoluble) and / or processes that adjust the pH of strong alkaline lignin solutions, as well as chemical methods that comprise, for example, lignin hydroxymethylation and / or lignin sulfonation. See, for example, J. Gilca et al., "Obtaining Lignin Nanoparticles by Sonication." Ultrason. Sonochem. 23, p. 369 to 376, (2015).
[10] Lignin nanoparticles were generally obtained, however, from aqueous lignin solutions, with or without an organic solvent by reducing the pH of the solution under shear, as described in, for example, C. Frangville, Chem. Phys. Chem 13, p. 4235, (2012) and patent publication CN103275331A, both of which are incorporated into the present invention by reference in their entirety. In addition, super-critical carbon dioxide has been used as an anti-solvent to obtain lignin nanoparticles from lignin solutions in acetone or dioxane, as described in, for example, Lu et al., Food Chemistry, 135, p. 63 (2012) and patent publication CN102002165A, both of which are incorporated into the present invention by reference in their entirety. Cross-linking agents, such as aldehydes, have also been used to modify lignin nanoparticles, as described in patent publication CN103254452. In addition, the dispersions of lignin nanoparticles were obtained directly from insoluble water lignin kraft by means of chemical derivatization in water, as exemplified in U.S. Patent 4,957,557, incorporated into the present invention by reference in its entirety. However, such methods of chemical derivatization in water, including those described in U.S. Patent 4,957,557, require the use of hazardous chemicals such as formaldehyde in order to prepare lignin-based nanoparticles in water.
[11] However, as suggested above, the methods described in the prior art for the preparation of lignin nanoparticles, and dispersions thereof, often do not have the necessary efficiency to make lignin a cost effective source of the raw material as well. as they present safety and environmental risks due to the fact that it requires the use of organic solvents, such as dioxane, and / or that requires process components under pressure. In addition, the methods described in the prior art generally produce dispersions of nanoparticles containing impurities of organic solvents that require further processing and additional cost. As such, there is an industrial need for an effective method of preparing costly lignin nanoparticles in water without the use of hazardous chemicals or solvents. Such lignin nanoparticles would be useful in "value-added processes" downstream and, therefore, have a better economic use than simply burning lignin as fuel.
[12] The methods are described in the present invention to provide economical and efficient methods for preparing stable dispersions of lignin nanoparticles (and / or lignin derivatives) in water. These methods do not require the use of hazardous chemicals, and may have less environmental impact than current methods in the prior art. In addition, the methods are described in the present invention which extend the scope of applications available for dispersions of lignin nanoparticles and derivatized from lignin nanoparticles, such as, for example, but without limitation, nanoparticle surfactants, such as defined below. In particular, a method of treating substrates (also referred to in the present invention as a "surface" or "interface") with dispersions of lignin nanoparticles or derivatized from lignin nanoparticles in which the lignin nanoparticles is described in the present invention is described. and / or derivatized from lignin nanoparticles can transmit rinse-resistant adsorption (as defined below in the present invention) of the particles to these surfaces, due to a strong surface affinity (as defined below in the present invention) to both inorganic surfaces and organic. In one embodiment, dispersions of lignin nanoparticles and / or derivatives of lignin nanoparticles can confer the properties of lignin or lignin derivatives, such as, for example, but not limited to, hydrophilia, hydrophobia, antimicrobials, anti-oxidants , anti-dust, UV protection, on a substrate. A "substrate", as used in the present invention, is defined to mean any solid surface on which a coating layer of material can be deposited by including, for example, but not limited to, adsorption.
[13] A lignin nanoparticle - polymer complex and its dispersion is also described in the present invention comprising lignin nanoparticles and / or derivatives of lignin nanoparticles and at least one water-dispersible and / or water-soluble polymer . A lignin nanoparticle - polymer complex, as described in the present invention, can also confer surface rinse resistance properties, in which the degree of resistance can be strongly influenced by the relationship of the lignin nanoparticles and / or nanoparticle derivatives. of lignin to the water-dispersible polymer and / or water-soluble polymer. In addition, the lignin nanoparticle - polymer complex, as described in the present invention, can function as a tunable nanoparticle surfactant.
[14] A "nanoparticle surfactant" is defined in the present invention as: (a) two materials with a hydrophilic and hydrophobic character, at least one of which is a nanoparticle, or (b) in the form of a single nanoparticle having two or more domains of hydrophilic and hydrophobic character, and in which the nanoparticle surfactant can confer properties normally associated with surfactants. The "tunable" properties of the nanoparticle surfactant are defined in the present invention as the ability to modify the type and / or quantity of the polymer in the lignin nanoparticle - polymer complex mentioned above without chemically bonding the water-dispersible polymer and / or polymer water-soluble lignin nanoparticle and / or lignin nanoparticle derivatized. In one embodiment, the lignin nanoparticles - polymer complexes, as described above, can confer properties of both (i) the water-dispersible polymer and / or water-soluble polymer and (ii) the lignin, including, for example, but without limitation, the hydrophilic, hydrophobic, antimicrobial, and anti-dust characteristics, depending on the water-dispersible polymer and / or water-soluble polymer used. SUMMARY
[15] The inventive concept (s) presently described and / or claimed comprises (s) dispersions of lignin nanoparticles, methods of preparing dispersions of lignin nanoparticles, and their uses. In addition, the inventive concept (s) presently described and / or claimed encompasses the lignin nanoparticle - polymer complexes and dispersions thereof, comprising derivatized and / or not derivatized from lignin nanoparticles and the water-dispersible polymer and / or water-soluble polymer and methods of doing the same.
[16] The inventive concept (s) presently described and / or claimed further comprises a method of treating a substrate with at least one of the dispersions of nanoparticles of lignin and / or dispersions of derivatives of lignin nanoparticles, in which the nanoparticles adsorb to the substrate. The inventive concept (s) presently described and / or claimed further comprises a method of using at least one of the dispersions of lignin nanoparticles, dispersions of derivatized from lignin nanoparticles, and / or dispersions of lignin nanoparticles - polymer complexes to provide rinse-resistant properties for substrates or function as nanoparticle surfactants. BRIEF DESCRIPTION OF THE FIGURES
[17] Figure 1 is an illustration of the etherification reaction mechanisms for, carboxylation, and addition of lignin polymerization graft.
[18] Figure 2 is a graphical representation that illustrates that a network of lignin nanoparticles - polymer complexes is formed when nanoparticles and / or derivatized from nanoparticles of lignin are added to a polymer dispersible in water and / or polymer soluble in water in a proportion that supports the formation of the complex. The proportion of lignin nanoparticles and / or derivatives of lignin nanoparticles for the water-dispersible polymer and / or water-soluble polymer can vary depending on the properties and functionality of the polymer and lignin nanoparticles and / or derivatives of nanoparticles of lignin. The lignin nanoparticles / polymer complexes thus formed demonstrate strong surface interactions. Optionally, the network of lignin nanoparticles - polymer complexes can be deposited on a surface while the network is still forming.
[19] Figure 3 is a graphical representation that illustrates that, by one modality, in the indicated proportions of lignin nanoparticles to be dispersed in water and / or water-soluble polymer, a maximum viscosity occurs demonstrating the formation of a nanoparticle - lignin la - polymer complex.
[20] Figure 4 is an image obtained with an AFM microscope of a dispersion of nanoparticles prepared from BioChoice ™ lignin (Domtar Inc., West, Montreal, QC) isolated from black liquor using LignoBoost® process (Innventia AB, Stockholm, Sweden) through the neutralization of BioChoice ® lignin with potassium carbonate, using the methods described in the present invention, in which the dispersion of nanoparticles of ligand was diluted to active particles of 100 ppm and cast on a mica surface.
[21] Figure 5 is an image obtained with an AFM microscope of the dispersion of lignin nanoparticles in Figure 4 at greater magnification.
[22] Figure 6 is a series of images obtained with an AFM microscope from a glass slide cover.
[23] Figure 7 is a series of images obtained with an AFM microscope of a glass sliding cover rinsed with tap water.
[24] Figure 8 is a series of images obtained with an AFM microscope of a delimitation glass cover treated with lignin no particulate.
[25] Figure 9 is a series of images obtained with an AFM microscope formed in-situ in lignin nanoparticles from a delimiting glass cover.
[26] Figure 10 is an AFM microscope image of a dispersion of lignin nanoparticles prepared by both derivatization of BioChoice ™ lignin (Domtar Inc., West, Montreal, QC) with glycerol carbonate and neutralizing BioChoice ™ lignin (Domtar Inc., West, Montreal, QC) with potassium carbonate, using the methods described in the present invention, in which the dispersion of lignin nanoparticles was diluted to 100 ppm of active particles and launched onto a mica surface.
[27] Figure 11 is an AFM microscope image of a dispersion of a lignin nanoparticle - polymer complex formed using the process described in the present invention of adding a dispersion of derivatized nanoparticles of lignin with glycerol carbonate with an aqueous solution of polyvinylpyrrolidone, in which the weight ratio of polyvinylpyrrolidone to derivatives of lignin nanoparticles is about 1: 4, and yet the lignin nanoparticle - polymer complex has been diluted to 100 ppm of active particles and launched on a mica surface.
[28] Figure 12 is a graphical representation that illustrates that, by a modality, in the indicated proportions of lignin nanoparticles to be dispersed in water and / or water-soluble polymer, a maximum viscosity occurs demonstrating the formation of a na-particle of lignin - polymer complex.
[29] Figure 13 is a photographic image documenting that treating a vinyl surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties compared to an untreated vinyl surface. .
[30] Figure 14 is a photographic image documenting that treating a laminate surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties, compared to an untreated laminate surface.
[31] Figure 15 is a photographic image documenting that treating a vinyl surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties compared to an untreated vinyl surface. .
[32] Figure 16 is a photographic image documenting that treating a ceramic surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties, compared to an untreated ceramic surface.
[33] Figure 17 is a photographic image documenting that treatment of an aluminum surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties, compared to an untreated aluminum surface.
[34] Figure 18 is a photographic image documenting that treating a stainless steel surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties, compared to an untreated stainless steel surface. .
[35] Figure 19 is a photographic image documenting that treating a polypropylene surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties, compared to an untreated polypropylene surface.
[36] Figure 20 is a photographic image documenting that treating a glass surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties compared to an untreated glass surface. .
[37] Figure 21 is a photographic image documenting that treating a felt surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties, compared to a felt fabric surface. untreated.
[38] Figure 22 is a photographic image also documenting that treating a polypropylene surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better improved properties compared to an untreated polypropylene surface. .
[39] Figure 23 is a photographic image also documenting that treating an aluminum surface with a dispersion of a lignin nanoparticle - polymer complex provides the surface with better wetting properties, compared to an aluminum surface. untreated DETAILED DESCRIPTION OF THE INVENTIVE CONCEPT (S)
[40] Before explaining at least one embodiment of the concept (s) of the present invention presently described (s) and / or claimed (s) in detail, it is to be understood that the concept (s) ) of the present invention presently described (s) and / or claimed (s) is not limited in its application to the details of construction and the arrangement of the components or steps or methodologies set out in the following description or illustrated in the drawings. The concept (s) of the present invention presently described and / or claimed is (are) capable of other modalities or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology in the present invention employed is for the purpose of description and should not be considered as limiting.
[41] Unless otherwise defined, the technical terms used in connection with the concept (s) of the present invention currently described (s) and / or claimed (s) must have the meanings that are commonly understood through people who are well versed in the technique. In addition, unless otherwise indicated in the context, terms in the singular must include pluralities and terms in the plural include the singular.
[42] All patents, published patent applications and non-patent publications mentioned in the specification are indicative of the level of expertise through the people who are knowledgeable in the technique to which the concept (s) of the present invention presently exist. described (s) and / or claimed (s) belongs. All patents, published patent applications and non-patent publications referenced anywhere in this patent application are expressly incorporated into the present invention by reference in their entirety to the same extent as if each individual patent or publication were specifically and individually indicated to be incorporated by reference.
[43] All articles and / or methods described in the present invention can be made and executed without undue experimentation in the light of this description. While the articles and methods of the concept (s) of the present invention presently described and / or claimed (s) have been described in terms of preferred modalities, it will be evident from the people who are knowledgeable in the art that variations can be applied to the articles and / or methods and in the steps or in the sequence of steps of the method described in the present invention without departing from the concept, spirit and scope of the concept (s) of the present invention ( and / or claimed (s). All such similar substitutes and apparent modifications to those people who are skilled in the art are considered to be within the spirit, scope and concept (s) of the present invention presently described and / or claimed (s).
[44] As used in accordance with this description, the following terms, unless otherwise indicated, are to be understood as having the following meanings.
[45] The use of the word "one" or "one" when used in conjunction with the term "comprising" may mean "one", but it is also consistent with the meaning of "one or more", "at least one" and "one or more than one". The use of the term "or" is used to mean "and / or" unless it is explicitly stated to refer to alternatives only if the alternatives are mutually exclusive, although the description supports a definition that refers only to alternatives and "and / or". Throughout this application, the term "about" is used to indicate that a value includes the inherent variation of error for the quantification device, being the method used to determine the value, or the variation that exists between the study subjects. For example, but not by way of limitation, when the term "about" is used, the designated value may vary by plus or minus twelve percent, or eleven percent, or ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent. The use of the term "at least one" will be understood to include both one and any amount more than one, including, but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40 , 50, 100, etc. The term "at least one" can extend up to 100 or 1000 or more, depending on the period to which it is linked. In addition, quantities of 100/1000 should not be considered limiting as lower or upper limits can also produce satisfactory results. In addition, the use of the term "at least one of X, Y, and Z" will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y, and Z. The use of the terminology number ordinal (ie "first", "second", "third", "fourth", etc.) is solely for the purpose of differentiating between two or more items and, unless otherwise stated, is not to imply any sequence or order or importance for one item over another or any order of addition.
[46] As used in the present invention, the words "with understanding" (and any form of understanding, such as "understand" and "understand"), "possessing" (and any form of possessing, such as "possess" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "includes" and "contains") are inclusive or open and do not exclude, additional non-recited elements or method steps. The term "or combinations thereof" as used in the present invention refers to all exchanges and combinations of the items listed above in the term. For example, "A, B, C or their combinations" is intended to include at least one of: A, B, C, AB, AC, AC, or ABC and, if order is important in a context particular, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repetitions of one or more articles or terms, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA, CABABB, and so on. The person skilled in the art will understand that there is usually no limit to the number of items or conditions in any combination, unless it is otherwise evident from the context.
[47] The concept (s) of the present invention presently described and / or claimed encompasses a method (s) for the preparation of a dispersion of lignin nanoparticles in water comprising , consisting of, or consisting essentially of: (a) combining (i) a base, which is not an inorganic bivalent base, (ii) ligin, and (iii) water to form a lignin composition comprising, consisting of , or consisting essentially of lignin in the range of from about 1 to about 70% by weight, or from about 5 to about 40% by weight, or from about 15 to about 30% by weight, and has a pH in a range that favors the formation of a stable dispersion of lignin nanoparticles (as defined in more detail below) without dissolving the lignin in water to form a solution (as defined in more detail below), and (b) heating of the lignin composition while stirring at a temperature in the range of about 30 to about 100 ° C, or in the range of about 70 up to about 100 ° C, or in the range of about 80 to about 100 ° C to form a dispersion of lignin nanoparticles. Optionally, additional water can be added after the heating and stirring step of the lignin composition. The water can be at a temperature in the range of about 0 ° C to about 70 ° C, or about 5 to about 35 ° C.
[48] In an alternative embodiment, the method for preparing a dispersion of lignin nanoparticles in water, as described above, can be carried out under pressure and the composition of the ligin can be heated, with stirring, to a temperature in the range of about 100 to about 200 ° C, or from about 100 to about 150 ° C, or from about 100 to about 120 ° C, or from about 100 to about 110 ° C, wherein the temperature is related to the pressure and the pressure can be in the range of about 1 to about 40 atm, or about 1 to about 20 atm, or from about 1 to about 15 atm, or from about 1 to about 10 atm, or from about 1 to about 5 atm.
[49] In one embodiment, the lignin composition can be heated to the temperature ranges described above within 140 minutes, or within 40 minutes, or 25 minutes, or 10 minutes, or within 2.5 minutes, or within 1 minute, or within 30 seconds, or less than 10 seconds from the combination of the base with lignin and water.
[50] The base can be added either as a solid or phase solution in any of the mixing and / or heating steps in order to have a smooth reaction. In an additional embodiment, the base can be added in one step, several steps, or continuously throughout the mixture and / or heating steps.
[51] In one embodiment, lignin and water are combined before adding the base, forming a mixture of lignin and water with a pH less than or equal to 6, or less than 5.5, or about 2 at about 5.5. The base can then be added until the pH is in a range that favors the formation of a stable dispersion of lignin nanoparticles without dissolving the lignin in water to form a solution.
[52] In one embodiment, the base is added until the pH is in the range of 7 to 9, or 7 to 10, or 7-10.5. As a person skilled in the art would appreciate, however, different types of lignin have varying levels of solubility in water and, as such, the appropriate pH range for the formation of nanoparticle dispersions using the method described above may vary according to the type of lignin or combinations of lignin and / or lignin nanoparticles to be dispersed. Such variations in pH ranges are understood in the present invention to encompass the inventive concept (s) presently claimed and / or described.
[53] The base, as described in the present invention, is a composition that can increase the pH of, for example, but without limitation, the mixture of lignin and water, and can be selected from the group consisting of alkaline hydroxides , ammonium hydroxide, alkyl substituted ammonium hydroxides, organic amines, alkali carbonates or bicarbonates, ammonium carbonates or bicarbonates, alkyl substituted ammonium carbonates or bicarbonates, and combinations thereof.
[54] In one embodiment, the base can be selected from the group consisting of ammonium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, triethanolamine, and combinations thereof.
[55] The lignin in the method described above for the preparation of nanoparticle dispersions lignin, can be in any form, including, for example, but not limited to, lignin isolate, (for example, kraft lignin isolated from LignoBoost® (Innventia AB, Stockholm, Sweden) or LignoForce ™ (Innovations Fp, point processes-Clair, PQ)), derivatized from lignin, lignin nanoparticles, and / or combinations thereof. As used in the present invention, "lignin isolate" refers to lignin that has been relatively unmodified, as compared to a "ligin derivatized" that has been modified by chemical reaction to obtain different properties than natural lignin.
[56] In one embodiment, lignin comprises ligin isolate. The lignin isolate can be obtained, produced, or "isolated" from a process selected from the group consisting of Kraft, solvent extraction, biofuel processing, organosolv, Bjorkman process, vapor explosion, cellulolytic enzyme , acid hydrolysis, soda lime, LignoBoost® (Innventia AB, Stockholm, Sweden), LignoForce ™ (Innovations FP, Point-Clair, PQ), and combinations thereof. In one embodiment, lignin is Kraft lignin obtained through the kraft process of converting wood to wood pulp. In another embodiment, lignin is isolated from kraft lignin by at least one of the LignoBoost® process (Innventia AB, Stockholm, Sweden). In yet another modality, lignin is water insoluble sulfite lignin obtained from the conversion process of wood into wood pulp. In an alternative embodiment, the lignin can be phenol-formaldehyde resins.
[57] Lignin can also be any type of lignin, or lignin side as described above, that has undergone any of the appropriate method (s) to derivatize lignin, such as, for example , but without limitation, etherification or graft polymerization of the hydroxyl lignin functions with at least one of polyether and polycarbonate. As such, "lignin derivatized", as used in the present invention, refers to any type of lignin that has undergone any of the appropriate method (s) to derivatize lignin, such as, for example, but not limited to, etherification or graft polymerization of the hydroxyl functions of lignin with at least one of polyether and polycarbonate, and including, without limitation, any of the methods detailed below. Additional methods of lignin derivatization are described in John J. Meister, Plstic Engineering, "Modification of Lignin", pp. 67 to 144 (1. Ed., 2000), the total content of which is incorporated into the present invention by reference in its entirety. The following are still other non-limiting ways in which lignins can be derived:
[58] Lignin can be derived by heat treatment at temperatures ranging from about 120 to about 200 ° C to increase its molecular weight, after which lignin can be selectively reduced, for example, but without limitation, hydrogenation or, alternatively, heat-treated lignin, can be oxidized, for example, but without limitation, hydrogen peroxide or chlorine dioxide, in order to improve selective functionalities;
[59] Lignin can be derivatized by alkylating the hydroxyl group (s) of lignin by reacting lignin with alcohol in the presence of a catalyst, or by reacting lignin with at least one of the halides alkyl, alkyl sulfates, epoxy alkylene, such as methyl chloride, dimethyl sulfate, diethyl sulfate, or ester monochloroacetate salt, epichlorohydrin, N- (3-chloro-2-hydroxypropyl) trimethylammonium chloride, ethylene oxides, propylene oxides, butylene oxides, or combinations thereof. Potential reaction sites on lignin may be the α-hydroxy ketone group (s), carbonyl group (s), carboxyl group (s), aromatic group (s), and the hydroxyl group (s) primary and / or secondary. The aromatic hydroxyl group (s) can be alkylated by adding Michael with unsaturated compounds of R1R2C = CR3R4, where R1, R2 R3 and R4 are hydrogen or alkyl groups that can support various features. Typical unsaturated compounds include, for example, but are not limited to, (meth) acrylates, (meth) acrylamides, vinyl phosphonate, vinyl esters, vinyl ethers, vinylamides, and combinations thereof;
[60] Lignin can be derivatized by means of methylation and amination, attaching lignin with at least one of the functionalities (a) CH2OR through reaction with formaldehyde in water or with an alcohol, or (b) R CH 2 N (R ' ) "If combined with an amine, where R, R 'and R' 'are hydrogen or alkyl groups that can support various functionalities. Potential reaction sites may be the aromatic ring (s) and the (s) lignin ketone function (s);
[61] Lignin can be derivatized by means of the carboxylation of at least one oxidation, halogenated carboxylic acid alkylation, or by the Kolb-Schmitt reaction, in which CO2 is reacted with the (s) lignin phenol group (s) for adding an aromatic ring carboxyl acid;
[62] Lignin can be derivatized by means of sulfomethylation and sulfonation, which increases at least one of the groups consisting of methylene sulfonate (CH2SO3-) or sulfonate (SO3 ~), and combinations thereof with lignin. Sulfomethylation can occur in aromatic bearing rings with at least one hydroxyl group or in the α-carbon of a carbonyl group. The sulfite generally reacts with ligin by substituting with benzyl hydroxyl, alkoxy or methylolyl groups, where the methylolyl group is generally the derivative of ligin reacting with formaldehyde naturally or synthetically;
[63] Lignin can be derivatized by phosphorylation, which increases at least one lignin phosphate group. Phosphorylation can be carried out by reacting the lignin hydroxyl group (s) with POCI3, phosphorus pentoxide, polyphosphoric acid, or combinations thereof;
[64] Lignin can be derivatized through the esterification of lignin, which is carried out by reacting the lignin hydroxyl group (s) with a carboxylic acid anhydride or chloride, or, alternatively, through transesterification;
[65] In addition, lignin can be derivatized under anhydrous conditions, where the aromatic lignin ring (s) can be alkylated or acylated via intermediates of carbocation. Such a reaction can be useful when it is necessary to add additional hydrophobics to lignin. For example, the reaction of the aromatic ring (s) of the ligand with styrene can increase the affinity of lignin for hydrophobic surfaces; and / or
[66] Lignin can also be derivatized by polymerization graft to introduce lignin polymer chains, which is usually done by polymerizing chain growth, such as radical polymerization or by opening polymerization ring, or, alternatively, through polycondensation in which the lignin molecules can be cross-linked together. Many studies have been done to graft lignin with vinyl monomers through radical polymerization and, as such, it is well known in the art.
[67] Other methods of lignin derivatization are known to those skilled in the art and are considered to be part of the description contained in the present invention. In addition, lignin derivatives or lignin derivatized in the form of nanoparticles of any method, including those described in the present invention, can also be dispersed in water using the process of dispersing the lignin nanoparticles described above.
[68] In an alternative embodiment, one or more solvents may be added to the lignin composition, although this is not necessary for the inventive concept (s) presently described and / or claimed ) for the preparation of dispersions of nanoparticles in lignin water. If a solvent is used, the solvent can be selected from the group consisting of alcohols, glycols, polyhydric alcohols, ketones, ethers, dialkyl sulfoxide, water-miscible solvent amides, and combinations thereof. Additional solvents will be apparent to those skilled in the art and are contemplated for use in the present invention.
[69] Lignin can also be in the form of nanoparticles obtained from any type of lignin that has been subjected to a process to chemically or mechanically modify lignin in lignin nanoparticles. As used in the present invention, the term "nanoparticle" means particles that are predominantly less than 600 nm in size. The definition of "dispersion of lignin nanoparticles" is defined later in this document.
[70] In one embodiment, lignin nanoparticles are obtained from a mechanical process such as grinding lignin or using ultrasound over lignin. In another embodiment, lignin nanoparticles are synthesized from a chemical process selected from at least one of the lignin hydroxymethylation and chemical vapor deposition. As a person skilled in the art would appreciate based on the above, the process by which lignin nanoparticles are obtained is immaterial - lignin nanoparticles from any source or produced according to any process are contemplated for use with (s) ) inventive concept (s) presently described and / or claimed.
[71] In one embodiment, lignin comprises the derivative of lignin produced by a method (s) comprising, consisting of, or consisting essentially of: (i) mixing lignin with a carbonate compound containing ester in a molar ratio in the range of about 10: 1 to about 1: 1000, or from about 5: 1 to about 1: 100, or from about 3: 1 to about 1: 3 of the phenolic hydroxyl function of lignin for the carbonate ester to form a lignin mixture, (ii) removing residual moisture in the lignin mixture, and (iii) heating the lignin mixture to a temperature in the range of about 120 to about 190 ° C, in the presence of a catalyst that can be selected from the group consisting of alkaline carbonate, alkaline earth carbonate, and combinations thereof. Optionally, more of the carbonate ester can be fed into the reaction mixture for a higher polyether content of grafted functions. Residual moisture from the mixture is removed by vacuum drying. Residual moisture would be well known to those skilled in the art. Additionally and / or alternatively, the mixture is heated to a temperature in the range of about 150 to about 160 ° C for about 20 minutes to about 5 hours, or about 20 minutes to about 3 hours, or about 20 minutes to about 1 hour, in which time is dependent on the fact that additional carbonate or whether the ester-containing compound is necessary for a higher polyether content of grafted functions.
[72] In another embodiment, the derived lignin described above can be produced and dispersed by means of a method comprising the steps of: (i) mixing lignin with an ester-carbonate-containing compound and a base to form a mixture of lignin, wherein the lignin is mixed with the ester containing carbonate compound in a molar ratio ranging from about 10: 1 to about 1: 1000, or from about 5: 1 to about 1: 100, or from about 3: 1 to about 1: 3 of the phenolic hydroxyl function of lignin to the carbonate ester (ii) the removal of residual moisture in the lignin mixture, and (iii) heating the lignin mixture in the presence of a catalyst, wherein the catalyst is selected from the group consisting of alkaline carbonate, alkaline earth carbonate, and combinations thereof, at a temperature of about 150 to 160 ° C for about 20 minutes to about 2 hours, or between about 20 minutes to an hour, (iv) allow the lignin mixture to cool to at a temperature of about 100 to 130 ° C, (v) adding water and, optionally, a second base, to the mixture with stirring to form an aqueous mixture of lignin and (vi) refluxing the aqueous lignin mixture at about 100 ° C to form a homogeneous liquid nanoparticle dispersion.
[73] The ester-carbonate-containing compound is at least one of a cyclic or linear carbonate ester, and combinations thereof. Cyclic or linear carbonate esters comprise, for example, but without limitation, dimethyl carbonate, diethyl carbonate, glycerol carbonate, ethylene carbonate, propylene carbonate and butylene carbonate. Optionally, the carbonate ester can be added in combination with a solvent, in which the solvent is inert, such as, for example, but not limited to, dioxane, dimethylsulfoxide, and N, N-dimethylformamide, although the addition of a solvent may be unnecessary. The carbonate ester-containing compound can have a general formula of R5O-C (= O) -OR6, where R5 and R6 are selected from the group consisting of alkyl, cyclic alkyl, cyclic alkylene groups, and combinations thereof , wherein alkyl, cyclic alkyl and cyclic alkylene optionally comprise additional functional groups.
[74] As regards Figure 1, a cyclic carbonate ester can be used for the etherification and carboxylation step of lignin. However, graft polymerization of a polyether and / or a polycarbonate to lignin requires the use of a cyclic carbonate ester. The cyclic carbonate ester can be glycerol carbonate, which has been found to improve the solubility in lignin water and increase the functionality of hydroxyl groups.
[75] The source of lignin for any of the derived lignins, as described in the present invention, can be obtained from any process, including, for example, but not limited to, a process selected from the group consisting of Kraft, solvent extraction, biofuel processing, organosolv, Bjorkman process, steam explosion, cellulolytic enzyme, acid hydrolysis, soda lime, LignoBoost® (Innventia AB, Stockholm, Sweden), LignoForce ™ (Innovations FP, Point-Clair, PQ ), and their combinations.
[76] In one embodiment, the inventive concept (s) presently described and / or claimed encompasses a method for preparing a dispersion of aqueous lignin nanoparticles which comprises heating and mixing a heterogeneous composition comprising at least one of lignin, derivatized from lignin, and combinations thereof, and water, in which at least part of the lignin and / or derivatized lignin is not soluble in water in the continuous phase .
[77] The inventive concept (s) presently described and / or claimed (s) also encompasses a lignin nanoparticle - polymer complex, wherein the lignin nanoparticle - polymer complex comprises a polymer and at least one of a lignin nanoparticle, derivatized from lignin nanoparticle, and combinations thereof, in which the lignin nanoparticle - polymer complex is formed by the association of lignin polymer instead of chemical bonding . In one embodiment, the lignin polymer association can be at least one donor-acceptor bond (i.e., pi-pi interaction bond), hydrogen bond, polar-polar interaction, and hydrophobic interaction. It was found that the lignin nanoparticles, and derivatized from lignin nanoparticles in the same way, such interactions improve the donor-acceptor with the polymer in the lignin nanoparticle - polymer complex. Since the chemical bonds do not depend to form the lignin nanoparticle - polymer complex, the properties of the polymer will be transmitted directly to the lignin nanoparticles, and then on the surfaces / interfaces treated with the nanoparticle. lignin - polymer complex due to improved adsorptivity of the lignin nanoparticle - polymer complex on such surfaces / interfaces.
[78] The inventive concept (s) presently described and / or claimed (s) also encompasses a dispersion of lignin nanoparticles - polymer complex comprising, consisting of, or consisting essentially of in a lignin nanoparticle - polymer complex, comprising the polymer and at least one dispersion of a lignin nanoparticle and / or a dispersion of derivatives of lignin nanoparticles, in which the dispersion of lignin nano-particle - complex of polymer comprises the lignin nanoparticle - polymer complex in the range of from about 0.01 to about 70% by weight, or from about 0.1 to 40% by weight, or from about 5 to about 40% by weight, or from about 15 to about 30% by weight, and a solvent, in the range of about 30 to about 99.99% by weight, or from about 60 to about 99.9 % by weight, or from about 60 to 95% by weight, or from about 70 to about 85% by weight. In one embodiment, the solvent is water. In an alternative embodiment, the lignin nanoparticle - polymer complex is present in the range of about 1 to about 30% by weight, where the active ingredients comprise at least one of a lignin nanoparticle and / or a nanoparticle of lignin derivatized and a water-dispersible polymer and / or water-soluble polymer. In one embodiment, the dispersion of lignin nanoparticles and / or dispersion of lignin nanoparticle derivatives (as described above) are added to the water-dispersible polymer and / or water-soluble polymer in a weight ratio in the range of about 0.1: 99.9 to about 99.9: 0.1 dispersion of water-dispersible polymer lignin nanoparticles and / or water-soluble polymer, or in the range of about 1:99 to about 99: 1 dispersion of lignin nanoparticles to the water dispersible polymer and / or water soluble polymer, or in the range of about 5: 95 to about 95: 1, or about 20:80 to about 80:20, or from about 1: 5 to 5: 1, or from about 0.1: 99.9 to about 1: 2, or from about 2.5: 1 to about 20 : 1 of the dispersion of lignin nanoparticles into the water-dispersible polymer and / or water-soluble polymer.
[79] Furthermore, if the water-dispersible and / or water-soluble polymer is hydrophilic and the lignin nanoparticles act from a hydrophobic capacity, or vice versa, the lignin nanoparticle - polymer complex becomes a surfactant of nanoparticles as defined above. A similar class of materials currently of academic interest is described in, for example, Kim BJ, Langmuir 23, 7804 (2007) and K. Smith and Larson-DC Pit, Langmuir 28, 11725, (2012), both of which are incorporated into the present invention by reference in its entirety. By attaching a hydrophilic polymer to a hydrophobic surface through the interaction between lignin and polymer nanoparticles, the surface will become more hydrophilic. Such surface hydrophilization can be adjusted to be rinsing water or resistant to rinsing with water, depending on several factors such as the type of polymer, the binding strength of lignin nanoparticles with the polymer, and the presence of amphiphilic species, such as surfactants and polymeric surfactants.
[80] The association of lignin polymer impacts the measured size of the lignin nanoparticles in the dispersion and can therefore be influenced by the selection of the polymer and the relative concentration of the dispersion of lignin nanoparticles added to the polymer.
[81] In another embodiment, the lignin nanoparticle - polymer complex also comprises, consists of, or consists essentially of a crosslinking agent that stabilizes the size of the lignin nanoparticles. An example of a chemical crosslinking process as described in U.S. Patent 4,957,557, for example, US 4,957,557, however, describes the use of formaldehyde, a dangerous chemical, as the crosslinking agent. In contrast to this prior art, the inventive concept (s) presently described and / or claimed (s) do not necessarily need dangerous chemicals, such as formaldehyde, for the crosslinking reaction occurs.
[82] The water-dispersible polymer and / or water-soluble polymer, capable of interacting with lignin to form a lignin nanoparticle - polymer complex, can be selected from the group consisting of a heterocyclic polymer, a derivative of lignin soluble in water, a poly (alkylene oxide), a functionalized poly (alkylene oxide), polyvinyl alcohol, cellulose derivatives, poly-naphthalene sulfonate, polysaccharide derivatives, co-polymers containing the above listed polymer blocks or segments, and their combinations. In one embodiment, the polymer to be dispersed in water and / or water soluble polymer is a heterocyclic polymer. In particular, but without limitation, the polymer is a heterocyclic polymer selected from the group consisting of polyvinylpyrrolidone, polyvinyl caprolatam, polyvinylimidazole, polypyridine compounds, polypyridine oxide compounds, polypyridine carboxylate compounds, copolymers and the materials of these materials combinations thereof. In an alternative embodiment, the polymer to be dispersed in water and / or water-soluble polymer is a derivative of water-soluble lignin. In particular, but without limitation, water-soluble lignin is a lignosulfonate. In another embodiment, the polymer to be dispersed in water and / or water-soluble polymer is a poly (alkylene oxide). In particular, but without limitation, poly (alkylene oxide) is selected from the group consisting of poly (ethylene oxide), poly (propylene oxide), poly (butylene oxide) and combinations thereof. In addition, in one embodiment, the water-dispersible polymer is a functionalized poly (alkylene oxide), where the functionalized poly (alkylene oxide) is a polyetheramine, specifically from the JEFFAMINE® polyetheramine family produced by Huntsman International LLC (The Woodlands, TX). In an additional alternative embodiment, the polymer to be dispersed in water and / or water-soluble of the polymer is hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and combinations thereof. In one embodiment, the polymer to be dispersed in water and / or water-soluble polymer is physically adsorbed to the lignin nanoparticles and / or derivatized from the lignin nanoparticle as described above.
[83] In an alternative embodiment, the polymer to be dispersed in water and / or water-soluble polymer can also be linked to lignin nanoparticles by means of coordination bonds through metal ions, such as alkaline earth elements, transition metals, that is, Fe3 +, Fe2 +, Al3 +, Zn2 +, Ca2 +, Mg2 +, Ti4 +, and their combinations.
[84] If necessary, any crosslinking agents known in the prior art can be applied to bind the water-dispersible polymer and / or water-soluble polymer to the lignin nanoparticle and / or derivatized from the lignin nanoparticle prepared using the described methods. Such cross-linking agents can be selected from the group consisting of a dialdehyde, polyaldehyde, dianhydride, polyanhydride, diisocyanate, polyisocyanate, diepoxide, polyepoxide, and combinations thereof. In one embodiment, the crosslinking agent is at least one of dialdehyde and polyaldehyde. In particular, but without limitation, the cross-linking agent is selected from the group consisting of glyoxal, glutaraldehyde, epichlorohydrin, and combinations thereof.
[85] The inventive concept (s) presently described and / or claimed (s) also encompasses a method (s) for preparing the lignin nanoparticle - polymer complex of a dispersion (as described above) comprising, consisting of, or consisting essentially of, the steps of: (i) combining at least one of a dispersion of lignin nanoparticles (as described above), a dispersion of derivatized lignin nanoparticles ( as described above), and combinations thereof and an aqueous solution of a polymer (as described above), and (ii) mixing to form a lignin nanoparticle - a dispersion polymer complex, wherein the lignin nanoparticle dispersion - polymer complex comprises the lignin nanoparticle - polymer complex in the range of about 0.01 to about 70% by weight, or from about 0.1 to about 40% by weight, from about 1 to about 30% by weight. Lignin nanoparticles - polymer complexes can be formed in the dispersion by adding lignin nanoparticles and / or derivatized from lignin nanoparticles to the polymer solution in any proportion. If a mesh is needed for any specific application, the optimal ratio of polymer to lignin ratio can be located by titrating the polymer solution with the dispersion of lignin nanoparticles, while mixing to maximum viscosity is achieved allowing formation of a network of the lignin nanoparticle - polymer complex, as illustrated in Figure 3. It is seen that such a network will be especially effective for deposition on and subsequent surface modification, through the lignin nanoparticle - complex of polymer. For the purpose of stabilizing lignin nanoparticles from aggregation, a smaller proportion of lignin polymer is preferable for the formation of the network. In one embodiment, the dispersion of lignin nanoparticles and / or dispersion of lignin nanoparticle derivatives as described above are added to the polymer in a proportion in the range of about 0.1: 99.9 to 99.9: 0.1 of the dispersion of lignin nanoparticles for the polymer, or in the range of about 1:99 to about 99: 1 of the dispersion of lignin nanoparticles for the polymer, or in the range of about 5: 95 to about 95: 5, or between about 20:80 to about 80:20, or about 1: 5 to 5: 1, or about 0.1: 99.9 to about 1: 2, or from about 2.5: 1 to about 20: 1 of the dispersion of lignin nanoparticles into the polymer. In another modality, the critical regime, suggesting an adequate proportion of dispersion of lignin nanoparticles to the polymer in order to form a lignin nanoparticle - polymer complex, can be indicated by means of an increase in the viscosity of the composition.
[86] A key component of the inventive concept (s) just described and / or claimed is that dispersions of lignin nanoparticles, derivatized from lignin nanoparticles, and lignin nanoparticles - polymer complexes described in the present invention above have been found to have a greater affinity for surfaces, which are not limited by means of adsorption theories, such as: (i) distinctive hydrophilic-hydrophobic domains of anisotropic lignin nanoparticles , (ii) accessibility of hydrogen bonds, (iii) accessibility of coordination bonds, and (iv) the reactivity of the stabilized / captured radicals inside the nucleus of lignin nanoparticles. The species of chemical reactive radicals could be generated during lignin isolation, processing or in contact with air. It is generally accepted that the dark color of lignin is partly attributed to the presence of radicals. Regardless of the theory or the perceived mechanism, the dispersion of lignin nanoparticles, derivatized from lignin nanoparticles, and lignin nanoparticles - polymer complexes described above, were found to demonstrate a strong surface affinity of both organic and inorganic materials , such as, for example, but not limited to, ceramic, vinyl, stainless steel, aluminum, laminate, glass, fabric, and combinations thereof, and provide rinse-resistant properties, for example, hydro-filicity on such treated surfaces. "Surface affinity" is defined in the present invention as having good adhesion to surfaces which, for example, but without limitation, results in the dispersion of lignin nanoparticles, dispersion of lignin nanoparticle derivatives, dispersions of lignin nanoparticles - polymer complex, and combinations thereof, being able to withstand being rinsed with a water surface once it has been applied. As used in the present invention, the term "rinse resistant" and / or "rinse resistance" means that the properties attributable to lignin nanoparticles, derivatized from lignin nanoparticles and / or lignin nanoparticles - polymer complexes will remain for treated surfaces, even after rinsing the surfaces with water or another solvent.
[87] Thus, the inventive concept (s) presently described and / or claimed (s) also encompasses a method of providing water-resistant properties for rinsing surfaces comprising the steps of (a) treating a surface by contacting the surface with at least one of a dispersion of lignin nanoparticles, dispersions of derivatives of lignin nanoparticles, and / or dispersion of lignin nanoparticles - complexes polymer, and combinations thereof, in which the concentrations of lignin nanoparticles, derivatized from lignin nanoparticles, lignin nanoparticles - polymer complexes, and / or combinations thereof, are in the range of about 0.01 to about 70% by weight, or from about 0.1 to about 50% by weight, or from about 10 to about 30% by weight, or from about 15 to about 25% by weight, or about 0.01% to about 5%, or about 0.1% BY WEIGHT to about 2%, or about 0.2% at about 1%, and (b) rinsing the surface with water, and optionally (c) drying the treated surface. In one embodiment, the drying step includes the air drying process of the treated surface. By drying in air, oxidation is left to occur on the surface, to cure the lignin nanoparticles or nanoparticle of lignin - complex on the surface. Of course, other processes for drying a treated surface are known to those skilled in the art and are contemplated for use in the present invention. In one embodiment, at least one dispersion of lignin nanoparticles, the dispersion of lignin nanoparticle derivatized, and / or one dispersion of lignin nanoparticle - polymer complex is diluted before treating the surface in such a way that concentrations of lignin nanoparticles, derivatized from lignin nanoparticles, lignin nanoparticles - polymer complexes, and / or combinations thereof, are in the range of about 0.01 to about 70% by weight, or about from 0.1 to about 50% by weight, or from about 10 to about 30% by weight, or from about 15 to about 25% by weight, or from about 0.01% to about 5 %, or from about 0.1% by weight to about 2%, or from about 0.2% to about 1%.
[88] As such, the lignin dispersions, dispersions of lignin derivatives, and dispersions of lignin nanoparticles - polymer complexes described in the present invention are suitable for functions such as, but not limited to, felt cleaning and conditioning, cleaning hard surfaces, for example, but not limited to cars and countertops, and as a rinse aid for dishes and laundry. In one embodiment, dispersions of lignin nanoparticles and / or derivatives of lignin nanoparticles and / or lignin nanoparticles - polymer complexes can confer properties comprising, for example, but not limited to, hydrophilia, hydrophobia, antimicrobial, UV protection, anti-oxidation and anti-dust on the surface (s). In an alternative embodiment, the lignin nanoparticles - polymer complexes (as described above) can impart tunable properties comprising, for example, but not limited to, hydrophilic, hydrophobic, antimicrobial, UV protection, anti-oxidation and anti-dust, depending on the polymer that is used to form the lignin nanoparticle - polymer complex.
[89] In one embodiment, the inventive concept (s) presently described and / or claimed (s) also encompasses a method for providing hydrophilic properties resistant to rinsing with water from surfaces comprising steps of (i) treating a surface by contacting the surface with at least one of the dispersions described above of lignin nanoparticles, derivatized from lignin nanoparticles, lignin nanoparticles - polymer complexes, and combinations thereof with water, where the concentrations of lignin nanoparticles, derivatized from lignin nanoparticles, lignin nanoparticles - polymer complexes, or combinations thereof are in the range of about 5 to about 50% by weight, or about 10 to about 30% by weight, or from about 15 to about 25% by weight, or from about 0.01 to about 5% by weight, or from about 0.1 to about 2% by weight weight, or about 0.2 to 1% by weight, and (ii) rinsing the surface c with water, and optionally (ii) drying the treated surface. In one embodiment, the drying step includes the air drying process of the treated surface. In one embodiment, at least one dispersion of lignin nanoparticles, dispersion of the derivatives of the lignin nanoparticles, and / or a dispersion of the lignin nanoparticle - polymer complex is diluted before surface treatment.
[90] In one embodiment, the concentration of lignin nanoparticles, derivatives of lignin nanoparticles, lignin nanoparticles - polymer complexes, and combinations of them can be at any concentration considered effective, optionally, active particles above 200 ppm. In one embodiment, a concentration greater than about 10 ppm of active particles is considered to be effective. In an alternative embodiment, a concentration greater than 100 ppm of active particles is considered effective. In an alternative embodiment, surfactants can be added to dispersions of lignin nanoparticles, derived lignin nanoparticles, lignin nanoparticles - polymer complexes, and combinations thereof to reduce the surface affinity of particles and dispersions in complexes described above. In another embodiment, the pH of the diluted dispersion of lignin nanoparticles can be reduced to about 2.5 and still maintain, for example, hydrophilization properties and surface affinity properties for exposures, such as, but not limited to , rinsing the surface. However, it has been found that if the pH drops below a certain level, for example, below about 2, the long-term stability of the dispersion can be negatively influenced and the particles can no longer remain dispersed.
[91] Alternatively, dispersions of lignin nanoparticles, derivatized from lignin nanoparticles, lignin nanoparticles - polymer complexes, and combinations thereof (as described above), can be used separately or together, as additives in a wide range variety of applications, due to its amphiphilic-type polymer properties and affinity of resistance to rinsing with water with surfaces. For example, but without limitation, dispersions of lignin nanoparticles, derivatized from lignin nanoparticles, lignin nanoparticles - polymer complexes, and combinations thereof described in the present invention can be used as emulsifiers, dispersants, non-surfactant based detergents, scale and corrosion inhibitors, plastics and composite materials compatibles, primary coatings, and coating additives, and can be used for felt and passivation and conditioning yarn, hard surface cleaning, hydrophilic coating, improved oil recovery , increased adhesion of adhesives, metal treatment, encapsulation and controlled delivery, surface rinse and antimicrobial and anti-dust surfaces. EXAMPLES
[92] BioChoice ™ lignin (West, Montreal, QC) isolated from black liquor and obtained from Domtar Paper Co. (West, Montreal, QC), which operates a LignoBoost® process originally developed by Innova AB, Stockholm, Sweden, has been used in the following examples, unless otherwise specified below or in the tables. Overview of Analytical Equipment Used in the Examples
[93] Particle size characterizations were made using a ZetaPlus instrument from Brookhaven Instruments Corporation (Holtsvill, NY) measuring samples that comprise 0.01% by weight of solids in water, at the following definitions: Ref. Fluid = 1.1330; Angle = 90; Wavelength = 658 nm; Execution Duration = 5 minutes (final data with an average of five repetitions); Actual Index Ref = 1,600; e Dust filter setting = 30.00.
[94] Centrifuge separations of nanoparticle solutions were performed using an Eppendorf 5430 Centrifuge from Eppendorf North America (Hauppauge, NY) equipped with a FA- 45-48-11 rotor at a fixed angle at 9000 rpm (8060 xg = RCF), when using the internal line (radius of 8.9 cm). The centrifuge tubes used were Utrafree® Durapore PVDF membranes with the polypropylene filter cup / filtrate collection tubes with a capacity of 0.5 mL of EMD Millipore (Billerica, MA). The typical rotation time was 90 minutes. For centrifugation separations, the nanoligin dispersions were diluted to 5 percent solids by weight. 6 to 8 tubes of tared centrifuge filters containing 100 nm membrane filters were loaded with the respective 5 weight percent dispersions and then centrifuged at 9000 rpm for 90 min. Weights of the total solution that passed through the membrane (filtrate) and the wet solid retained in the membrane (material retained) were determined by difference in relation to the empty tared tubes. The filtered solutions were combined, an aliquot taken, weighed, dried in an oven (150 ° C, 60 min) and the solids content determined by the weight difference. This was repeated with the retentate to determine the retained solids. The percentage by weight of the solids that passed through the filter and the percentage that was not determined as follows: (Total filtrate weight) x (filtrate solids) = weight of filtrate solids; (Total Retained Weight) x (retentate solids) = retained solids weight; [Weight of filtrate solids / (weight of filtrate solids + weight of solids retained)] x100 = percentage of filtrate; [Weight of retentate solids / (weight of filtrate solids + weight of retentate solids)] x100 = percentage of retentate.
[95] In assessing the stability of lignin nanoparticle dispersions, the dispersions were observed and were considered "stable" if they remained homogeneous and had not had visible separation, settling in, or precipitating after four days in ambient conditions.
[96] In addition, as used in the examples, "dry base" is the weight remaining after heating at 150 ° C for 60 minutes in an oven and "parts of water" includes water that comes in with the lignin powder. In addition, as used in the present invention, "nanoligin" is to be understood to be interchangeable with lignin "nanoparticles". Differentiating a Lignin Solution from Lignin Nano-particle Dispersions
[97] Lignin solutions (molecules separated from lignin in solution) are well known and can be easily prepared by heating and mixing the lignin in water to a pH of 9.5 or higher. After the solution is formed, the pH can be reduced to 7.5 to 9.0 and the lignin remains in the solution, the specific pH varies with the type and source of lignin. Lignin solutions may have "some" low level of lignin nanoparticles contained in them. For the purpose of the present invention described and / or claimed, the differentiation of a dispersion of lignin nanoparticles from a lignin solution is presented as follows:
[98] The nanoparticle dispersion must meet the following criteria: (1) Less than 85% by weight of the lignin (by dry weight) passes through a 100 nm centrifuge filter, when a 5% lignin is used in weight (in dry weight) of dispersion under the conditions described above for the equipment for centrifugal separation; (2) The concentration percentage by weight at 0.01 results from lignin at an "effective particle size" between 5 and 600 nm and a signal strength greater than 85 kilacounts per second, as analyzed using the settings and instrument particle size as previously described in relation to the characterization of the particle size section; and (3) the dispersion is stable - that is, homogeneous and does not separate for at least four days.
[99] A lignin solution exists when substantially all of the lignin is solubilized, meaning that 85 weight percent or more of dry weight lignin is in soluble form. A lignin solution can be identified using the following criteria: (1) More than 85% by weight of lignin (by dry weight) passes through a 100 nm centrifuge filter, when 5% lignin is used in weight (in dry weight) of dispersion according to the conditions described below for centrifuge separations; (2) a concentration of 0.01 weight percent results in a signal strength of less than 85 kilacounts per second, as analyzed using the particle size settings and instrument described in the particle size characterization equipment.
[100] In addition, a situation may exist, as identified by means of one or more of the following tables, where lignin can be added to water under certain conditions that cause lignin to form neither a solution nor a dispersion due to lignin instability causing it to visibly separate in the phase.
[101] Samples 1 to 9 in Table 1 demonstrate the above distinction between a lignin solution and a dispersion of lignin nanoparticles, as presently described and / or claimed, using samples with a concentration of 5% by weight of particles of lignin there and a 100 nm filter under 8060 xg force for 90 minutes, where "nm" means nanometers, "kcps" means kilacounts per second, and "ps" means particle size.


[102] The data in Table 1 shows that the particle yield (percentage of solids, which are in the form of particles) correlates with the particle size signal strength, in kilacounts per second (Kcps). For definition purposes, a sample with a signal strength less than 85 Kcps for a 0.01 percent by weight solution is considered a solution, and a sample with a signal strength greater than 85 Kcps for a percentage of dispersion of 0.01 by weight and an effective particle size less than 600 nanometers is considered to be a dispersion of nanoparticles.
[103] It should be noted that the distinction between a solution and a dispersion, as defined above and illustrated in Table 1, will exist for any composition produced using the "general procedure", as set out below, even in view of the many variables that can be modified in it. That is, despite the fact that the process is used to produce a dispersion of lignin nanoparticles, the distinctions defined above between a solution and the dispersion will be applied. For samples 1 to 9, in particular, however, the general procedure described below was used, in which: (1) one sample used potassium hydroxide as the base, equipment to configure "C", and the potassium hydroxide was added to a final pH of 11.0; (2) Sample 2 used potassium hydroxide as a base, equipment to configure "C", and potassium hydroxide was added up to a final pH of 9.9; (3) sample 3 was a commercial product Zalta DS26-330 and Solenis LLC ™ lignin sulfonate (Wilmington, DE) was used; (4) The sample of 4 used potassium hydroxide as base, equipment to configure "A", and potassium hydroxide was added to a ratio of mole base per g of dry lignin 0.000853; (5) Sample 5 used sodium hydroxide as the base, equipment to configure "A", and sodium hydroxide was added to a ratio of mole base per g of dry lignin 0.000833; (6) Sample 6 used potassium carbonate as a base, equipment to configure "C", and potassium carbonate was added to a base ratio of mol per g of dry lignin 0.000694; (7) The sample of 7 used potassium carbonate as a base, equipment to configure "A", and potassium carbonate was added to a ratio of mole base per g of dry ligand 0.000588; (8) Sample 8 used potassium carbonate as the base, equipment to configure "C", and potassium carbonate was added to a ratio of mole base per g of dry lignin 0.000641; (9) sample 9 used potassium carbonate as a base, equipment to configure "C", and potassium carbonate was added to a ratio of mole base per g of dry lignin 0.000694; each sample was heated to 92 ° C for 5 minutes. Preparation and Results of Lignin Nanoparticle Dispersions for Microscopy Analysis and Surface Modification Analysis to Provide Rinse Resistance Properties Using Microscopy Analysis
[104] 60.23 parts of BioChoice ™ (Domtar Inc, West, Montreal, QC) kraft lignin of about 27% moisture were mixed with 2.98 parts of potassium carbonate in 99.88 parts of water. The mixture was heated to reflux, with stirring, within 15 minutes until a homogeneous liquid dispersion was obtained. During heating to reflux, it was observed that the mixture became from a grayish suspension to the viscous black liquid at about 80 ° C, indicating the initial formation of a dispersion of lignin nanoparticles. After cooling to about 70 ° C, the dispersion was diluted with cold water. The dispersion was clear, free of material in particular, with a pH of 8.3. The lignin nanoparticles were present in the dispersion at about 25% by weight as measured by balancing moisture at 100 ° C until a constant weight was obtained. The particle sizes of the lignin nanoparticles were determined to be in the range of about 40 to 100 nm (see Figure 4 and Figure 5), in which a diluted sample of the dispersion was dropped onto mica and measured using an AFM microscope.
[105] Analysis of surface modification to provide rinse-resistant wetting properties using atomic force microscopy (AFM) using an Asilum Research MFP-3D atomic force microscope in AC mode using silicon beams (AC240TS- R3, Asilum Research) with an average spring constant of about 2 N / m. The 2D height images with frame in the amplitude image analysis section, and the 3D height images are shown in Figures 6 to 9, as described below.
[106] The microscopic delimiting glass cover was used as the surface, whose AFM images were obtained as a control before and after the rinse water tap and dried (Figures 6 and 7). No water film or laminated water was observed with the coverslips, although some of the thin, flat coatings were rinsed, exposing the glass surface.
[107] The treated surfaces were prepared by immersion in the sliding cover in 0.1% of the lignin dispersion, as described above, prepared by diluting the above dispersion comprising 25% by weight of liginine nanoparticles with water. from the tap. The slides were then immediately rinsed under running tap water for 30 seconds. A thin film of water was observed on the treated surface, before and after rinsing, indicating that the surface became more hydrophilic. The rinse slide was then air dried for AFM images. The images (Figure 8) show that lignin nanoparticles were attached to the surface after rinsing with tap water. The denser lignin nanoparticles attached to the residual hydrophobic coating were also observed.
[108] Separately, a lignin solution was prepared from the same source of lignin, which was used to prepare the dispersion of lignin nanoparticles described above - that is, BioChoice ™ (Domtar Inc., West, Montreal, QC) lignin kraft. This solution was obtained by dissolving the lignin in alkaline water and then carefully adjusting the pH back to pH = 9, where the lignin precipitates if the pH has been further reduced. This solution was diluted to 0.1% with tap water and was used to treat the glass cover slip in the same way as the lignin nanoparticles. Surprisingly, lignin nanoparticles were not detected by dynamic light scattering, but the ligand solution demonstrated hydrophilization of the coated hydrophobic delimiting glass cover and water sheets were observed before and after rinsing. with tap water. AFM showed smaller nanoparticles "sticking" to the washed glass cover and denser to the hydrophobic coating (Figure 9). The particle size is in the range of less than a few nanometers. Preparation and Results of Lignin Nanoparticle Dispersions Using Different Process Conditions
[109] A series of experiments were carried out varying one or more processing conditions from a general procedure for the preparation of a dispersion of lignin nanoparticles, in order to determine the impact of variables such as the rate of increase of temperature, the maximum temperature, the amount of base, type of base, etc., on the formation of a dispersion of lignin nanoparticles as defined and used in the present invention. The general procedure used for each of the following samples in Tables 2-9 was as follows:
[110] Five to forty-five parts (dry basis) of lignin powder were dispersed in 95 to 55 parts of water at 20 to 90 ° C, with very good agitation for 5 to 20 min, which had a pH in a range from 2.0 to 5.5. A base, or a combination of bases, such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, ammonium hydroxide, etc. was added to the dispersion after the lignin powder. The dispersion was then heated for an amount of time. The water at five to thirty-five degrees Celsius was then added, so that the solids resulting from the dispersion were between 5 to 40% by weight of the dispersion and then allowed to cool to room temperature, typically over a period of 15 180 minutes.
[111] Tables 2 to 9 identify the specific process conditions for each sample by noting that the samples in Table 9 differ from the general procedure. The procedure in Table 9 differs first by preparing a 20 wt% lignin solution by heating the lignin and water to 90 ° C while maintaining a pH of 10.0-12.0 with potassium hydroxide for 30 min (Examples 88 and 93) and the remaining examples in Table 9 start with the aliquots of this solution and the pH is gradually reduced with 10% by weight sulfuric acid while the sample is mixed vigorously at the temperature indicated in Table 9 to determine whether Nanodispersions could be obtained in this way.
[112] In addition, there were no different equipment configurations that were used for the various experimental samples presented in Tables 2 to 9, which are in the present invention identified as any "a", "b", "installation equipment. c ", or" d ". The following describes the various configuration equipment for each:
[113] "a" configuration equipment: A 400 mL cylindrical glass vessel with a jacket (11.43 cm (4.5 inches) high by 2.75 in diameter - not including liner), equipped with a top shaker equipped with a high shear mixer blade for blending or a moderately blended shaker anchor, and a thermocouple to monitor the temperature. The sample was heated using circular steam through the jacket. When this configuration was used, 22.5 g of liginine (dry base) was used. The initial grams of the charged water can be determined from the initial solids provided in Tables 2 to 9, the base grams can be determined from the rates of the "mole base of lignin grams" provided in the tables, and the grams of water of final dilution added can be determined from the final solids indicated in the tables.
[114] Configuration equipment "b": A 250 mL 3-neck jacketed glass bottom flask equipped with a stirrer on top with a half moon stirrer for mixing, a thermocouple to monitor temperature, and a reflux condenser, to keep the water from evaporating from the flask. The sample was heated using hot oil circulating through the jacket. When this configuration was used, 22.5 g of lignin (dry basis) was used. The initial grams of charged water can be determined from the initial solids provided in the tables, the base grams can be determined from the "mole base of lignin grams" rates provided in the tables, and the grams of final dilution water added can be determined from the final solids indicated in the tables.
[115] "C" configuration equipment: A 1-L kettle-type adjustment glass reactor with jacket with a top stirrer equipped with a top stirrer equipped with two A340 holders for mixing, a thermocouple to monitor temperature, and a reflux condenser to keep water from evaporating from the container. The sample was heated using hot oil circulating through the jacket. When this configuration was used, 180 g of lignin (dry basis) was used. The initial grams of charged water can be determined from the initial solids provided in the tables, the base grams can be determined from the "mole base of lignin grams" rates provided in the tables, and the grams of final dilution water added can be determined from the final solids indicated in the tables.
[116] "d" configuration equipment: A Mettler Toledo RC1e high temperature calorimeter for adjustment (Mettler-Toledo AutoChem Inc., Columbia, MD) with 1-L kettle type glass reactor that was fit with a adjusting the upper stirrer with a mixing tape, a thermocouple to monitor the temperature, and a reflux condenser to keep the water from evaporating from the container. The sample was heated using hot oil circulating through the jacket. For cases where temperatures above 99 ° C were used, the reactor was closed and run under pressure. When this configuration was used, 184 g of lignin (dry basis) was used. The initial grams of loaded water can be determined from the initial solids provided in the tables, the base grams can be determined from the "mole base of lignin grams" rates provided in the tables, and the grams of final dilution water added can be determined from the final solids indicated in the tables.
[117] Table 2 shows the impact of the top temperature when heating the base, lignin, and water to form a dispersion of stable lignin nanoparticles. This table demonstrates that at a temperature above 65 ° C it is necessary to form a stable dispersion of nanolignin of adequate yield. The lower end of the temperature range that will be successful in nanodispersion formations varies depending on the lignin system (for example, BioChoice ™ lignin and Protobind 2400 ligin isolated from wheat straw (Green Valor Enterprises LLC, Media, PA)) having different results when a temperature of 70 to 72 ° C was used to form the nanodispersion). It is anticipated that lignin from an alternative source, with a lower softening point would form nanolignin dispersions at lower temperatures and a lignin with a higher softening point would form nanolignin dispersions at temperatures above 99 ° C .
[118] Table 3 demonstrates the impact of the rate of temperature rise on the formation of stable dispersions of nanolignin particles. This table demonstrates that the rate of temperature rise to reach the top temperature can vary significantly and nanolignin dispersions are still formed.
[119] Table 4 shows the impact of the top temperature for the formation of a stable dispersion of nanolignin particles. This table shows that the time taken at the upper temperature can vary significantly and the nanolignin dispersions are still formed.
[120] Table 5 demonstrates the impact of the initial temperature for the formation of stable dispersions of nanolignin particles. This table shows that the initial temperature at which the lignin is introduced can vary considerably and even the nanoligin dispersions are formed.
[121] Table 6 demonstrates the impact of the pH type and final base for the formation of stable dispersions of nanolignin particles. This table demonstrates that the type of base used can vary widely, including both inorganic and organic bases. The final pH generally ranges from 7 to 8.8 to form the stable dispersions of nanoligin for most bases. A final pH value greater than 9.0 results in the formation of a solution, instead of a dispersion, except when ammonium hydroxide is used as the base, in which case a stable dispersion is formed only up to a pH of 10.2 .
[122] Table 7 demonstrates the impact of lignin concentration and the dilution step on the formation of nanoparticles and quality dispersion. This table shows that (a) a better dispersion was formed (lower particle size, dispersion stability), when a dilution step took place after the last heating step, and (b) the Nanolignin dispersions are formed over a wide range of lignin concentrations, from 5 to 40 weight percent lignin. It should be noted that, in some cases, the table shows that the final solids were larger than the initial solids, which is due to some water evaporation during the process.
[123] Table 8 demonstrates the impact of the lignin source and the type of formation of stable dispersions of nanolignin particles. This table demonstrates that the process works with different sources and types of lignin.
[124] Table 9 shows unsuccessful attempts to make nanolignin dispersions ranging from high pH to low pH.










Derivatization and later dispersion of lignin nanoparticles in water
[125] Lignin nanoparticle derivatized dispersions were prepared using two different proportions of lignin and glycerol carbonate, in the present invention referred to as Examples A and B.
[126] For example A, 60 parts of BioChoice ™ (Domtar Inc, West, Montreal, QC) kraft lignin of about 27% moisture content were mixed with 30 parts of glycerol carbonate and 3 parts of potassium carbonate. For Example B, 60 parts of lignin nanoparticles were mixed with 60 parts of potassium carbonate and 3 parts of glycerol carbonate. Both mixtures were vacuum dried to remove any residual water, while mixing and then heated to a temperature of approximately 160 ° C for about 20 minutes and then cooled to 120 ° C. A homogeneous viscous liquid was observed. After cooling to 120 ° C, 98 parts of water were mixed with the reaction product. The mixture was vigorously stirred and heated to reflux until a homogeneous liquid dispersion was obtained. For both Examples A and B, derivatives of lignin nanoparticles were present in the dispersion at about 37% by weight as measured by balancing moisture at 100 ° C until a constant weight was obtained. The particle sizes of the lignin nanoparticles were determined to be in the range of about 30 to 100 nm (see Figure 10), as measured by an AFM microscope in a similar manner to that described in the previous example. In addition, the dispersions appeared to be clear and had a pH of about 8.8. Lignin nanoparticles - Polymer complex
[127] A lignin nanoparticle - polymer complex was produced as a dispersion by adding a 2 wt% aqueous solution of the lignin nanoparticle derivatized dispersion of Example A to a 2 wt% aqueous solution of polyvinylpyrrolidone (K-90 PlasdoneR from Ashland, Inc.). The dispersion of lignin nanoparticle derivatized was added to the polyvinylpyrrolidine to increase the proportions while mixing and to control the viscosity of the mixture. In a 1: 4 weight ratio of polyvinylpyrrolidone to the derivatized lignin nanoparticles, a viscosity peak was observed (Figure 3), indicating that a network of lignin nanoparticles - polymer complex had been formed. This dispersion was found to have a particle size in the range between 15 and 40 nm (see Figure 11), as measured using an AFM microscope with the procedure described in the example above. A similar relationship of lignin polymer to nanoparticles also resulted in maximum viscosity values when using the dispersion of lignin nanoparticles described above and the dispersion of lignin nanoparticles derived from Example B. It was also found that such nanoparticles of lignin - polymer complexes are more stable and also have wetting and hydrophilizing properties in more acidic conditions up to a pH of about 2.5. However, it was observed that the particles appear to grow more at a pH of about 2 to 3.
[128] A second lignin nanoparticle - polymer complex was produced as a dispersion by adding a dispersion of aqueous lignin nanoparticles comprising 23% by weight of solids from a 10% by weight aqueous solution of polyvinyl alcohol ( PVA 88-50) and mixed. The viscosity of the mixture was monitored using a Brookfield® viscometer (Middleboro, MA) as increasing amounts of lignin nanoparticles were added at room temperature. As can be seen in Figure 12, a dramatic increase in viscosity was observed when the weight ratio of active lignin to active polyvinyl alcohol went beyond 1: 3, indicating that a network of lignin - polymer complex nanoparticles had been formed. As also shown in Figure 12, when a 5 wt.% Solution of polyvinyl alcohol (PVA 88-50) was used in the same process, an increase in viscosity was also observed, although less dramatic and requiring a larger portion of lignin nanoparticles, in this way, it also indicates the formation of a network of lignin nanoparticles - polymer complex. Surface modification to provide rinse-resistant wetting properties
[129] It has been observed that the application of dispersions of lignin nanoparticles, derivatized from lignin nanoparticles, and / or lignin nanoparticles - polymer complexes provides organic and inorganic surfaces with excellent wetting properties.
[130] The following procedure was used to demonstrate the wetting properties for surfaces provided: 1) a dispersion was prepared using one of the methods described above, 2) the dispersion was applied to the surfaces of an article until the surface was completely wet, 3) the surface was rinsed with tap water, followed by rinsing the surface with the water that had been dyed. After rinsing with dyed water, the treated surfaces were compared with untreated surfaces of similar materials. FIGURES 13 to 20 illustrate such comparisons corresponding to the surfaces of vinyl, laminate, vinyl, ceramic, aluminum, stainless steel, polypropylene and glass, respectively. The treated surfaces shown in Figures 13 to 20 were treated with a diluted dispersion of a lignin nanoparticle - polymer complex prepared by adding an aqueous solution of 2% by weight of the dispersion of the lignin nanoparticle derivative of Example A from a 2% by weight aqueous solution of polyvinylpyrrolidone (K-90 PlasdoneR from Ashland, Inc.) until a 1: 4 weight ratio of polyvinylpyrrolidone to the lignin derivatives of lignin was reached. The mixture was further diluted with water to about 0.5% by weight. As can be seen in Figures 13 to 20, treating a surface with such a dispersion of a lignin nanoparticle - polymer complex clearly provides better wetting properties on untreated surfaces.
[131] An additional procedure was used to demonstrate such wetting properties by observing contact angles: 1) the surface of an article was dried at 50 ° C, and 2) drops of water were added to the surface. Droplets on surfaces were observed to distinguish the wetting properties provided on treated surfaces (i.e., how well the droplets spread on the surfaces) compared to untreated surfaces. Figures 21 to 23 illustrate these observations corresponding to the felt, polypropylene, and aluminum fabric surfaces, respectively. The treated surfaces shown in Figures 21 to 23 were treated with a dispersion of a lignin nanoparticle - polymer complex prepared by adding an aqueous solution of 2% by weight of the dispersion of the lignin nanoparticle derivative of Example A from one 2 wt% polyvinylpyrrolidone aqueous solution (PlasdoneR K-90 from Ashland, Inc.) until a 1: 4 weight ratio of polyvinylpyrrolidone to the lignin nanoparticle derivatized. The mixture was further diluted with water to about 0.5% by weight. As can be seen in Figures 21 to 23, treating a surface with such a dispersion of nanoparticles of a lignin complex clearly provides the improved properties on the untreated surfaces. Furthermore, it has been observed that dispersions of nanoparticles of lignin - polymer complexes are able to confer these wetting properties when applied at concentrations as low as 200 ppm in aqueous solution. Impact of Nanolignin Dispersions on Hydrosheeting Behavior
[132] Another procedure was used to characterize the surface modification properties of lignin nanoparticles. In particular, the hydrosheeting behavior of lignin nanoparticles was compared with controls selected from water, a lignin solution, and polyvinylpyrrolidone on aluminum and / or polypropylene substrates. The test method consisted of diluting several samples of dispersions of lignin nanoparticles to four weight percent with deionized water - the two dispersions of lignin nanoparticles corresponding to sample 16 in Table 2 and sample 38 in Table 6 - and visually comparing the hydrosheeting behavior of lignin nanoparticle dispersions against the aforementioned controls. A rectangular substrate bar of 5.08 cm (2 inches) by 10.16 cm (4 inches) by 0.64 cm (0.25 inches) was immersed in the respective dispersion of the sample or solution for 60 seconds, the bar was removed and the excess solution was allowed to drain for about 15 seconds, after which the 16.51 cm (6.5 inch) bars were placed under a continuous running tap, tap water at 40 ° C during the time specified in the table. The results are shown in Table 10, which demonstrates that the substrate surfaces treated with the nanolignin dispersion, are completely wet and the water flows through the surface in a persistent way, even in the form of a leaf (effect remains after 45 minutes of rinse). In comparison, substrates treated with traditional wetting agents lose their effect in a shorter time than substrates treated with nanolignin solution (the wetting effect is not as persistent). In this way, the improved wetting characteristics of substrates treated with nanoligin dispersions are more persistent than when the substrates are treated with other common wetting agents.
[133] From the above description, it is clear that the concept (s) described in the present invention is (are) well adapted to carry out the objective and obtain the advantages mentioned in the present invention. invention, as well as those inherent in the inventive concept (s) described in the present invention. Although exemplary embodiments of the inventive concept (s) described in the present invention have been described for the purposes of this description, it will be understood that numerous changes can be made that will readily be evident by through people who are skilled in the art and who are carried out without departing from the scope of the inventive concept (s) described in the present invention and defined (s) by means of the appended claims. Sample Sample Conc. (%) Substrate Rinsing time duration Visual hydro-sheeting result Visual rinsing time result Visual hydro-sheeting result Water control 100 Aluminum 20 seconds Water flowed in channels Many drops remained when water stopped flowing 45 min Water flowed in channels Many drops remained when water stopped flowing Nanolignin dispersion 4 Aluminum 20 seconds Water flowed as a single leaf None of the drops remained when water stopped flowing 45 min Water flowed as a single leaf None of the drops remained when water stopped flowing Lignin Solution 4 Aluminum 20 seconds Water flowed like a single leaf None of the drops remained when water stopped flowing 45 min Water flowed in some channels Some drops remained when water stopped flowing Polyvinyl - pyrolidone 4 Aluminum 20 seconds Water flowed like a single leaf None of the drops remained when the water stopped flowing 45 min Water flowed in some channels Some dro ps remained when water stopped flowing Water control 100 Polypropylene 20 seconds Water flowed in channels Many drops remained when water stopped flowing 45 min Water flowed in channels Many drops remained when water stopped flowing Nanolignin dispersion 4 Polypropylene 20 seconds Water flowed like a single leaf None of the drops remained when the water stopped flowing 45 min Water flowed like a single leaf None of the drops remained when the water stopped flowing

权利要求:
Claims (16)
[0001]
1. Method for preparing an aqueous dispersion of lignin nanoparticles, characterized by the fact that it comprises the steps of: - combining (a) lignin, and (b) water, to form an aqueous composition - adjusting the pH of the composition aqueous with a base, where the base is not an inorganic divalent base, to form a lignin composition that does not form a lignin solution, comprising from 1 to 70% by weight of lignin, and - heat the lignin composition during mixing to form a stable dispersion of lignin nanoparticles.
[0002]
2. Method according to claim 1, characterized by the fact that the base is selected from the group consisting of alkali hydroxides, ammonium hydroxide, alkyl substituted ammonium hydroxides, organic amines, carbonates or alkali bicarbonates, carbonates or ammonium bicarbonates, ammonium carbonates substituted by alkyl or bicarbonates, and combinations thereof.
[0003]
3. Method according to claim 1 or 2, characterized by the fact that the base is selected from the group consisting of ammonium hydroxide, potassium carbonate, potassium hydroxide, sodium carbonate , sodium hydroxide, triethanolamine, and combinations thereof.
[0004]
Method according to any of claims 1 to 3, characterized by the fact that lignin and water are combined before adding the base, forming a mixture of lignin and water with a pH less than or equal to 6.
[0005]
5. Method according to any of claims 1 to 4, characterized by the fact that lignin is produced from a process selected from the group consisting of Kraft, solvent extraction, biofuel processing, organosolv, Bjorkman process , steam explosion, cellulolytic enzyme, acid hydrolysis, soda lime, and combinations thereof.
[0006]
6. Method according to any of claims 1 to 5, characterized by the fact that lignin is derivatized from lignin.
[0007]
Method according to any of claims 1 to 6, characterized in that the lignin composition comprises from 5 to 40% by weight of lignin.
[0008]
Method according to any of claims 1 to 7, characterized in that the lignin composition comprises from 15 to 30% by weight of lignin.
[0009]
Method according to any of claims 1 to 8, characterized in that the lignin composition is heated to a temperature in the range of 50 ° C to 120 ° C, where the lignin composition is at a higher pressure at 1 atm during temperatures in the range of 100 ° C to 120 ° C.
[0010]
Method according to any of claims 1 to 9, characterized in that the lignin composition is heated to a temperature in the range of 70 ° C to 100 ° C.
[0011]
11. Method according to claim 4, characterized by the fact that the base is added until the mixture has a pH in the range of 7 to 9.
[0012]
12. Method according to claim 4, characterized by the fact that the base is ammonium hydroxide.
[0013]
13. Method according to claim 12, characterized by the fact that ammonium hydroxide is added until the mixture has a pH in the range of 7 to 10.5.
[0014]
14. Method according to claim 1, characterized by the fact that the stable dispersion of lignin nanoparticles comprises (i) nanoparticles having an effective particle size in the range of 30 to 600 nanometers, and (ii) an intensity of signal in the range of 85 to 550 counts per kilosecond for a concentration of 0.01% by weight of lignin nanoparticles in the dispersion.
[0015]
15. Method according to claim 1 or 14, characterized by the fact that the stable dispersion of lignin nanoparticles comprises (i) nanoparticles having an effective particle size in the range of 70 to 350 nanometers, and (ii) a signal strength in the range of 200 to 550 counts per kiloseconds for a concentration of 0.01% by weight of lignin nanoparticles in the dispersion.
[0016]
16. Method according to any of claims 1 to 15, characterized by the fact that the stable dispersion of lignin nanoparticles remains homogeneous for at least 4 days under ambient conditions.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112016012411B1|2021-03-30|METHOD FOR PREPARING A WATER DISPERSION OF LIGNINE NANOPARTICLES

---

Sipponen et al.2017|All-lignin approach to prepare cationic colloidal lignin particles: stabilization of durable Pickering emulsions

---

Xue et al.2016|Aggregation-induced emission: the origin of lignin fluorescence

---

RU2602119C2|2016-11-10|Suspension of self-binding particles, method of its production and use

---

Song et al.2014|Characteristics of ultrafiltration membranes fabricated from polysulfone and polymer-grafted silica nanoparticles: Effects of the particle size and grafted polymer on the membrane performance

---

KR20140063734A|2014-05-27|Water-based polymer emulsions for opaque films and coatings applications on flexible substrates

---

EP2970599B1|2017-11-22|Optimized emulsion drying process for making micronized polyetherimide polymers

---

KR20130016117A|2013-02-14|Aqueous coating composition for improved liquid stain repellency

---

Li et al.2016|Direct preparation of hollow nanospheres with kraft lignin: A facile strategy for effective utilization of biomass waste

---

Jafarzadeh et al.2015|Effect of TiO2 nanoparticles on structure and properties of high density polyethylene membranes prepared by thermally induced phase separation method

---

Lisperguer et al.2013|Structure and thermal properties of maleated lignin-recycled polystyrene composites

---

Jayalakshmi et al.2015|Cellulose acetate graft-| for modification of AMC ultrafiltration membranes to mitigate organic fouling

---

Ghavidel et al.2020|Pickering/Non‐Pickering Emulsions of Nanostructured Sulfonated Lignin Derivatives

---

Xu et al.2018|Effects of modified nanocrystalline cellulose on the hydrophilicity, crystallization and mechanical behaviors of poly |

---

Tavangar et al.2020|Morphological and performance evaluation of highly sulfonated polyethersulfone/polyethersulfone membrane for oil/water separation

---

JP5943997B2|2016-07-05|Surface active comb copolymer

---

Song et al.2015|Perfluoropolyether/poly | triblock copolymers with controllable self-assembly behaviour for highly efficient anti-bacterial materials

---

Feng et al.2018|Synthesis of a benzyl-grafted alginate derivative and its effect on the colloidal stability of nanosized titanium dioxide aqueous suspensions for Pickering emulsions

---

Ibrahim et al.2006|Preparation and characterization of polystyrene–poly | amphiphilic block copolymers via atom transfer radical polymerization: Potential application as paper coating materials

---

Huang et al.2019|Directed 2D nanosheet assemblies of amphiphilic lignin derivatives: Formation of hollow spheres with tunable porous structure

---

Wei et al.2015|Color changing Pickering emulsions stabilized by polysiloxane microspheres bearing phenolphthalein groups

---

CN105820350B|2019-04-09|Phenolate methylolation and carboxy methylation lignin and preparation method thereof

---

Mahdavi et al.2016|An efficient nanofiltration membrane based on blending of polyethersulfone with modified | copolymer

---

KR20200045515A|2020-05-04|Method for manufacturing thermoplastic polymer particles, thermoplastic polymer particles produced thereby, and articles made therefrom

---

CN105949349B|2018-10-02|A kind of chitosan-based hyper-dispersant and preparation method thereof

同族专利:

---

公开号 | 公开日

---

CA2930604C|2018-09-04|

---

EP3080138A1|2016-10-19|

---

US10035928B2|2018-07-31|

---

KR20160097275A|2016-08-17|

---

CN105829406A|2016-08-03|

---

MX2016007241A|2016-12-09|

---

AU2014361863B2|2018-05-31|

---

AU2014361863A1|2016-06-02|

---

CA2930604A1|2015-06-18|

---

WO2015089456A1|2015-06-18|

---

PL3080138T3|2021-06-14|

---

US20150166836A1|2015-06-18|

---

EP3080138B1|2019-06-05|

---

CN105829406B|2020-06-30|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3956261A|1975-10-10|1976-05-11|Westvaco Corporation|Lignin adducts|

---

US4454066A|1982-11-01|1984-06-12|Westvaco Corporation|Reduction of lignin color|

---

US4957557A|1988-10-11|1990-09-18|Westvaco Corporation|Submicron lignin dispersions|

---

US5008378A|1988-10-11|1991-04-16|Westvaco Corporation|Submicron lignin dispersions|

---

US5192361A|1992-01-27|1993-03-09|Westvaco Corporation|Submicron lignin-based binders for water-based black ink formulations|

---

US5972047A|1998-03-10|1999-10-26|Westvaco Corporation|Amine modified sulfonated lignin for disperse dye|

---

US5989299A|1998-05-26|1999-11-23|Westvaco Corporation|Mixtures of amine modified lignin with sulfonated lignin for disperse dye|

---

US7691982B2|2004-09-24|2010-04-06|Nippon Shokubai Co., Ltd.|Dispersant using kraft lignin and novel lignin derivative|

---

WO2007100861A1|2006-02-28|2007-09-07|Cellular Bioengineering, Inc.|Polymer composition and method for removing contaminates from a substrate|

---

CA2799798C|2010-06-03|2015-01-20|Fpinnovations|Method for separating lignin from black liquor|

---

CN102002165A|2010-09-15|2011-04-06|东北林业大学|Method for preparing nano lignin by using supercritical anti-solvent technology|

---

CN103275331B|2013-05-23|2015-08-12|广西大学|A kind of take black liquid as the preparation method of the lignin nanoparticle of raw material|

---

CN103254452B|2013-05-23|2014-10-29|广西大学|Preparation method of lignin nanoparticle|

---

AU2014361863B2|2013-12-12|2018-05-31|Solenis Technologies, L.P.|Lignin nanoparticle dispersions and methods for producing and using the same|US9914870B2|2013-01-22|2018-03-13|Carnegie Mellon University|Lignin-containing polymers and compositions including lignin-containing polymers|

---

FI126737B|2013-11-26|2017-04-28|Upm-Kymmene Corp|A process for treating lignin and preparing a binder composition|

---

AU2014361863B2|2013-12-12|2018-05-31|Solenis Technologies, L.P.|Lignin nanoparticle dispersions and methods for producing and using the same|

---

ES2895101T3|2013-12-16|2022-02-17|Ren Fuel K2B Ab|Composition comprising esters of lignin and oil or fatty acids|

---

KR20180026716A|2015-07-07|2018-03-13|솔레니스 테크놀러지스, 엘.피.|Methods for inhibiting the deposition of organic contaminants in pulp and paper making systems|

---

US20190037837A1|2016-02-05|2019-02-07|Max-Planck-Gesellschaft Zur Förderung Der Wissenschaften Ev|Lignin biomaterial as agricultural drug carrier|

---

CN107043462B|2017-05-25|2019-04-26|湖南师范大学|A method of nano lignin is prepared using reversed-phase emulsion|

---

CN111801154A|2017-10-26|2020-10-20|阿尔托大学注册基金会|Aqueous lignin dispersion and method for producing same|

---

CN108409984B|2018-03-26|2020-07-31|中南大学|Method for rapidly and synchronously preparing lignin nanoparticles and carbon quantum dots|

---

CN108420751A|2018-04-12|2018-08-21|北京林业大学|A kind of preparation method of the nano lignin particle with uvioresistant effect|

---

AT521393B1|2018-06-27|2021-02-15|Univ Wien Tech|Process for the production of lignin particles as part of a continuous process|

---

IT201800006815A1|2018-06-29|2019-12-29|AN ORGANIC-INORGANIC HYBRID MATERIAL COMPRISING A METAL AND LIGNIN, PROCESSES FOR PREPARING THE SAME AND USES THEREOF / HYBRID ORGANIC-INORGANIC MATERIAL INCLUDING METAL AND LIGNIN, PROCESSES FOR ITS PREPARATION AND USES|

---

EP3830194A1|2018-07-30|2021-06-09|Washington State University|Plant-based compositions for the protection of plants from cold damage|

---

CN109320738A|2018-09-30|2019-02-12|杭州市第人民医院|A method of preparing lignin nanoparticle|

---

SE542795C2|2018-10-08|2020-07-07|Stora Enso Oyj|Process for preparing a resin|

---

SE542796C2|2018-10-08|2020-07-07|Stora Enso Oyj|Process for preparing a resin|

---

CN111171343A|2018-11-12|2020-05-19|中国科学院过程工程研究所|Emulsion preparation method based on steam-exploded lignin|

---

WO2020109671A1|2018-11-29|2020-06-04|Aalto University Foundation Sr|Lignin particle based hydrogel and the method for preparation of lignin colloidal particles by solvent evaporation process|

---

US10941524B2|2018-11-30|2021-03-09|Solenis Technologies, L.P.|Pulp mixture|

---

CN109627466A|2018-12-12|2019-04-16|天津科技大学|A kind of preparation method of lignin nano spherical particle|

---

CN110205866B|2019-05-29|2021-12-24|盐城工学院|Method for improving water vapor barrier property of food packaging paper|

---

CN110241658B|2019-05-29|2021-12-14|盐城工学院|Method for improving water vapor and grease barrier property of food packaging paper|

---

US11155683B2|2019-09-13|2021-10-26|Nanophase Technologies Corporation|Lipophillically dispersed phenolic polymer particles|

---

WO2021251987A1|2020-06-12|2021-12-16|Renmatix, Inc.|Method of dispersing hydrophobic substances in aqueous cleansing system|

---

WO2022016117A1|2020-07-16|2022-01-20|Nanophase Technologies Corporation|Particulates of polyphenolics and dispersions thereof|

---

WO2022038310A1|2020-08-16|2022-02-24|Aalto University Foundation Sr|Functional colloidal lignin particles and methods of preparation thereof|

法律状态:
2019-05-28| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

---

2020-10-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

---

2021-01-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201361915442P| true| 2013-12-12|2013-12-12|

---

US61/915,442|2013-12-12|

---

PCT/US2014/070119|WO2015089456A1|2013-12-12|2014-12-12|Lignin nanoparticle dispersions and methods for producing and using the same|

---