Method for improving nanocellulose dispersion in elastomeric compounds and compositions comprising nanocellulose dispersed in elastomeric compounds

Abstract

To provide nanocellulose dispersion compositions containing an anti-agglomerant and a nanocellulose, and methods of making the nanocellulose dispersion compositions.SOLUTION: These compositions can promote improved dispersibility of nanocellulose fibrils and nanocellulose crystals in polymer matrices, such as in elastomer formulations for use in tire production.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] (Reference to Related Application) This application was filed as a PCT international application on October 21, 2019, and claims the benefit of priority to U.S. Provisional Patent Application Nos. 62 / 748,564 and 62 / 748,574, filed on October 22, 2018, the disclosures of which are incorporated herein by reference in their entireties.

[0002] The present disclosure relates to methods for improving the dispersion of nanocellulose and the resulting nanocellulose dispersion compositions for use in polymer formulations, more particularly for use in elastomer formulations intended for tires and other end-use applications. [Background technology]

[0003] Nanocellulose has recently attracted attention as a nanomaterial for various applications, including plastics and elastomers. Because nanocellulose is derived from biomass rather than hydrocarbon materials, its use in these applications aims to improve the performance of the resulting composites and the sustainable nature of future materials. However, one of the challenges of nanocellulose is its dispersibility in hydrophobic, nonpolar solvents and matrices (including plastics and elastomers). Whether nanocellulose is in crystalline or fibril form, nanocellulose typically bonds to itself during drying, resulting in large aggregates of nanocellulose in the polymer composite structure.

[0004] For example, when nanocellulose is mixed into an elastomeric compound, it is desirable to ensure that the nanocellulose is well dispersed, thereby eliminating large aggregates and realizing the full benefits of incorporating nanocellulose into the elastomeric matrix. Large aggregates of any polymer additive can cause stress concentrations and lead to premature failure of the polymer composite. Summary of the Invention [Problem to be solved by the invention]

[0005] It therefore becomes important to devise ways to significantly improve the dispersibility of nanocellulose in polymer formulations, and this is a key issue facing the development, growth, and commercialization of nanocellulose in many end-use applications. It is therefore towards these ends that the present invention is generally directed. [Means for solving the problem]

[0006] This Summary is provided to introduce selected concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify essential or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0007] In accordance with the purposes of the present invention, as embodied and broadly described herein, the present disclosure relates in one aspect to a method for adding partitioning agents during or before the nanocellulose drying process, such that the partitioning agents remain intact and prevent nanocellulose crystals and nanocellulose fibrils from binding together, resulting in a nanocellulose dispersion composition that can be readily dispersed in polymeric formulations such as elastomers and plastics.

[0008] Thus, in one aspect of the present invention, a method for deflocculating nanocellulose in an aqueous system to improve its dispersibility in a polymer is disclosed, the method comprising: (a) combining the aqueous dispersion of nanocellulose with a deflocculating agent to form a mixture; and (b) drying the mixture to form a nanocellulose dispersion composition (NDC). The deflocculating agent can include carbon black filler, elastomer latex, wax, or any combination thereof.

[0009] In another aspect, a method for deflocculating nanocellulose in an aqueous system using a deflocculating agent is disclosed, the method comprising: (A) combining an aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture; and (B) drying the mixture to form a nanocellulose dispersion composition (NDC). The deflocculating agent is stable in the NDC and can space nanocellulose particles apart to reduce or prevent aggregation of the nanocellulose particles in the NDC. The deflocculating agent can include carbon black filler, elastomer latex, wax, or any combination thereof.

[0010] Nanocellulose dispersion compositions are also provided, as may be produced by any of the methods disclosed herein. The nanocellulose dispersion compositions (NDCs) may comprise (i) a deflocculating agent, including carbon black filler, elastomer latex, wax, or any combination thereof; and (ii) nanocellulose. Aspects of the invention also relate to polymer compositions, such as those comprising (I) a polymer; and (II) any of the nanocellulose dispersion compositions disclosed herein.

[0011] The foregoing summary and the following detailed description are exemplary and explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered limiting. Furthermore, features or variations in addition to those described herein may be provided. For example, particular aspects and embodiments may be directed to combinations and subcombinations of various features described in the detailed description. [Brief explanation of the drawings]

[0012] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects and, together with the description, serve to explain certain principles of the invention. [Figure 1A] Figure 1A is a backscattered scanning electron microscope (SEM) image of a model passenger tire tread compound mixed using a reference carbon black grade, N234. The scales in Figure 1A and Figure 1B are the same (scale bar = 300 μm). [Figure 1B] Figure 1B is a secondary scanning electron microscope (SEM) image of a model passenger tire tread compound mixed using the reference carbon black grade, N234. The scales in Figure 1A and Figure 1B are the same (scale bar = 300 μm). [Figure 2A] 2A and 2B are backscattered SEM images of the compound dispersion of Example 2 in which a portion of the carbon black has been replaced with dried lignin-coated nanocellulose fibrils (LCNF) according to various embodiments of the present disclosure. The scales in Figures 2A and 2B are the same (scale bar = 300 μm). [Figure 2B] 2B is a secondary SEM image of the compound dispersion of Example 2 in which a portion of the carbon black has been replaced with dried lignin-coated nanocellulose fibrils (LCNF) in accordance with various embodiments of the present disclosure. The scales in Figures 2A and 2B are the same (scale bar = 300 μm). [Figure 3A]3A and 3B are backscattered SEM images of the compound dispersion of Example 3, in which a portion of the carbon black has been replaced with LCNF as part of a nanocellulose dispersion composition (NDC) comprising LCNF, surface-modified carbon black (SMCB), and TDAE oil, according to various embodiments of the present disclosure. The scales in Figures 3A and 3B are the same (scale bar = 300 μm). [Figure 3B] 3B is a secondary SEM image of the compound dispersion of Example 3 in which a portion of the carbon black has been replaced with LCNF as part of a nanocellulose dispersion composition (NDC) comprising LCNF, surface-modified carbon black (SMCB), and TDAE oil, according to various embodiments of the present disclosure. The scales in Figures 3A and 3B are the same (scale bar = 300 μm). [Figure 4A] 4A is a backscattered SEM image of a model truck tire tread compound dispersion of Example 4 according to various embodiments of the present disclosure. The scales in Figures 4A and 4B are the same (scale bar = 300 μm). [Figure 4B] 4B is a secondary SEM image of a model truck tire tread compound dispersion of Example 4 according to various embodiments of the present disclosure. The scales in FIGS. 4A and 4B are the same (scale bar=300 μm). [Figure 5A] 5A and 5B are backscattered SEM images of the compound dispersion of Example 5, in which a portion of the carbon black has been replaced with dry LCNF, according to various embodiments of the present disclosure. The scales in Figures 5A and 5B are the same (scale bar = 300 μm). [Figure 5B] 5B is a secondary SEM image of the compound dispersion of Example 5 in which a portion of the carbon black has been replaced with dry LCNF, according to various embodiments of the present disclosure. The scales in Figures 5A and 5B are the same (scale bar = 300 μm). [Figure 6A] 6A and 6B are backscattered SEM images of the compound dispersion of Example 6, in which a portion of the carbon black has been replaced with LCNF as part of the NDC comprising LCNF and natural rubber latex, in accordance with various embodiments of the present disclosure. The scales in Figures 6A and 6B are the same (scale bar = 300 μm). [Figure 6B] 6A and 6B are secondary SEM images of the compound dispersion of Example 6, in which a portion of the carbon black has been replaced with LCNF as part of the NDC comprising LCNF and natural rubber latex, in accordance with various embodiments of the present disclosure. The scales in FIGS. 6A and 6B are the same (scale bar = 300 μm). DETAILED DESCRIPTION OF THE INVENTION

[0013] Additional aspects of the invention will be set forth in part in the specification that follows, and in part will be obvious from the specification or may be learned by the practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as set forth in the claims.

[0014] The present invention may be understood more readily by reference to the following detailed description of the invention and the examples included therein.

[0015] It is to be understood that before the present compounds, compositions, articles, systems, devices, and / or methods are disclosed and described, they are not limited to particular synthetic methods, unless otherwise specified, or to particular reagents, unless otherwise specified, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, exemplary and representative methods and materials are described herein.

[0016] All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in which the publications are cited.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0018] The test methods utilized herein are known and understood by those skilled in the art. Where necessary, reference to a specific test method is provided. For example, interference microscopy (IFM) was performed using ASTM D2663, Standard Test Method for Carbon Black-Dispersion in Rubber, Method D.

[0019] As used herein, unless specifically stated to the contrary, the singular forms "a," "an," and "the" include plural alternatives. Thus, for example, reference to a "polymer" or a "deflocculating agent" includes mixtures or combinations of two or more polymers or deflocculating agents, respectively, unless specifically stated otherwise.

[0020] Although compositions and methods are described herein in terms of "comprising" various components or steps, unless otherwise specified, these compositions and methods may also "consist essentially of" or "consist of" various components or steps. For example, a nanocellulose dispersion composition (NDC) consistent with embodiments of the present invention may comprise (i) a deflocculating agent and (ii) nanocellulose; alternatively, it may consist essentially of (i) a deflocculating agent and (ii) nanocellulose; or alternatively, it may consist of (i) a deflocculating agent and (ii) nanocellulose.

[0021] Ranges can be expressed herein as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, it will be understood that the use of "about" the antecedent indicates that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant, both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values ​​disclosed herein, and that each value is also herein disclosed as "about" that particular value, in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each component between two specified components is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0022] As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which the event or circumstance occurs as well as instances in which it does not occur.

[0023] Disclosed are components used in methods for preparing the compositions of the invention, as well as the compositions themselves. These and other materials are disclosed herein, and when combinations, subsets, interactions, groups, etc. of these materials are disclosed, specific reference to the various individual and collective combinations and permutations of each of these compounds cannot be made expressly disclosed, but each is understood to be specifically contemplated and described herein. For example, when a particular compound is disclosed and contemplated, and numerous modifications that can be made to numerous molecules comprising the compound are contemplated, each and every combination and permutation of possible compounds and modifications is specifically contemplated unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C is disclosed in addition to a class of molecules D, E, and F, then one example of a combined molecule, AD, is disclosed, and then AE, AF, BD, BE, BF, CD, CE, and CF, are considered disclosed, even if each is not individually listed but each is considered individually and collectively to mean the combination. Similarly, any subset or combination of these is also disclosed. Thus, for example, the subgroups AE, BF, and CE would be considered disclosed. This concept applies to all aspects of this application, including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, where there are various additional steps that may be performed, it is understood that each of these additional steps may be performed in any specific aspect or combination of aspects of the methods of the invention.

[0024] As briefly described above, the present disclosure provides a method for deflocculating nanocellulose, which exists in an individual fibril or crystalline state in an aqueous system, wherein a deflocculating agent remains stable and spaced between the nanocellulose particles upon drying, preventing the individual nanocellulose fibrils or crystals from bonding together and agglomerating. In one aspect, the present disclosure provides a method for deflocculating nanocellulose, and in another aspect, the present disclosure provides nanocellulose compositions suitable for various polymeric and elastomeric compounds, improving nanocellulose dispersion in these polymeric and elastomeric compounds so that the full benefits of nanocellulose addition can be realized. For example, the benefits of improved nanocellulose dispersion in elastomeric materials may include, but are not limited to, lower hysteresis or heat buildup, lower compound weight, and other performance characteristics of tire compounds, both for tread and non-tread compounds, that may be important in the overall performance of the tire.

[0025] It should be noted that nanocellulose in the present disclosure can include any nanocellulose, whether in crystalline or fibril form, and whether it has already been processed or modified in some other way. The source of nanocellulose can be any suitable source, whether made from wood pulp or other biomass materials and by any industrial process. Biomass fibers are composed of cellulose structural building blocks that can be industrially extracted in various shapes and sizes, including cellulose nanocrystals (NCs) and cellulose nanofibrils (NFs). The specific size and shape of nanocellulose, whether in width or / or length, can range from the nanoscale to the micron scale. NFs typically have dimensions of 5-20 nm in width and 500-2000 nm in length, and contain both amorphous and crystalline domains of cellulose. NCs typically have widths of 5-8 nm and lengths of 100-300 nm, and are primarily crystalline. While these ranges and dimensions are typical, the present invention encompasses all NC and NF materials, regardless of particle shape or particle size / dimensions.

[0026] For virtually all non-aqueous applications in which nanocellulose is used, improving its dispersibility and the resulting utility and benefits for these applications has been a major obstacle to the implementation of this technology. Therefore, it has become important to find economical and practical methods and processes to improve dispersion and highly disperse nanocellulose in polymers such as elastomeric compounds. The use of deflocculating agents during or before the nanocellulose drying process itself, instead of post-treatment techniques, can help achieve this goal.

[0027] Regarding the improvement of nanocellulose dispersion, various chemical surface modification approaches have been attempted after drying, and while some have been ultimately successful, these typically require extreme measures that are difficult to scale up to commercial quantities and have proven uneconomical. Generally, these methods are based on lyophilization (freeze-drying) of nanocellulose, an established experimental method to prevent irreversible interparticle bonding in nanocellulose. Lyophilization is neither economical nor scalable for commercial production of nanocellulose.

[0028] Therefore, a simpler and more economical method is desired to provide a method for deflocculating nanocellulose to prevent bonding between nanocellulose particles before or during drying, resulting in improved dispersion of nanocellulose in polymers such as plastics and elastomers.

[0029] <Nanocellulose dispersion composition> Nanocellulose can be produced by breaking down biomass into submicron cellulose nanofibrils or nanocrystals using, for example, chemical, mechanical, or a combination of chemical and mechanical means. Other methods for producing nanocellulose, such as bacterial nanocellulose and tunicate nanocellulose, are also available. Nanocellulose production typically involves two major steps. The first step is the purification of biomass to remove most non-cellulosic components, such as lignin, hemicellulose, extractives, and inorganic contaminants. This is typically accomplished by conventional pulping and bleaching. For the production of cellulose nanofibrils, the second step typically requires mechanical refining of the purified biomass fibers. For cellulose nanocrystals, the second step typically requires acid hydrolysis of the purified fibers followed by high-shear mechanical treatment. Newer manufacturing processes, such as the versatile AVAP® process, can produce either cellulose nanocrystals or cellulose nanofibrils by chemical fractionation of biomass using SO2 and ethanol (to varying degrees), followed by mechanical treatment. Regardless of the type of nanocellulose, after the final mechanical treatment step, nanocellulose is usually suspended in aqueous solution as a stable gel at concentrations above a threshold (usually above 2 wt% solids). Upon drying and water removal, the nanocellulose particles usually irreversibly bond and aggregate, thus resulting in poor dispersion in polymer systems.

[0030] As described herein, to reduce or prevent the nanocellulose from binding to itself during drying, an anti-agglomerating agent can be added to the aqueous nanocellulose dispersion, which interacts sufficiently with the surface of the nanocellulose and / or distributes evenly among the nanocellulose particles to reduce or prevent nanocellulose aggregation.

[0031] A first method for deflocculating nanocellulose in an aqueous system to improve its dispersibility in a polymer can include (a) combining an aqueous dispersion of nanocellulose with a deflocculating agent to form a mixture, and (b) drying the mixture to form a nanocellulose dispersion composition (NDC). A second method for deflocculating nanocellulose in an aqueous system using a deflocculating agent can include (A) combining an aqueous dispersion of nanocellulose with a deflocculating agent to form a mixture, and (B) drying the mixture to form a nanocellulose dispersion composition (NDC). The deflocculating agent can be stable in the NDC and can space the nanocellulose particles apart, reducing or preventing aggregation of the nanocellulose particles in the NDC. Cellulose dispersion compositions produced by any of the methods disclosed herein are also encompassed by the present invention. The nanocellulose dispersion composition (NDC) can include at least a deflocculating agent and nanocellulose, and the deflocculating agent can include a carbon black filler, an elastomer latex, or a wax, or any combination of these materials.

[0032] In steps (a) and (A) of the first and second methods, the aqueous dispersion of nanocellulose can be combined with a deflocculating agent to form a mixture. The aqueous dispersion of nanocellulose can contain any suitable amount of nanocellulose, but generally has at least about 2% solids by weight and up to 10% solids by weight (e.g., about 2% to about 5% solids by weight).

[0033] Any suitable vessel and conditions can be used to combine the aqueous nanocellulose dispersion with the deflocculating agent, and can be done batchwise or continuously. By way of example, the nanocellulose dispersion and deflocculating agent can be combined in a suitable vessel (e.g., tank) at atmospheric pressure, optionally with stirring or mixing, and at any suitable temperature, typically in the range of about 15°C to about 60°C.

[0034] The amount of anti-agglomerating agent used relative to nanocellulose is not particularly limited, but the weight ratio of anti-agglomerating agent to nanocellulose in the nanocellulose dispersion composition is typically in the range of about 0.25:1 to about 25:1. In some embodiments, the weight ratio of anti-agglomerating agent to nanocellulose is in the range of about 0.25:1 to about 25:1, about 0.25:1 to about 15:1, about 0.3:1 to about 10:1, about 0.5:1 to about 25:1, about 0.7:1 to about 15:1, about 0.75:1 to about 15:1, about 1:1 to about 10:1, about 1.2:1 to about 12:1, about 1.8:1 to about 8:1, about 1.5:1 to about 10:1, about 4:1 to about 15:1, or about 0.25:1. The weight ratio can be 0.4:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, or 25:1. When multiple deflocculating agents are used, the total amount of deflocculating agents is used to determine the weight ratio.

[0035] The type of nanocellulose in the aqueous nanocellulose dispersion or nanocellulose dispersion composition (NDC) is not particularly limited. In one embodiment, for example, the nanocellulose can include nanocellulose crystals (NC), nanocellulose fibrils (NF), or a combination thereof. The nanocellulose can further include lignin as surface lignin and / or as lignin contained in the bulk particles. In another embodiment, the nanocellulose can include lignin-coated nanocellulose crystals (LCNC), lignin-coated nanocellulose fibrils (LCNF), or a combination thereof. Generally, these lignin-coated materials are more hydrophobic. In yet another embodiment, the nanocellulose can include hydrophilic cellulose nanocellulose crystals (CNC), hydrophilic cellulose nanocellulose fibrils (CNF), or a combination thereof.

[0036] Typically, suitable deflocculating agents are compatible with polymers (e.g., elastomers, tire compounds) and reduce nanocellulose clumping in NDC and polymer compounds. Typically, the deflocculating agent in or used to form the nanocellulose dispersion composition can include carbon black filler, elastomer latex, wax, or any combination thereof. Any suitable rubber latex can be used, illustrative examples of which include, but are not limited to, natural rubber (NR), isoprene rubber (IR), emulsion styrene butadiene rubber (ESBR), and the like. Mixtures or combinations of two or more rubber latex materials can be used.

[0037] The wax component may include, but is not limited to, microcrystalline waxes including unbranched alkane paraffin waxes, branched paraffin waxes and ceresin waxes (either natural mineral, petroleum refined or lignin refined), polyethylene waxes, functionalized polyethylene waxes, and the like, or any combination thereof.

[0038] The carbon black of the present invention can comprise any carbon black suitable for use with the NDC and / or elastomeric material, if present. In one embodiment, the carbon black can comprise (or consist essentially of, or consist of) furnace carbon black. Additionally or alternatively, the carbon black filler can comprise (or consist essentially of, or consist of) a surface-modified furnace carbon black, such as oxidized furnace carbon black. In another embodiment, the carbon black can comprise a carbon black suitable for use in rubber, e.g., in tires. In another embodiment, the carbon black can comprise a carbon black suitable for use in tire treads or tire carcasses. In various embodiments, the carbon black can comprise N900 series carbon black, N800 series carbon black, N700 series carbon black, N600 series carbon black, N500 series carbon black, N400 series carbon black, N300 series carbon black, N200 series carbon black, N100 series carbon black, or mixtures thereof. Various physical properties of exemplary carbon blacks that may be useful in the present invention are listed below. It should be understood that these values ​​and ranges are intended to be exemplary in nature, and the present invention is not limited to any particular ranges, values, or combinations.

[0039] Carbon black may have a viscosity of about 8 mPa s, as determined by, for example, ASTM method D6556-14. 2 / g ~ approx. 140m 2 / g; approx. 20m 2 / g ~ approx. 140m 2 / g; approx. 45m 2 / g ~ approx. 140m 2 / g; approx. 60m 2 / g ~ approx. 140m 2 / g; approx. 90m 2 / g ~ approx. 140m 2 / g; approx. 95m 2 / g ~ approx. 135m 2 / g;About 100m 2 / g ~ approx. 130m2 / g; approx. 105m 2 / g ~ approx. 125m 2 / g; approx. 110m 2 / g ~ approx. 125m 2 / g; approx. 115m 2 / g ~ approx. 125m 2 / g; approx. 110m 2 / g ~ approx. 120m 2 / g; approx. 115m 2 / g ~ approx. 120m 2 / g; approx. 115m 2 / g ~ approx. 121m 2 / g; or approximately 116m 2 / g ~ approx. 120m 2 In another embodiment, the carbon black can have a nitrogen surface area of ​​about 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130, 132, 134, 136, 138, or 140 m 2 In other embodiments, the carbon black can have a nitrogen surface area of ​​about 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, or 140 m 2 In yet another embodiment, the carbon black can have a nitrogen surface area of ​​about 118 m / g. 2 / g In other aspects, the carbon blacks of the present invention may have nitrogen surface areas greater than or less than any of the values ​​specifically recited herein, and the present invention is not limited to any particular nitrogen surface area value.

[0040] Carbon black has a thickness of approximately 8 m based on the statistical thickness-to-surface area method (STSA, ASTM D6556-14). 2 / g ~ approx. 125m 2 / g; approx. 20m 2 / g ~ approx. 125m 2 / g; approx. 45m 2 / g ~ approx. 125m 2 / g; approx. 60m 2 / g ~ approx. 125m 2 / g; approx. 80m 2 / g ~ approx. 125m 2 / g; approx. 85m 2 / g ~ approx. 120m 2 / g; approx. 90m 2 / g ~ approx. 115m 2 / g; approx. 95m 2 / g ~ approx. 110m 2 / g; approx. 95m 2 / g ~ approx. 105m 2 / g; approx. 98m 2 / g ~ approx. 104m 2 / g; or approximately 99m 2 / g ~ approx. 103m 2 In another embodiment, the carbon black can have an external surface area of ​​about 101 m / g. 2 In another embodiment, the carbon black can have an external surface area of ​​about 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125 m 2 / g. In various embodiments, the external surface area of ​​the carbon black is the specific surface area available to the rubber compound. In other embodiments, the carbon black of the present invention can have an external surface area greater than or less than any of the values ​​specifically recited herein, and the present invention is not limited to any particular external surface area value.

[0041] The carbon blacks of the present invention can have a pH of about 2.5 to about 4, about 2.8 to about 3.6, or about 3 to about 3.4, as measured, for example, by ASTM Method D1512-15 using either Test Method A or Test Method B. In another aspect, the carbon blacks of the present invention can have a pH of about 3.2. In other aspects, the carbon blacks of the present invention can have a pH greater than or less than any of the values ​​specifically recited herein, and the present invention is not limited to any particular pH value.

[0042] The carbon black of the present invention has a viscosity of, for example, about 55 cm as measured by ASTM method D6086-09a. 3 / 100g~approx.67cm 3 / 100g(50GM); approx. 60cm 3 / 100g~approx. 65cm 3 / 100g(50GM);approx. 25cm 3 / 100g~approx.60cm 3 / 100g; approx. 30cm 3 / 100g~60cm 3 / 100g; approx. 35cm 3 / 100g~60cm 3 / 100g; approx. 40cm 3 / 100g~60cm 3 / 100g; approx. 45cm 3 / 100g~60cm 3 / 100g; approx. 50cm 3 / 100g~approx.60cm 3 / 100g(75GM); approx. 53cm 3 / 100g~approx.58cm 3 / 100g(75GM); approx. 45cm 3 / 100g~approx. 55cm 3 / 100g (100GM); or approx. 47cm 3 / 100g~approx.53cm 3 In another embodiment, the carbon black may have a void volume of about 62.2 cm / 100 g (100 GM). 3 Void volume of 50GM / 100g: approx. 55.3cm 3 / 100g void volume of 75GM; and / or approximately 50.4 cm 3 In other embodiments, the void volume of the carbon black may be greater or less than any value specifically recited herein, and the invention is not limited to any particular void volume.

[0043] The carbon black of the present invention can have a moisture content of about 2.5% to about 4.5% by weight; about 3% to about 4% by weight; or about 3.2% to about 3.8% by weight, as measured, for example, by ASTM Method D1509-15. In another embodiment, the carbon black of the present invention can have a moisture content of about 3.5% by weight. It should be understood that the moisture content of carbon black materials can and does vary, depending, for example, on environmental and / or storage conditions, and therefore the specific moisture content of a given sample of carbon black can vary. In other embodiments, the carbon black of the present invention can have a moisture content greater or less than any value specifically recited herein, and the present invention is not limited to any particular moisture content value.

[0044] In one embodiment, the carbon black of the present invention is an oxidized carbon black, such as an oxidized furnace carbon black. Various methods exist for oxidizing carbon black, such as ozone treatment, and the specific method for oxidizing carbon black can vary, provided that multiple oxygen-containing functional groups are present on the surface of the carbon black as desired. Typical oxygen-containing functional groups that may be present on the surface of oxidized carbon black include, for example, carboxyl, hydroxyl, phenol, lactone, aldehyde, ketone, quinone, and hydroquinone groups. In various embodiments, the amount and type of functional groups present on the surface of the oxidized carbon black can vary depending on the intensity and type of oxidation treatment. In one embodiment, the carbon black is oxidized by ozone treatment.

[0045] The carbon black of the present invention can have a volatile matter content of about 0.5% to about 6.5% by weight, about 1% to about 6.5% by weight, about 1.5% to about 6.5% by weight, about 2% to about 6.5% by weight, about 2.5% to about 6.5% by weight, about 3% to about 6.5% by weight, about 3.5% to about 6.5% by weight, about 4% to about 6.5% by weight, about 4.5% to about 6.5% by weight, about 5% to about 6% by weight, or about 5.2% to about 5.8% by weight. In another embodiment, the carbon black of the present invention can have a volatile matter content of at least about 4.5% by weight, at least about 5% by weight, at least about 5.5% by weight, or even more. In another embodiment, the carbon black of the present invention can have a volatile matter content of about 5.5% by weight. In still other aspects, the volatile matter content of the carbon black may be greater or less than any value specifically recited herein, and the present invention is not limited to any particular volatile matter content value.

[0046] The carbon black of the present invention can have an oxygen content of about 0.25% by weight to about 5.5% by weight; about 0.5% by weight to about 5.5% by weight; about 1% by weight to about 5.5% by weight; about 1.5% by weight to about 5.5% by weight; about 2% by weight to about 5.5% by weight; about 2.5% by weight to about 5.5% by weight; about 3% by weight to about 5% by weight; about 3.5% by weight to about 4.5% by weight; or about 3.7% by weight to about 4.3% by weight. In another embodiment, the carbon black of the present invention can have an oxygen content of at least about 3.5% by weight, at least about 4% by weight, or even more. In another embodiment, the carbon black of the present invention can have an oxygen content of about 4% by weight. In still other embodiments, the oxygen content of the carbon black can be greater or less than any of the values ​​specifically recited herein, and the present invention is not limited to any particular oxygen content value.

[0047] Optionally, a hydrocarbon oil can be used together with a deflocculating agent. For example, in step (a) or step (A), the aqueous dispersion of nanocellulose can be combined with a deflocculating agent and a hydrocarbon oil to form a mixture. In one embodiment, the hydrocarbon oil can include an aliphatic hydrocarbon, while in another embodiment, the hydrocarbon oil can include an aromatic hydrocarbon. However, in another embodiment, the hydrocarbon oil can include a mixture or combination of aliphatic and aromatic hydrocarbons. Any suitable aliphatic and / or aromatic hydrocarbon can be used, although it is beneficial for the hydrocarbon to be in a liquid phase at the conditions when the aqueous nanocellulose dispersion and the deflocculating agent are combined. An illustrative, non-limiting example of a suitable hydrocarbon oil that can be used as a deflocculating agent is treated distillate aromatic extract (TDAE) oil.

[0048] Optionally, the aqueous cellulose dispersion, the deflocculating agent, and the optional hydrocarbon oil can be mixed under high shear to ensure uniform distribution of the individual components. High shear mixing techniques include, but are not limited to, homogenization, sigma blade mixing, rotor-stator mixing, and static in-line mixing.

[0049] In steps (b) and (B) of the first and second methods, the mixture can be dried to form a nanocellulose dispersion composition (NDC). Any suitable equipment and drying technique can be used. In one embodiment, the aqueous mixture can be subjected to a suitable drying process to remove water. Drying techniques can include, but are not limited to, evaporation, spray drying, freeze drying, spin-flash drying, high-shear mixing, drying, and drum drying. The resulting nanocellulose dispersion composition contains the deflocculating agent and nanocellulose and generally contains less than 1.5 wt.% water / moisture. During the drying process and in the dry state, one or more coupling chemicals can optionally be introduced into the NDC composition, for example, to modify the surface of the nanocellulose and enable subsequent coupling of the cellulose surface with the rubber matrix during vulcanization of a rubber compound prepared using the NDC.

[0050] Coupling agents are well known to those skilled in the art and can, in various embodiments, include mono- and / or di-functional silanes based on mercapto, alkoxy, vinyl, amino, and methacryloxy chemistries, including common di-functional sulfur-containing coupling silanes such as 3,3'-bis-(triethoxysilylpropyl)-tetrasulfide.

[0051] Advantageously, a nanocellulose dispersion composition (NDC) that can include (i) a deflocculating agent and (ii) nanocellulose has superior nanocellulose dispersion in a polymer composition relative to nanocellulose without the deflocculating agent, typically 25% or more, or 50% or more, as determined by interference microscopy (IFM). For example, if the amount of undispersed material (based on area) via IFM was 12% for nanocellulose without the deflocculating agent, a 25% improvement would result in an area fraction of undispersed material of 9%, and a 50% improvement would result in an area fraction of undispersed material of 6%.

[0052] <Polymer Composition> The present invention, in some variations, also relates to and encompasses any compositions, formulations, and products comprising any of the nanocellulose dispersion compositions disclosed herein (and their respective properties or characteristics, such as, inter alia, the relative amounts of deflocculating agent and nanocellulose, the type of deflocculating agent, and the type of nanocellulose). In certain aspects of the present invention, polymer compositions are disclosed, which in this aspect can comprise any suitable polymer(s) and any of the nanocellulose dispersion compositions disclosed herein.

[0053] The amount of nanocellulose dispersion composition used in the polymer composition is not particularly limited, but the weight ratio of polymer to nanocellulose composition (polymer:NDC) is usually about 100:1 to about 1:1, about 80:1 to about 10:1, about 75:1 to about 2:1, about 60:1 to about 5:1, about 50:1 to about 1:1, about 40:1 to about 4:1, about 75:1 to about 25:1, The polymer:NDC weight ratio can range from about 90:1 to about 15:1, or about 100:1, 98:1, 96:1, 94:1, 92:1, 90:1, 85:1, 80:1, 75:1, 70:1, 65:1, 60:1, 55:1, 50:1, 45:1, 40:1, 35:1, 30:1, 25:1, 20:1, 15:1, 10:1, 8:1, 6:1, 4:1, 2:1, or 1:1. In some embodiments, the polymer:NDC weight ratio can fall within the range of about 75:1 to about 1.5:1, or about 50:1 to about 2:1.

[0054] In one embodiment, the polymer in the polymer composition can include a thermoplastic polymer, while in another embodiment, the polymer can include a thermoset polymer. In another embodiment, the polymer can include, alone or in any combination, an epoxy, an acrylic, an ester, a urethane, a silicone, and / or a phenolic. In yet another embodiment, the polymer can include, alone or in any combination, polyethylene (e.g., an ethylene homopolymer or an ethylene-based copolymer), polypropylene, polybutylene terephthalate, acrylonitrile butadiene styrene (ABS), polyamide, polyimide, polystyrene, polycarbonate, ethylene vinyl acetate (EVA) copolymer, and / or polyolefin-styrene (e.g., ethylene-styrene).

[0055] In another aspect, the polymer used in the formulation / composition can include any suitable rubber or elastomer, alone or in any combination, non-limiting examples of which include natural rubber (NR), epoxidized natural rubber (ENR), synthetic cis-polyisoprene (IR), emulsion styrene butadiene rubber (eSBR), solution styrene butadiene rubber (sSBR), polybutadiene rubber (BR), butyl rubber (IIR / CIIR / BIIR), chloroprene rubber (CR), nitrile elastomer (NBR), hydrogenated nitrile elastomer (HNBR), carboxylated nitrile elastomer (XNBR), ethylene propylene rubber (EPM / EPDM), fluoroelastomer (FPM / FKM), polyurethane rubber (AU / EU / PU), and the like, and any combination thereof. [Example]

[0056] The present invention is further illustrated by the following examples, which should not be construed as imposing limitations on the scope of the present invention in any way. After reading the description herein, it should be clearly understood that various aspects, embodiments, modifications, and equivalents thereof, which may spontaneously suggest themselves to those skilled in the art, may be employed without departing from the spirit of the present invention or the scope of the appended claims.

[0057] Furthermore, these examples are in no way intended to limit the scope or range of available deflocculating agents or available nanocellulose materials that can be used to prepare nanocellulose dispersion compositions for use in polymer blends, but are provided as examples only to demonstrate the concept of combining deflocculating agents with nanocellulose to form highly dispersible NDC.

[0058] The nanocellulose crystals or nanocellulose fibrils in these examples were produced using the AVAP® process described above and a proprietary method that deposits lignin on the surface of the fibrils or crystals, making them more hydrophobic and more compatible with polymers and elastomers.

[0059] In Example 1, a model passenger tire tread compound was mixed using a reference carbon black grade, N234. This compound was included as a reference to demonstrate typical carbon black dispersion levels. N234 comprised 100% of the filler in this compound, corresponding to 75 phr in the compound formulation. A detailed description of a representative compound formulation (phr values) and standard mixing procedures are summarized in Tables 1-2. As shown in the SEM images in Figures 1A and 1B, N234 carbon black exhibited excellent dispersion. Figure 1A is a backscattered electron image of a razor-cut compound surface, and Figure 1B is a secondary electron image of the same area. Dispersion, as quantified by interference microscopy (IFM), generally ranged from 98 to 100% dispersion, with an area fraction of undispersed carbon black of 0.8%.

[0060] Example 2 was prepared using the same mixing procedure as Example 1; however, a small portion (6.7 wt%) of the N234 was replaced with dried lignin-coated nanocellulose fibrils (LCNF). LCNF accounted for 6.7 wt% of the total filler loading, representing 5 phr of the compound formulation. The remaining filler loading consisted of N234 (93.3 wt%), representing 70 phr of the compound formulation. Figures 2A and 2B show that nanocellulose dispersion was very poor, as evidenced by large aggregates of nanocellulose fibrils visible throughout the compound cross-section in backscattered (Figure 2A) and secondary (Figure 2B) SEM images. The area fraction of undispersed material, as quantified by interference microscopy (IFM), was 9.11%.

[0061] Example 3 was manufactured using the same procedure as Example 2. Instead of adding dried, stand-alone LCNFs as in Example 2, Example 3 used NDC, which contained LCNFs treated with surface-modified carbon black (SMCB, N234) as a deflocculating agent, TDAE oil, and natural rubber latex. The weight ratio of LCNFs:SMCB:TDAE oil:NR latex was 1:1:1:1. The NDC was prepared by mixing an aqueous dispersion of nanocellulose with SMCB, TDAE oil, and NR latex, followed by high-shear homogenization and drying to a water content of less than 1.5 wt%. The total NDC content was 20 phr, and the LCNFs added to the final compound were 6.7 wt% of the total filler loading, corresponding to 5 phr in the compound formulation.

[0062] Figures 3A and 3B show the nanocellulose dispersion obtained when LCNF / SMCB / TDAE / NR NDC was added to a rubber compound mixer. Figure 3A is a backscattered electron image of a razor-cut compound surface, and Figure 3B is a secondary electron image of the same area. The area fraction of undispersed material is 2.78% (quantified by IFM), with smaller and fewer nanocellulose aggregates present in the cross section, a significant improvement over Example 2 (Figures 2A and 2B). The dispersion is more similar to that of N234 carbon black in Example 1 (Figures 1A and 1B), with only minor undispersed areas.

[0063] In Example 4, a model truck tire tread compound was mixed using a reference carbon black grade, N234. This compound was included as a reference to demonstrate typical carbon black dispersion levels. N234 comprised 100% of the filler in this compound, corresponding to 50 phr in the compound formulation. A detailed description of a representative compound formulation (phr values) and standard mixing procedures are summarized in Tables 1 and 3. As shown in the SEM images in Figures 4A and 4B, N234 carbon black exhibited excellent dispersion. Figure 4A is a backscattered electron image of a razor-cut compound surface, and Figure 4B is a secondary electron image of the same area. Dispersion, as quantified by interference microscopy (IFM), generally ranged from 98 to 100% dispersion, with an area fraction of undispersed carbon black of 0.15%.

[0064] Example 5 was prepared using the same mixing procedure as Example 4; however, a small portion (10 wt%) of the N234 was replaced with dried lignin-coated nanocellulose fibrils (LCNF). LCNF accounted for 10 wt% of the total filler loading, representing 5 phr of the compound formulation. The remaining filler loading consisted of N234 (90 wt%), representing 45 phr of the compound formulation. Figures 5A and 5B show that nanocellulose dispersion was very poor, as evidenced by large aggregates of nanocellulose fibrils visible throughout the compound cross-section in backscattered (Figure 5A) and secondary (Figure 5B) SEM images. The area fraction of undispersed material, as quantified by interference microscopy (IFM), was 11.52%.

[0065] Example 6 was prepared using the same mixing procedure as Example 1. Instead of adding dry, stand-alone LCNFs as in Example 5, Example 6 used the same NDC as Example 3. In this particular example, NR latex was used for the NDC because it is a common material in truck tread recipes; however, other latex elastomer materials can also be used. The weight ratio of LCNF:SMCB:TDAE oil:NR latex was 1:1:1:1. The NDC was prepared in a similar manner to Example 3. The total NDC content was 20 phr, and the LCNFs added to the final compound were 10 wt% of the total filler loading, corresponding to 5 phr in the compound formulation. Figures 6A and 6B show the nanocellulose dispersion obtained when the LCNF / SMCB / TDAE / NR NDC was added to a rubber compound. Figure 3A is a backscattered electron image of a razor-cut compound surface, and Figure 3B is a secondary electron image of the same area. The area fraction of undispersed material, as quantified by IFM, was 2.44%, a significant improvement over Example 5. Note that some of the undispersed areas in the SEM cross section are significantly smaller than those in Figures 5A / 5B. The measured dispersion level of nanocellulose in this compound is similar to that of Example 4.

[0066] [Table 1]

[0067] [Table 2]

[0068] [Table 3]

[0069] The present invention has been described above with reference to many embodiments and specific examples. Many variations will suggest themselves to those skilled in the art in light of the above detailed description. All such obvious variations are intended to fall within the scope of the appended claims. Other aspects of the present invention can include, but are not limited to (embodiments described as "comprising" can alternatively be "consisting essentially of" or "consisting of"):

[0070] Aspect 1. A polymer composition comprising: (I) polymers; (II) a nanocellulose dispersion composition (NDC) comprising: (i) a deflocculating agent comprising a carbon black filler, an elastomer latex, a wax, or any combination thereof; and (ii) nanocellulose; and (III) Carbon black additives.

[0071] Aspect 2. The polymer composition of aspect 1, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) ranges from about 100:1 to about 1:1.

[0072] Aspect 3. The polymer composition of aspect 1, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) ranges from about 50:1 to about 2:1.

[0073] Embodiment 4. The polymer composition of any one of embodiments 1-3, wherein the polymer comprises a thermoplastic resin.

[0074] Embodiment 5. The polymer composition of any one of embodiments 1-3, wherein the polymer comprises an elastomer.

[0075] Aspect 6. The polymer composition of any one of Aspects 1-3, wherein the polymer comprises natural rubber (NR), epoxidized natural rubber (ENR), synthetic cis-polyisoprene (IR), emulsion styrene butadiene rubber (eSBR), solution styrene butadiene rubber (sSBR), polybutadiene rubber (BR), butyl rubber (IIR / CIIR / BIIR), chloroprene rubber (CR), nitrile elastomer (NBR), hydrogenated nitrile elastomer (HNBR), carboxylated nitrile elastomer (XNBR), ethylene propylene rubber (EPM / EPDM), fluoroelastomer (FPM / FKM), polyurethane rubber (AU / EU / PU), or the like, or any combination thereof.

[0076] Embodiment 7. The polymer composition of any one of embodiments 1-6, wherein the anti-agglomerating agent is compatible with the polymer and reduces aggregation of the nanocellulose.

[0077] Aspect 8. The polymer composition of any one of aspects 1-7, wherein the nanocellulose dispersion composition has greater nanocellulose dispersibility in the polymer composition than the dispersibility of nanocellulose without the deflocculating agent.

[0078] Embodiment 9. The polymer composition of any one of embodiments 1-8, wherein the nanocellulose comprises nanocellulose crystals (NC), nanocellulose fibrils (NF), or a combination thereof.

[0079] Example 10. The polymer composition of any one of Examples 1-9, wherein the nanocellulose comprises lignin-coated nanocellulose crystals (LCNCs), lignin-coated nanocellulose fibrils (LCNFs), or a combination thereof.

[0080] Example 11. The polymer composition of any one of Examples 1-10, wherein the nanocellulose comprises hydrophilic cellulose nanocellulose crystals (CNCs), hydrophilic cellulose nanocellulose fibrils (CNFs), or a combination thereof.

[0081] Example 12. The polymer composition of any one of Examples 1-11, wherein the nanocellulose dispersion composition (NDC) further comprises a hydrocarbon oil.

[0082] Aspect 13. The polymer composition of aspect 12, wherein the hydrocarbon oil comprises an aliphatic hydrocarbon, an aromatic hydrocarbon, or a combination thereof.

[0083] Aspect 14. The polymer composition of aspect 12, wherein the hydrocarbon oil comprises a treated distillate aromatic extract (TDAE) oil.

[0084] Aspect 15. The polymer composition of any one of Aspects 1-14, wherein the elastomer latex comprises natural rubber (NR), isoprene rubber (IR), emulsion styrene-butadiene rubber (ESBR), or any combination thereof.

[0085] Aspect 16. The polymer composition of any one of aspects 1-15, wherein the wax comprises an unbranched alkane paraffin wax; a natural mineral, petroleum-refined, or lignin-refined branched paraffin wax or ceresin wax; a polyethylene wax; a functionalized polyethylene wax; or any combination thereof.

[0086] Aspect 17. The polymer composition of any one of Aspects 1-16, wherein the carbon black filler and the carbon black additive each independently comprise furnace carbon black and / or surface-modified furnace carbon black.

[0087] Embodiment 18. The polymer composition of any one of embodiments 1-17, wherein the carbon black filler and the carbon black additive are each independently characterized by: Approximately 90m 2 / g ~ approx. 140m 2 / g nitrogen surface area; Approximately 80m 2 / g ~ approx. 125m 2 external surface area in / g; pH of about 2.5 to about 4; Approximately 55cm 3 / 100g~approx.67cm 3 / 100g of 50GM void volume; Approximately 50cm 3 / 100g~approx.60cm 3 / 100g 75GM void volume; Approximately 45cm 3 / 100g~approx. 55cm 3 / 100g 100GM void volume; a moisture content of about 2.5% to about 4.5% by weight; a volatile matter content of about 4.5% to about 6.5% by weight; an oxygen content of about 2.5% to about 5.5% by weight; or Any combination of them.

[0088] Aspect 19. The polymer composition of any one of Aspects 1 to 18, wherein the deflocculating agent comprises the carbon black filler, the elastomer latex, or the wax.

[0089] Aspect 20. The polymer composition of any one of Aspects 1-18, wherein the deflocculating agent comprises at least two of the carbon black filler, the elastomer latex, and the wax.

[0090] Aspect 21. The polymer composition of any one of aspects 1 to 20, wherein the weight ratio of the deflocculating agent to the nanocellulose ranges from about 0.5:1 to about 25:1.

[0091] Embodiment 22. The polymer composition of any one of embodiments 1 to 21, wherein the weight ratio of the deflocculating agent to the nanocellulose ranges from about 1:1 to about 10:1.

[0092] Example 23. The polymer composition of any one of Examples 1-22, wherein the nanocellulose dispersion composition (NDC) is produced by a method comprising: (a) combining the aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture; and (b) drying the mixture to form the nanocellulose dispersion composition (NDC).

[0093] Example 24. The polymer composition of any one of Examples 1 to 22, wherein the nanocellulose dispersion composition (NDC) is produced by a method comprising: (A) combining the aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture; and (B) drying the mixture to form the nanocellulose dispersion composition (NDC); wherein the anti-agglomerating agent is stable in the NDC and spaced between nanocellulose particles to reduce or prevent agglomeration of the nanocellulose particles in the NDC.

[0094] Aspect 25. A method for deflocculating nanocellulose in an aqueous system to improve its dispersibility in a polymer, the method comprising: (a) combining the aqueous dispersion of nanocellulose with a deflocculating agent to form a mixture, wherein the deflocculating agent comprises a carbon black filler; and (b) drying the mixture to form a nanocellulose dispersion composition (NDC).

[0095] Aspect 26. A method for deflocculating nanocellulose in an aqueous system using a deflocculating agent, the method comprising: (A) combining the aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture, wherein the deflocculating agent comprises a carbon black filler; and (B) drying the mixture to form a nanocellulose dispersion composition (NDC); wherein the anti-agglomerating agent is stable in the NDC and spaced between nanocellulose particles to reduce or prevent agglomeration of the nanocellulose particles in the NDC.

[0096] Aspect 27. The method of aspect 25 or 26, wherein the weight ratio of the anti-agglomerating agent to the nanocellulose ranges from about 0.5:1 to about 25:1.

[0097] Aspect 28. The method of aspect 25 or 26, wherein the weight ratio of the anti-agglomerating agent to the nanocellulose ranges from about 1:1 to about 10:1.

[0098] Embodiment 29. The method of any one of embodiments 25 to 28, wherein the nanocellulose comprises nanocellulose crystals (NC), nanocellulose fibrils (NF), or a combination thereof.

[0099] Aspect 30. The method of any one of aspects 25 to 29, wherein the nanocellulose comprises lignin-coated nanocellulose crystals (LCNCs), lignin-coated nanocellulose fibrils (LCNFs), or a combination thereof.

[0100] Aspect 31. The method of any one of aspects 25 to 30, wherein the nanocellulose comprises hydrophilic cellulose nanocellulose crystals (CNCs), hydrophilic cellulose nanocellulose fibrils (CNFs), or a combination thereof.

[0101] Aspect 32. The method of any one of Aspects 25-31, wherein the deflocculating agent further comprises an elastomer latex, a wax, or a combination thereof.

[0102] Aspect 33. The method of any one of aspects 25 to 32, wherein the aqueous dispersion of nanocellulose is combined with the deflocculating agent and a hydrocarbon oil.

[0103] Aspect 34. The method of aspect 33, wherein the hydrocarbon oil comprises an aliphatic hydrocarbon, an aromatic hydrocarbon, or a combination thereof.

[0104] Aspect 35. The method of aspect 33, wherein the hydrocarbon oil comprises a treated distillate aromatic extract (TDAE) oil.

[0105] Aspect 36. The method of any one of Aspects 32 to 35, wherein the elastomer latex comprises natural rubber (NR), isoprene rubber (IR), emulsion styrene-butadiene rubber (ESBR), or any combination thereof.

[0106] Aspect 37. The method of any one of aspects 32 to 36, wherein the wax comprises an unbranched alkane paraffin wax; a natural mineral, petroleum-refined, or lignin-refined branched paraffin wax or ceresin wax; a polyethylene wax; a functionalized polyethylene wax; or any combination thereof.

[0107] Embodiment 38 The method of any one of embodiments 25 to 37, wherein the carbon black filler comprises furnace carbon black and / or surface-modified furnace carbon black.

[0108] Embodiment 39. The method of any one of embodiments 25-38, wherein the carbon black filler is characterized by: Approximately 90m 2 / g ~ approx. 140m 2 / g nitrogen surface area; Approximately 80m 2 / g ~ approx. 125m 2 external surface area in / g; pH of about 2.5 to about 4; Approximately 55cm 3 / 100g~approx.67cm 3 / 100g of 50GM void volume; Approximately 50cm 3 / 100g~approx.60cm 3 / 100g 75GM void volume; Approximately 45cm 3 / 100g~approx. 55cm 3 / 100g 100GM void volume; a moisture content of about 2.5% to about 4.5% by weight; a volatile matter content of about 4.5% to about 6.5% by weight; an oxygen content of about 2.5% to about 5.5% by weight; or Any combination of them.

[0109] Embodiment 40. A nanocellulose dispersion composition (NDC) produced by the method of any one of embodiments 25 to 38.

[0110] Embodiment 41. A nanocellulose dispersion composition (NDC) comprising: (i) a deflocculating agent comprising a carbon black filler; and (ii) Nanocellulose.

[0111] Aspect 42. The composition of aspect 40 or 41, wherein the anti-agglomerating agent is compatible with the polymer and reduces aggregation of the nanocellulose.

[0112] Aspect 43. The composition of any one of aspects 40-42, wherein the nanocellulose dispersion composition has greater nanocellulose dispersibility in the polymer blend than the dispersibility of nanocellulose without the deflocculating agent.

[0113] Aspect 44. The composition of any one of aspects 40 to 43, wherein the nanocellulose comprises nanocellulose crystals (NC), nanocellulose fibrils (NF), or a combination thereof.

[0114] Aspect 45. The composition of any one of aspects 40 to 44, wherein the nanocellulose comprises lignin-coated nanocellulose crystals (LCNCs), lignin-coated nanocellulose fibrils (LCNFs), or a combination thereof.

[0115] Aspect 46. The composition of any one of aspects 40 to 45, wherein the nanocellulose comprises hydrophilic cellulose nanocellulose crystals (CNCs), hydrophilic cellulose nanocellulose fibrils (CNFs), or a combination thereof.

[0116] Aspect 47. The composition of any one of Aspects 40-46, wherein the anti-agglomerating agent further comprises an elastomer latex, a wax, or a combination thereof.

[0117] Aspect 48. The composition of any one of aspects 40 to 47, wherein the nanocellulose dispersion composition (NDC) further comprises a hydrocarbon oil.

[0118] Aspect 49. The composition of Aspect 48, wherein the hydrocarbon oil comprises an aliphatic hydrocarbon, an aromatic hydrocarbon, or a combination thereof.

[0119] Aspect 50. The composition of aspect 48, wherein the hydrocarbon oil comprises a treated distillate aromatic extract (TDAE) oil.

[0120] Aspect 51. The composition of any one of aspects 47 to 50, wherein the elastomer latex comprises natural rubber (NR), isoprene rubber (IR), emulsion styrene-butadiene rubber (ESBR), or any combination thereof.

[0121] Aspect 52. The composition of any one of aspects 47 to 51, wherein the wax comprises an unbranched alkane paraffin wax; a natural mineral, petroleum-refined, or lignin-refined branched paraffin wax or ceresin wax; a polyethylene wax; a functionalized polyethylene wax; or any combination thereof.

[0122] Aspect 53. The composition of any one of Aspects 40-52, wherein the carbon black filler comprises furnace carbon black and / or surface-modified furnace carbon black.

[0123] Embodiment 54. The composition of any one of embodiments 40-53, wherein the carbon black filler is characterized by: Approximately 90m 2 / g ~ approx. 140m 2 / g nitrogen surface area; Approximately 80m2 / g ~ approx. 125m 2 external surface area in / g; pH of about 2.5 to about 4; Approximately 55cm 3 / 100g~approx.67cm 3 / 100g of 50GM void volume; Approximately 50cm 3 / 100g~approx.60cm 3 / 100g 75GM void volume; Approximately 45cm 3 / 100g~approx. 55cm 3 / 100g 100GM void volume; a moisture content of about 2.5% to about 4.5% by weight; a volatile matter content of about 4.5% to about 6.5% by weight; an oxygen content of about 2.5% to about 5.5% by weight; or Any combination of them.

[0124] Aspect 55. The composition of any one of aspects 40 to 54, wherein the weight ratio of the anti-agglomerating agent to the nanocellulose ranges from about 0.5:1 to about 25:1.

[0125] Aspect 56. The composition of any one of aspects 40 to 55, wherein the weight ratio of the anti-agglomerating agent to the nanocellulose ranges from about 1:1 to about 10:1.

[0126] Embodiment 57. A polymer composition comprising: (I) a polymer; and (II) A nanocellulose dispersion composition (NDC) according to any one of aspects 40 to 56.

[0127] Aspect 58. The polymer composition of aspect 57, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) ranges from about 100:1 to about 1:1.

[0128] Aspect 59. The polymer composition of aspect 57, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) ranges from about 50:1 to about 2:1.

[0129] Embodiment 60. The polymer composition of any one of embodiments 57-59, wherein the polymer comprises a thermoplastic resin.

[0130] Embodiment 61. The polymer composition of any one of embodiments 57-59, wherein the polymer comprises an elastomer.

[0131] Aspect 62. The polymer composition of any one of aspects 57 to 59, wherein the polymer comprises natural rubber (NR), epoxidized natural rubber (ENR), synthetic cis-polyisoprene (IR), emulsion styrene butadiene rubber (eSBR), solution styrene butadiene rubber (sSBR), polybutadiene rubber (BR), butyl rubber (IIR / CIIR / BIIR), chloroprene rubber (CR), nitrile elastomer (NBR), hydrogenated nitrile elastomer (HNBR), carboxylated nitrile elastomer (XNBR), ethylene propylene rubber (EPM / EPDM), fluoroelastomer (FPM / FKM), polyurethane rubber (AU / EU / PU), or the like, or any combination thereof.

[0132] Aspect 63. The polymer composition of any one of aspects 57 to 62, wherein the polymer composition further comprises a carbon black additive.

[0133] Aspect 64. The composition or method of any one of the preceding aspects, wherein the polymer composition, and / or the NDC, and / or the deflocculating agent does not comprise a carbon black material (e.g., a carbon black additive or a carbon black filler). Examples of embodiments of the present invention are listed in the following items [Aspect 1] to [Aspect 31]. [Aspect 1] A polymer composition comprising: (I) polymers; (II) a nanocellulose dispersion composition (NDC) comprising: (i) a deflocculating agent comprising a carbon black filler, an elastomer latex, a wax, or any combination thereof; and (ii) nanocellulose; and (III) Carbon black additives. [Aspect 2] 2. The polymer composition of embodiment 1, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) ranges from about 100:1 to about 1:1. [Aspect 3] 3. The polymer composition of claim 1 or 2, wherein the polymer comprises an elastomer. [Aspect 4] 4. The polymer composition of any one of aspects 1 to 3, wherein the nanocellulose dispersion composition has greater dispersibility of nanocellulose in the polymer composition than dispersibility of nanocellulose without the deflocculating agent. [Aspect 5] Aspect 5. The polymer composition of any one of aspects 1-4, wherein the nanocellulose comprises nanocellulose crystals (NC), nanocellulose fibrils (NF), or a combination thereof. [Aspect 6] Aspect 6. The polymer composition of any one of aspects 1-5, wherein the nanocellulose comprises lignin-coated nanocellulose crystals (LCNCs), lignin-coated nanocellulose fibrils (LCNFs), or a combination thereof. [Aspect 7] Aspect 7. The polymer composition of any one of aspects 1-6, wherein the nanocellulose comprises hydrophilic cellulose nanocellulose crystals (CNCs), hydrophilic cellulose nanocellulose fibrils (CNFs), or a combination thereof. [Aspect 8] Aspect 8. The polymer composition of any one of aspects 1 to 7, wherein the nanocellulose dispersion composition (NDC) further comprises a hydrocarbon oil. [Aspect 9] Aspect 9. The polymer composition of any one of aspects 1-8, wherein the elastomer latex comprises natural rubber (NR), isoprene rubber (IR), emulsion styrene-butadiene rubber (ESBR), or any combination thereof. [Aspect 10] Aspect 10. The polymer composition of any one of aspects 1-9, wherein the wax comprises an unbranched alkane paraffin wax; a natural mineral, petroleum-refined, or lignin-refined branched paraffin wax or ceresin wax; a polyethylene wax; a functionalized polyethylene wax; or any combination thereof. [Aspect 11] Aspect 11. The polymer composition of any one of aspects 1-10, wherein the carbon black filler and the carbon black additive each independently comprise furnace carbon black and / or surface-modified furnace carbon black. [Aspect 12] 12. The polymer composition of any one of aspects 1-11, wherein the carbon black filler and the carbon black additive are each independently characterized by: Approximately 90m 2 / g ~ approx. 140m 2 / g nitrogen surface area; Approximately 80m 2 / g ~ approx. 125m 2 external surface area in / g; pH of about 2.5 to about 4; Approximately 55cm 3 / 100g~approx.67cm 3 / 100g of 50GM void volume; Approximately 50cm 3 / 100g~approx.60cm 3 / 100g 75GM void volume; Approximately 45cm 3 / 100g~approx. 55cm 3 / 100g 100GM void volume; a moisture content of about 2.5% to about 4.5% by weight; a volatile matter content of about 4.5% to about 6.5% by weight; an oxygen content of about 2.5% to about 5.5% by weight; or Any combination of them. [Aspect 13] Aspect 13. The polymer composition of any one of aspects 1-12, wherein the deflocculating agent comprises at least two of the carbon black filler, the elastomer latex, and the wax. [Aspect 14] 14. The polymer composition of any one of aspects 1-13, wherein a weight ratio of the deflocculating agent to the nanocellulose ranges from about 0.5:1 to about 25:1. [Aspect 15] 15. The polymer composition of any one of aspects 1 to 14, wherein the nanocellulose dispersion composition (NDC) is produced by a method comprising: (a) combining the aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture; and (b) drying the mixture to form the nanocellulose dispersion composition (NDC). [Aspect 16] 15. The polymer composition of any one of aspects 1 to 14, wherein the nanocellulose dispersion composition (NDC) is produced by a method comprising: (A) combining the aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture; and (B) drying the mixture to form the nanocellulose dispersion composition (NDC); wherein the anti-agglomerating agent is stable in the NDC and spaced between nanocellulose particles to reduce or prevent agglomeration of the nanocellulose particles in the NDC. [Aspect 17] 1. A method for deflocculating nanocellulose in an aqueous system to improve its dispersibility in a polymer, the method comprising: (a) combining the aqueous dispersion of nanocellulose with a deflocculating agent to form a mixture, wherein the deflocculating agent comprises a carbon black filler; and (b) drying the mixture to form a nanocellulose dispersion composition (NDC). [Aspect 18] 1. A method for deflocculating nanocellulose in an aqueous system using a deflocculating agent, the method comprising: (A) combining the aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture, wherein the deflocculating agent comprises a carbon black filler; and (B) drying the mixture to form a nanocellulose dispersion composition (NDC); wherein the anti-agglomerating agent is stable in the NDC and spaced between nanocellulose particles to reduce or prevent agglomeration of the nanocellulose particles in the NDC. [Aspect 19] 19. The method of claim 17 or 18, wherein the deflocculating agent further comprises an elastomer latex, a wax, or a combination thereof. [Aspect 20] Aspect 20. The method of any one of aspects 17 to 19, wherein the aqueous dispersion of nanocellulose is combined with the deflocculating agent and a hydrocarbon oil. [Aspect 21] A nanocellulose dispersion composition (NDC) produced by the method of any one of aspects 17 to 20. [Aspect 22] A nanocellulose dispersion composition (NDC) comprising: (i) a deflocculating agent comprising a carbon black filler; and (ii) Nanocellulose. [Aspect 23] 23. The composition of claim 21 or 22, wherein the nanocellulose dispersion composition has greater dispersibility of the nanocellulose in the polymer blend than the dispersibility of the nanocellulose without the deflocculating agent. [Aspect 24] Aspect 24. The composition of any one of aspects 21-23, wherein the anti-agglomerating agent further comprises an elastomer latex, a wax, or a combination thereof. [Aspect 25] Aspect 25. The composition of any one of aspects 21 to 24, wherein the nanocellulose dispersion composition (NDC) further comprises a hydrocarbon oil. [Aspect 26] 26. The composition of any one of aspects 21-25, wherein a weight ratio of the anti-agglomerating agent to the nanocellulose ranges from about 0.5:1 to about 25:1. [Aspect 27] A polymer composition comprising: (I) a polymer; and (II) A nanocellulose dispersion composition (NDC) according to any one of aspects 21 to 26. [Aspect 28] 28. The polymer composition of embodiment 27, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) ranges from about 100:1 to about 1:1. [Aspect 29] 29. The polymer composition of claim 27 or 28, wherein the polymer comprises a thermoplastic resin. [Aspect 30] 29. The polymer composition of claim 27 or 28, wherein the polymer comprises an elastomer. [Aspect 31] Aspect 31. The polymer composition of any one of aspects 27 to 30, wherein the polymer composition further comprises a carbon black additive.

Claims

1. A nanocellulose dispersion composition (NDC) comprising: (i) a deflocculating agent comprising a carbon black filler and at least one elastomer latex and / or wax; and (ii) nanocellulose, including lignin-coated nanocellulose crystals (LCNCs), lignin-coated nanocellulose fibrils (LCNFs), or a combination thereof; And, the nanocellulose dispersion composition (NDC) is characterized by a moisture content of less than 1.5 wt.%; A nanocellulose dispersion composition (NDC) wherein the weight ratio of the anti-agglomerating agent to the nanocellulose is in the range of 0.5:1 to 25:

1.

2. 10. The composition of claim 1, wherein the nanocellulose dispersion composition (NDC) further comprises (iii) a hydrocarbon oil.

3. The composition of claim 2 , wherein the hydrocarbon oil comprises an aliphatic hydrocarbon, an aromatic hydrocarbon, or a combination thereof.

4. 3. The composition of claim 2, wherein the hydrocarbon oil comprises a treated distillate aromatic extract (TDAE) oil.

5. The composition of any one of claims 1 to 4, wherein the anti-agglomerating agent comprises an elastomer latex.

6. The composition of claim 5, wherein the elastomer latex comprises natural rubber (NR), isoprene rubber (IR), emulsion styrene-butadiene rubber (ESBR), or any combination thereof.

7. The composition of any one of claims 1 to 6, wherein the anti-agglomerating agent comprises a wax.

8. 8. The composition of claim 7, wherein the wax comprises an unbranched alkane paraffin wax; a natural mineral, petroleum-refined, or lignin-refined branched paraffin wax or ceresin wax; a polyethylene wax; a functionalized polyethylene wax; or any combination thereof.

9. The composition of any one of claims 1 to 8, wherein the carbon black filler comprises furnace carbon black and / or surface-modified furnace carbon black.

10. The composition of any one of claims 1 to 9, wherein the carbon black filler is characterized by: 90m ２ / g~140m ２ / g nitrogen surface area; 80m ２ / g~125m ２ / g external surface area; pH of 2.5 to 4; 55cm ３ / 100g~67cm ３ / 100g 50GM void volume; 50cm ３ / 100g~60cm ３ / 100g 75GM void volume; 45cm ３ / 100g~55cm ３ / 100g 100GM void volume; a moisture content of 2.5% to 4.5% by weight; a volatile matter content of 4.5% to 6.5% by weight; an oxygen content of 2.5% to 5.5% by weight; or Any combination of them.

11. A composition according to any one of claims 1 to 10, wherein the anti-agglomerating agent comprises a carbon black filler and at least one elastomer latex and / or wax, and the weight ratio of the anti-agglomerating agent to the nanocellulose is in the range of 0.7:1 to 15:

1.

12. A polymer composition comprising: (I) a polymer; and (II) A nanocellulose dispersion composition (NDC) according to any one of claims 1 to 11.

13. The polymer composition of claim 12, wherein the nanocellulose dispersion composition (NDC) comprises the anti-agglomerating agent and the nanocellulose, and the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) is in the range of 100:1 to 1:

1.

14. 10. A method for producing a nanocellulose dispersion composition (NDC) according to claim 1, said method comprising: (a) combining the aqueous dispersion of nanocellulose with the deflocculating agent to form a mixture; and (b) drying the mixture to form the nanocellulose dispersion composition (NDC).

15. 15. The method of claim 14, wherein the aqueous dispersion of nanocellulose is combined with the deflocculating agent and a hydrocarbon oil.

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