Nanocellulose dispersion composition containing carbon black for tire applications

Abstract

Disclosed are nanocellulose dispersion compositions comprising a splitting agent and nanocellulose, and methods for making the nanocellulose dispersion compositions. These nanocellulose dispersion compositions can be used in tire formulations with carbon black and a suitable elastomer to produce articles of manufacture for use in tire and tread applications.

Description

Technical Field

[0001] This application was filed on February 18, 2021 as a PCT international patent application, claiming priority to U.S. Provisional Patent Application No. 62 / 978,397, filed on February 19, 2020, the disclosure of which is hereby incorporated by reference in its entirety.

[0002] The present disclosure relates to a nanocellulose dispersion composition for use in polymer formulations, and more particularly to a nanocellulose dispersion composition for use in elastomer formulations intended for tire applications.

Background Art

[0003] Nanocellulose has recently received much attention as a nanomaterial with many different potential uses, such as in plastics and elastomers. The use of nanocellulose in these applications is intended to improve the performance of the resulting composite materials and the sustainable properties of the materials for the future, since nanocellulose is derived from biomass and not from hydrocarbon materials. However, one problem with nanocellulose is that, whether in crystalline or fibrillar form, nanocellulose usually binds to itself during drying, forming large aggregates of nanocellulose in the polymer composite structure, and thus has poor dispersibility in hydrophobic and nonpolar solvents and matrices (including plastics and elastomers).

[0004] For example, when mixing nanocellulose into an elastomer compound, good dispersion of the nanocellulose is desired to eliminate large aggregates and obtain sufficient benefits of incorporating the nanocellulose into the elastomer matrix. Large aggregates can cause stress concentration and may cause premature damage to the polymer composite material.

[0005] Therefore, it has become important to devise a method for significantly improving the dispersibility of nanocellulose in polymer formulations, which remains an important issue faced in the development, growth, and commercialization of nanocellulose in tires and other end-use applications. Therefore, these objectives are precisely what the present invention generally aims at. SUMMARY OF THE INVENTION

[0006] This summary is provided to introduce in a simplified form a selected set of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the subject matter claimed in the claims. Nor is this summary intended to be used to limit the scope of the subject matter claimed in the claims.

[0007] In accordance with the objectives of the present invention embodied and broadly described herein, the present disclosure, in one aspect, relates to a step of adding a splitting agent during or prior to a nanocellulose drying step such that the splitting agent remains intact and prevents the nanocellulose crystals and nanofibrils from binding to each other. As a result, a nanocellulose dispersion composition that can be easily dispersed in tire formulations such as elastomers and plastics for tires and other end-use applications is obtained.

[0008] A nanocellulose dispersion composition (NDC) is described herein, and the NDC can include (i) a dispersing agent including carbon black filler, an elastomer latex, a wax, or any combination thereof, and (ii) nanocellulose. This NDC can be used in a tire composition, and thus can include (I) a polymer, (II) any of the nanocellulose dispersion compositions disclosed herein, and (III) a carbon black additive. In some embodiments, the tire composition can be characterized by a dispersion index of at least about 90% as determined by interference microscopy (IFM), while in other embodiments, the tire composition can be characterized by a fatigue life at 100% tensile strain of at least about 300,000 cycles. The tire compositions disclosed herein can be used to manufacture various manufactured articles such as automotive tires, truck tires, and bus tires.

[0009] Both 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 restrictive. Further, features or variations may be provided in addition to those defined herein. For example, certain aspects and embodiments may be directed to various combinations and sub - combinations of the features described in the detailed description.

[0010] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate some aspects and together with the description serve to explain certain principles of the invention.

Brief Description of the Drawings

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Mode for Carrying Out the Invention

[0045] Additional aspects of the present invention are described in part below, in part are apparent from the description, or can be learned by the practice of the present invention. The advantages of the present invention are realized and achieved by 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 claimed.

[0046] Detailed Description The present invention can be more readily understood by reference to the following detailed description of the invention and the examples contained therein.

[0047] Before the compounds, compositions, articles, systems, devices, and / or methods are disclosed and described, it is to be understood that, unless otherwise specified, they can, of course, vary and are not limited to any particular synthesis method or, unless otherwise specified, any particular reagents. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although 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 hereinafter.

[0048] All publications mentioned in this specification are incorporated herein by reference to disclose and describe the methods and / or materials related to the citation of that publication.

[0049] Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0050] The test methods used in this specification are known to and understood by those skilled in the art. When appropriate, references are provided for specific test methods. For example, interference microscopy (IFM) was performed using ASTM D2663, Standard Test Methods for Carbon Black - Dispersion in Rubber, Method D to determine, for example, the dispersion index and the area ratio of undispersed materials, such as fillers like carbon black and nanocellulose.

[0051] As used in this specification, unless otherwise stated, the singular forms "a", "an", and "the" include plural alternatives. Thus, for example, references to "a polymer" or "a dispersing agent" include, unless otherwise specified, mixtures or combinations of two or more polymers or dispersing agents, respectively. ", unless otherwise specified, each include mixtures or combinations of two or more polymers or dispersing agents.

[0052] Compositions and methods are described herein using the term "comprising" various components or steps, but the compositions and methods can also, unless otherwise specified, "consist essentially of" or "consist of" various components or steps. For example, a nanocellulose dispersion composition (NDC) according to an aspect of the present invention can comprise (i) a dispersing agent and (ii) nanocellulose; alternatively, it can consist essentially of (i) a dispersing agent and (ii) nanocellulose; or alternatively, it can consist of (i) a dispersing agent and (ii) nanocellulose.

[0053] Ranges can be expressed herein as from a particular value and / or to a particular value as “about” and / or from another particular value. When such a range is expressed, other aspects include from and / or to a particular value. Similarly, when a value is expressed as an approximation, it is understood that the use of the antecedent “about” forms other aspects with the particular value. It is further understood that each endpoint of each range is significant, both in relation to other endpoints and independently of other endpoints. Also, many values are disclosed herein, and each value is also understood to be disclosed herein as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, “about 10” is also disclosed. Also, each unit between two particular units is understood to be disclosed. For example, if 10 and 15 are disclosed, 11, 12, 13, and 14 are also disclosed.

[0054] As used herein, the terms “optional” and “optionally” mean that the event or circumstance described thereafter may or may not occur, and the description includes examples where the event or circumstance occurs and examples where it does not occur.

[0055] What is disclosed are the components used in the method for preparing the compositions of the present invention and the compositions themselves. These and other materials are disclosed herein, and where combinations, subsets, interactions, groups, etc. of these materials are disclosed, specific mention of each and every individual and collective combination and arrangement of these compounds cannot be explicitly disclosed, but each is understood to be specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and numerous modifications that can be made to a number of molecules containing that compound are discussed, then each and every combination and arrangement of the compound and the possible modifications are specifically contemplated, unless specifically indicated to the contrary. Thus, if classes of molecules A, B, C and classes of molecules D, E, F are disclosed and A-D, an example of a combined molecule, is disclosed, then each, even if not individually described, is individually and collectively contemplated and it is meant that combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Similarly, any subset or combination of these is also disclosed. Thus, for example, sub-groups of A-E, B-F, and C-E are considered disclosed. This concept applies to all aspects of this application, including but not limited to the steps in the methods of making and using the compositions of the present invention. Thus, if there are various additional steps that can be performed, it is understood that each of these additional steps can be performed in a particular aspect or combination of aspects of the methods of the present invention.

[0056] As briefly described above, the present disclosure provides a method for the dispersion of nanocellulose present in an aqueous system in an individual fibril or crystalline state, which remains stable during drying and includes a splitting agent that prevents bonding - and aggregation - between individual nanocellulose fibrils and / or crystals, leaving spaces between the nanocellulose particles. In one aspect, the present disclosure provides a method for splitting nanocellulose, and in other aspects, the present disclosure provides a nanocellulose composition that is compatible with various polymer and elastomer compounds in order to improve the nanocellulose dispersion in these polymer and elastomer compounds so as to achieve sufficient benefits of nanocellulose addition. For example, the advantages of improving nanocellulose dispersion in an elastomeric material include a reduction in hysteresis or heat accumulation, which is considered important for the overall performance of tires for both tread compounds and non - tread compounds, a reduction in compound weight, and other performance characteristics of tire compounds, but are not limited thereto.

[0057] It should be noted that the nanocellulose of the present disclosure can include any nanocellulose, regardless of whether it is in a crystalline or fibrillar form and regardless of whether it has already been processed or modified in some other way. The source of the nanocellulose can be a suitable source, whether made from wood pulp or other biomass materials and whether made by any industrial process. Biomass fibers are composed of cellulose structural components that can be industrially extracted in various shapes and sizes, including cellulose nanocrystals (NC) and cellulose nanofibrils (NF). Further, the specific size and shape of the nanocellulose can be such that the width and / or length range from the nanoscale to the micron scale. NF typically has dimensions of width 5 - 20 nm and length 500 - 2000 nm and includes both amorphous and crystalline domains of cellulose. NC typically has a width of 5 - 8 nm and a length of 100 - 300 nm and is mainly crystalline. These ranges and dimensions are typical, but the present invention encompasses all NC materials and NF materials regardless of particle shape or particle diameter / dimension.

[0058] In virtually all non-aqueous applications where nanocellulose is used, the improvement of its dispersibility and the usefulness and advantages for these applications have been a major obstacle in the implementation of this technology. Therefore, it has become important to find an economical and practical method and process for improving dispersibility and highly dispersing nanocellulose in polymers such as elastomer compounds. Using a splitting agent during or before the drying process of nanocellulose itself, rather than a post-treatment technique, can help achieve this goal.

[0059] Regarding the improvement of nanocellulose dispersion, various efforts have been made on chemical surface modification after drying, and some have finally been successful. However, these have generally been found to be difficult to scale up to commercial quantities and are uneconomical, requiring extreme means. Generally, these methods are based on the freeze-drying of nanocellulose, which is a method established in the laboratory to prevent irreversible inter-particle bonding of nanocellulose. Freeze-drying is not economical for the commercial production of nanocellulose and is also not scalable.

[0060] Therefore, a simpler and more economical method is desired. Thus, a method for splitting nanocellulose is provided to prevent bonding between nanocelluloses before or during drying, resulting in improved nanocellulose dispersion in polymers such as plastics and elastomers.

[0061] Nanocellulose dispersion composition Nanocellulose can be produced, for example, by decomposing biomass into submicron cellulose nanofibers or nanocrystals using chemical means, mechanical means, or a combination of chemical and mechanical means. Other methods of providing nanocellulose, such as bacterial nanocellulose and tunicate nanocellulose, are also available. Typically, the production of nanocellulose is carried out in two initial stages. The first stage is the purification of biomass to remove most of the non-cellulose components in the biomass, such as lignin, hemicellulose, extractives, and inorganic contaminants. This is typically done by conventional pulping and bleaching. When producing cellulose nanofibers, the second stage typically involves mechanical refining of the purified biomass fibers. In the case of cellulose nanocrystals, the second stage typically involves acid hydrolysis of the purified fibers followed by high-shear mechanical treatment. In new production methods such as the highly versatile AVAP® method, either cellulose nanocrystals or cellulose nanofibers can be produced by chemical fractionation of biomass using SO2 and ethanol (at different concentrations) followed by mechanical treatment. Regardless of the type of nanocellulose, after the final mechanical treatment stage, the nanocellulose often suspends in an aqueous solution as a stable gel above a threshold concentration (typically a solids content greater than 2 wt%). When dried to remove water, the nanocellulose particles usually bind and aggregate irreversibly, resulting in poor dispersion into the polymer system.

[0062] To reduce or prevent the binding of nanocellulose to itself during drying, as described herein, a dispersing agent can be added to the aqueous nanocellulose dispersion, which sufficiently interacts with the surface of the nanocellulose and / or is uniformly distributed among the nanocellulose particles to reduce or prevent the aggregation of the nanocellulose.

[0063] The first method of dispersing nanocellulose in an aqueous system to improve its dispersibility in a polymer can include (a) combining an aqueous dispersion of nanocellulose with a dispersing agent to form a mixture, and (b) drying the mixture to form a nanocellulose dispersion composition (NDC). The second method of dispersing nanocellulose in an aqueous system with a dispersing agent can include (A) combining an aqueous dispersion of nanocellulose with a dispersing agent to form a mixture, and (B) drying the mixture to form a nanocellulose dispersion composition (NDC). The dispersing agent can be stabilized in the NDC and can space apart the nanocellulose particles to reduce or prevent aggregation of the nanocellulose particles in the NDC. The nanocellulose dispersion composition produced by any of the methods disclosed herein is also encompassed by the present invention. The nanocellulose dispersion composition (NDC) can include at least a dispersing agent and nanocellulose - the dispersing agent can include carbon black filler, elastomer latex, or wax, and any combination of these materials.

[0064] In steps (a) and (A) of the first and second methods, the aqueous dispersion of nanocellulose can be combined with the dispersing agent to form a mixture. The aqueous dispersion of nanocellulose can contain an appropriate amount of nanocellulose, but generally has at least about 2 wt% solids and at most 10 wt% solids (e.g., about 2 wt% to about 5 wt% solids).

[0065] Appropriate containers and conditions can be used to combine the aqueous nanocellulose dispersion and the dispersing agent, and this can be achieved batch - wise or continuously. By way of example, the nanocellulose dispersion and the dispersing agent can be combined in an appropriate container (e.g., a tank) at atmospheric pressure, optionally with stirring or mixing, at an appropriate temperature, often in the range of about 15°C to about 60°C.

[0066] The amount of the splitting agent used for nanocellulose is not particularly limited, but the weight ratio of the splitting agent to nanocellulose in the nanocellulose dispersion composition often ranges from about 0.1:1 to about 25:1. In some embodiments, the weight ratio of the splitting agent to nanocellulose is about 0.1:1 to about 10:1, about 0.1:1 to about 5:1, about 0.1:1 to about 2:1, about 0.1:1 to about 1:1, 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 within the range of about 0.1:1, 0.25:1, 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 using a plurality of splitting agents, the weight ratio is determined by the total amount of the splitting agents.

[0067] In the aqueous nanocellulose dispersion or the nanocellulose dispersion composition (NDC), the type of nanocellulose is also not particularly limited. In one embodiment, for example, the nanocellulose can include nanocellulose crystal (NC), nanocellulose fibril (NF), or a combination thereof. The nanocellulose may further include lignin as surface lignin and / or lignin contained in the bulk particles. In other embodiments, the nanocellulose can include lignin-coated nanocellulose crystal (LCNC), lignin-coated nanocellulose fibril (LCNF), or a combination thereof. Generally, these lignin-coated materials are more hydrophobic. In still other embodiments, the nanocellulose can include hydrophilic cellulose nanocellulose crystal (CNC), hydrophilic cellulose nanocellulose fibril (CNF), or a combination thereof.

[0068] Typically, suitable dispersants are compatible with polymers (such as elastomers, tire formulations), can reduce the aggregation of nanocellulose in NDC, and can reduce the aggregation in polymer formulations. In many cases, the dispersant in the nanocellulose dispersion composition, or the dispersant used to form the nanocellulose dispersion composition, can include carbon black fillers, elastomer latexes, waxes, or any combination thereof. Any suitable rubber latex can be used, examples of which include, but are not limited to, natural rubber (NR), isoprene rubber (IR), emulsion styrene butadiene rubber (ESBR), etc. Mixtures or combinations of two or more rubber latex materials can be used.

[0069] Examples of wax components include, but are not limited to, microcrystalline waxes (either natural minerals, petroleum-refined or lignin-refined) including unbranched alkane paraffin waxes, branched paraffin waxes, and ceresin waxes, polyethylene waxes, functionalized polyethylene waxes, etc., or any combination thereof.

[0070] The carbon black of the present invention, if present, can include carbon black suitable for use with the NDC and / or elastomeric materials employed. In one aspect, the carbon black can include (or consist essentially of, or consist of) furnace carbon black. Additionally or alternatively, the carbon black can include (or consist essentially of, or consist of) surface-modified furnace carbon black, such as oxidized furnace carbon black. In other aspects, the carbon black can include carbon black suitable for use in rubber, such as in tires. In other aspects, the carbon black can include carbon black suitable for use in tire treads or tire carcasses. In various aspects, the carbon black can include 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 can be useful in the present invention are listed below. It is to be understood that these values and ranges are intended to be essentially exemplary and that the present invention is not limited to any specific range, value, or combination.

[0071] The carbon black can be, for example, from about 8 m 2 / g to about 140 m 2 / g; from about 20 m 2 / g to about 140 m 2 / g; from about 45 m 2 / g to about 140 m 2 / g; from about 60 m 2 / g to about 140 m 2 / g; from about 90 m 2 / g to about 140 m 2 / g; from about 95 m2 / g ~ about 135 m 2 / g; about 100 m 2 / g ~ about 130 m 2 / g; about 105 m 2 / g ~ about 125 m 2 / g; about 110 m 2 / g ~ about 125 m 2 / g; about 115 m 2 / g ~ about 125 m 2 / g; about 110 m 2 / g ~ about 120 m 2 / g; about 115 m 2 / g ~ about 120 m 2 / g; about 115 m 2 / g ~ 121 m 2 / g; or about 116 m 2 / g ~ about 120 m 2 / g can have a nitrogen surface area. In other embodiments, the carbon black is about 90 m 2 / g, about 92 m 2 / g, about 94 m 2 / g, about 96 m 2 / g, about 98 m 2 / g, about 100 m 2 / g, about 102 m 2 / g, about 104 m 2 / g, about 106 m 2 / g, about 108 m 2 / g, about 110 m 2 / g, about 112 m 2 / g, about 114 m 2 / g, about 116 m 2 / g, about 118 m 2 / g, about 120 m 2 / g, about 122 m 2 / g, about 124 m 2 / g, about 126 m 2 / g, about 128 m 2 / g, about 130 m 2 / g, about 132 m 2 / g, about 134 m 2 / g, about 136 m 2 / g, about 138 m 2 / g, or about 140 m 2 / g can have a nitrogen surface area. In another embodiment, the carbon black is about 8 m 2 / g, about 10 m 2 / g, about 12 m 2 / g, about 14 m 2 / g, about 16 m 2 / g, about 18 m 2 / g, about 20 m 2 / g, about 22 m 2 / g, about 24 m 2 / g, about 26 m 2 / g, about 28 m 2 / g, about 30 m 2 / g, about 35 m 2 / g, about 40 m 2 / g, about 45 m 2 / g, about 50 m 2 / g, about 55 m 2 / g, about 60 m 2 / g, about 65 m 2 / g, about 70 m 2 / g, about 75 m 2 / g, about 80 m 2 / g, about 85 m 2 / g, about 90 m 2 / g, about 95 m 2 / g, about 100 m 2 / g, about 105 m 2 / g, about 110 m 2 / g, about 115 m 2 / g, about 120 m 2 / g, about 125 m 2 / g, about 130 m 2 / g, about 135 m 2 / g, or about 140 m 2 It can have a nitrogen surface area of / g. In yet other embodiments, the carbon black can have a nitrogen surface area of about 118 m 2 / g. In other embodiments, the carbon black of the present invention can have a nitrogen surface area greater than or less than any of the values specifically listed herein, and the present invention is not intended to be limited to any particular nitrogen surface area value.

[0072] The carbon black has a thickness based on the statistical thickness method (STSA, ASTM D6556-14) of about 8 m 2 / g to about 125 m 2 / g; about 20 m 2 / g to about 125 m2 / g; about 45 m 2 / g to about 125 m 2 / g; about 60 m 2 / g to about 125 m 2 / g; about 80 m 2 / g to about 125 m 2 / g; about 85 m 2 / g to about 120 m 2 / g; about 90 m 2 / g to about 115 m 2 / g; about 95 m 2 / g to about 110 m 2 / g; about 95 m 2 / g to about 105 m 2 / g; about 98 m 2 / g to about 104 m 2 / g; or about 99 m 2 / g to about 103 m 2 It can have an external surface area of / g. In other embodiments, the carbon black is about 101 m 2 / g. In other embodiments, the carbon black has a statistical thickness-based thickness of about 8 m 2 / g, about 10 m 2 / g, about 12 m 2 / g, about 14 m 2 / g, about 16 m 2 / g, about 18 m 2 / g, about 20 m 2 / g, about 22 m 2 / g, about 24 m 2 / g, about 26 m 2 / g, about 28 m 2 / g, about 30 m 2 / g, about 35 m 2 / g, about 40 m 2 / g, about 45 m 2 / g, about 50 m 2 / g, about 55 m 2 / g, about 60 m 2 / g, about 65 m 2 / g, about 70 m 2 / g, about 75 m 2 / g, about 80 m 2 / g, about 85 m 2 / g, about 90 m 2 / g, about 95 m 2 / g, about 100 m2 / g, about 105 m 2 / g, about 110 m 2 / g, about 115 m 2 / g, about 120 m 2 / g or about 125 m 2 It can have an external surface area of / g. In various embodiments, the external surface area of the carbon black is a specific surface area at which the rubber compound can be used. 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 listed herein, and the present invention is not intended to be limited to any specific external surface area value.

[0073] The carbon black of the present invention - such as furnace carbon black - can have a pH of about 2.5 to about 9, about 2.5 to about 7, or about 4 to about 7, as measured by ASTM method D1512-15 using either test method A or test method B. In one embodiment, the carbon black can be oxidized carbon black having a pH generally of about 2.5 to about 4, or about 2.8 to about 3.6, or about 3 to about 3.4; or alternatively about 3.2. In other embodiments, the carbon black of the present invention can have a pH greater than or less than any of the values specifically listed herein, and the present invention is not intended to be limited to any specific pH value.

[0074] The carbon black of the present invention can have, for example, about 55 cm 3 / 100 g to about 67 cm 3 / 100 g (50 GM); about 60 cm 3 / 100 g to about 65 cm 3 / 100 g (50 GM); about 25 cm 3 / 100 g to about 60 cm 3 / 100 g; about 30 cm 3 / 100 g to 60 cm 3 / 100 g; about 35 cm 3 / 100 g to 60 cm 3 / 100 g; about 40 cm 3 / 100 g to 60 cm3 / 100 g; about 45 cm 3 / 100 g to 60 cm 3 / 100 g; about 50 cm 3 / 100 g to about 60 cm 3 / 100 g (75 GM); about 53 cm 3 / 100 g to about 58 cm 3 / 100 g (75 GM); about 45 cm 3 / 100 g to about 55 cm 3 / 100 g (100 GM); or about 47 cm 3 / 100 g to about 53 cm 3 It can have a void volume of / 100 g (100 GM). In other embodiments, the carbon black can have a void volume of about 62.2 cm 3 50 GM void volume of / 100 g, about 55.3 cm 3 75 GM void volume of / 100 g, and / or about 50.4 cm 3 It can have a void volume of 100 GM of / 100 g. In other embodiments, the void volume of the carbon black of the present invention may be larger or smaller than any of the values specifically listed herein, and the present invention is not intended to be limited to any specific void volume.

[0075] The carbon black of the present invention can have a moisture content of, for example, about 2.5 wt% to about 4.5 wt%, about 3 wt% to about 4 wt%, or about 3.2 wt% to about 3.8 wt% as measured by ASTM method D1509-15. In other embodiments, the carbon black of the present invention can have a moisture content of about 3.5 wt%. It should be understood that the moisture content of the carbon black material can vary, for example, depending on the environment and / or storage conditions, and thus 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 than or less than any of the values specifically listed herein, and the present invention is not intended to be limited to any specific moisture content value.

[0076] In one aspect, the carbon black of the present invention is oxidized carbon black such as oxidized furnace carbon black. For example, there are various methods for oxidizing carbon black such as ozone treatment, and the specific method of oxidizing carbon black can be various as long as a plurality of desired oxygen-containing functional groups are present on the surface of the carbon black. Typical oxygen-containing functional groups that can be present on the surface of oxidized carbon black include, for example, carboxyl groups, hydroxyl groups, phenols, lactones, aldehydes, ketones, quinones, and hydroquinones. In various aspects, 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 the oxidation treatment. In one aspect, the carbon black is oxidized by treatment with ozone.

[0077] The carbon black of the present invention can have a volatile component content of about 0.5 wt% to about 6.5 wt%; about 1 wt% to about 6.5 wt%; about 1.5 wt% to about 6.5 wt%; about 2 wt% to about 6.5 wt%; about 2.5 wt% to about 6.5 wt%; about 3 wt% to about 6.5 wt%; about 3.5 wt% to about 6.5 wt%; about 4 wt% to about 6.5 wt%; about 4.5 wt% to about 6.5 wt%; about 5 wt% to about 6 wt% or about 5.2 wt% to about 5.8 wt%. In other aspects, the carbon black of the present invention can have a volatile component content of at least about 4.5 wt%, at least about 5 wt%, at least about 5.5 wt%, or more. In other aspects, the carbon black of the present invention can have a volatile component content of about 5.5 wt%. In still other aspects, the volatile component content of the carbon black can be greater than or less than any of the values specifically listed herein, and the present invention is not intended to be limited to any particular volatile component value.

[0078] The carbon black of the present invention can have an oxygen content of about 0.25 wt% to about 5.5 wt%; about 0.5 wt% to about 5.5 wt%; about 1 wt% to about 5.5 wt%; about 1.5 wt% to about 5.5 wt%; about 2 wt% to about 5.5 wt%; about 2.5 wt% to about 5.5 wt%; about 3 wt% to about 5 wt%; about 3.5 wt% to about 4.5 wt%; or about 3.7 wt% to about 4.3 wt%. In other embodiments, the carbon black of the present invention can have an oxygen content of at least about 3.5 wt%, at least about 4 wt%, or more. In other embodiments, the carbon black of the present invention can have an oxygen content of about 4 wt%. In yet 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 intended to be limited to any particular oxygen content value.

[0079] Optionally, the hydrocarbon oil can be used together with a separating agent. For example, in step (a) or step (A), an aqueous dispersion of nanocellulose can be combined with a separating agent and a hydrocarbon oil to form a mixture. The hydrocarbon oil can, in one embodiment, contain aliphatic hydrocarbons, while in other embodiments, the hydrocarbon oil can contain aromatic hydrocarbons. Further, in other embodiments, the hydrocarbon oil can contain a mixture or combination of aliphatic hydrocarbons and aromatic hydrocarbons. Suitable aliphatic hydrocarbons and / or aromatic hydrocarbons can be used, but it is beneficial for the hydrocarbon to be in the liquid phase under the conditions of combining the aqueous nanocellulose dispersion and the separating agent. An exemplary and non-limiting example of a suitable hydrocarbon oil that can be used as a separating agent is treated distillate aromatic extract (TDAE) oil.

[0080] Optionally, the aqueous nanocellulose dispersion, the separating agent, and any hydrocarbon oil can be mixed under high shear to ensure a 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.

[0081] 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 apparatus and drying technique can be used. In one aspect, the aqueous mixture can be exposed 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 - containing a dispersing agent and nanocellulose - contains generally less than 1.5 wt% water / moisture.

[0082] During the drying process and in the dried state, one or more coupling chemical substances can be optionally introduced into the NDC composition to, for example, modify the surface of the nanocellulose and enable subsequent coupling of the cellulose surface and the rubber matrix during vulcanization of a rubber compound prepared using the NDC. Coupling agents are well known to those skilled in the art and can include, in various aspects, monofunctional and / or bifunctional silanes based on mercapto, alkoxy, vinyl, amino, and methacryloxy chemistries, including common bifunctional sulfur - containing coupling silanes such as 3,3’ - bis - (triethoxysilylpropyl) - tetrasulfide.

[0083] Advantageously, a nanocellulose dispersion composition (NDC) that can contain (i) a dispersing agent and (ii) nanocellulose is typically more than 25% or more than 50% superior in nanocellulose dispersibility in a polymer formulation compared to a nanocellulose dispersion without a dispersing agent when measured by interference microscopy (IFM). For example, if the amount of undispersed material (area - based) by IFM was 12% for nanocellulose without a dispersing agent, with a 25% improvement, the area ratio of undispersed material would be 9%, and with a 50% improvement, the area ratio of undispersed material would be 6%.

[0084] Tire composition and articles thereof In some variations, the present invention is also directed to compositions, formulations, and manufactured articles that include any of the nanocellulose dispersion compositions (and their respective properties or characteristics such as the relative amounts of the dispersing agent and nanocellulose, the type of dispersing agent, and the type of nanocellulose) disclosed herein, and encompasses these. In certain aspects of the present invention, a tire composition is disclosed, and in this aspect, the tire composition can include a suitable polymer (one or more), any of the nanocellulose dispersion compositions disclosed herein, and a carbon black additive. The tire composition can often be referred to as a tire formulation, or a tire compound, etc.

[0085] The amount of the nanocellulose dispersion composition used in the tire composition is not particularly limited, but the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) often ranges from 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, about 90:1 to about 15:1, or about 100:1, about 98:1, about 96:1, about 94:1, about 92:1, about 90:1, about 85:1, about 80:1, about 75:1, about 70:1, about 65:1, about 60:1, about 55:1, about 50:1, about 45:1, about 40:1, about 35:1, about 30:1, about 25:1, about 20:1, about 15:1, about 10:1, about 8:1, about 6:1, about 4:1, about 2:1, or about 1:1. In some aspects, the weight ratio of polymer:NDC can fall within the range of about 75:1 to about 1.5:1, or about 50:1 to about 2:1.

[0086] In one aspect, the polymer in the tire composition can include a thermoplastic polymer, while in other aspects, the polymer can include a thermosetting polymer. In other aspects, the polymer can include, alone or in any combination, epoxies, acrylates, esters, urethanes, silicones, and / or phenols. In still other aspects, the polymer can include, alone or in any combination, polyethylene (e.g., ethylene homopolymer or 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).

[0087] In other aspects, the polymer used in the tire formulation / composition / compound can include, alone or in any combination, suitable rubbers or elastomers, 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), etc., and any combination thereof can be mentioned.

[0088] The total amount of carbon black present in the tire composition is not particularly limited, but is typically in the range of about 20 to about 150 phr. This includes not only the carbon black additive present in the formulation, but also the carbon black filler present in the NDC. In one embodiment, for example, the total amount of carbon black can be in the range of about 25 to about 125 phr, in other embodiments about 30 to about 100 phr, in still other embodiments about 35 to about 85 phr, and in still other embodiments about 40 to about 80 phr. In other embodiments, the total amount of carbon black can be in the range from the minimum carbon black content to the maximum carbon black content specifically listed herein, and the present invention is not intended to be limited to any particular phr amount of carbon black.

[0089] Similarly, the total amount of nanocellulose in the tire composition is not particularly limited, but is typically in the range of about 1 to about 15 phr. In some embodiments, the amount of nanocellulose can be in the range of about 1 to about 10 phr, about 1 to about 8 phr, about 1 to about 7 phr, or about 1 to about 6 phr, while in other embodiments, the amount of nanocellulose can be in the range of about 2 to about 15 phr, about 2 to about 10 hr, about 2 to about 7.5 phr, or about 2 to about 5 phr. Further, the amount of nanocellulose can be in the range from the minimum nanocellulose content to the maximum nanocellulose content specifically listed herein, and the present invention is not intended to be limited to any particular phr amount of nanocellulose.

[0090] Similarly, the total amount of hydrocarbon oil (e.g., TDAE oil) present in the tire composition is not particularly limited, but is typically in the range of about 1 to about 15 phr. This includes not only the hydrocarbon oil present in the formulation but also the hydrocarbon oil present in the NDC. In one embodiment, for example, the total amount of hydrocarbon oil can range from about 2 to about 12 phr, in another embodiment from about 2 to about 10 phr, in still another embodiment from about 3 to about 9 phr, and in yet another embodiment from about 4 to about 8 phr. In other embodiments, the total amount of hydrocarbon oil can range from the minimum hydrocarbon oil content to the maximum hydrocarbon oil content specifically listed herein, and the present invention is not intended to be limited to any specific phr amount of hydrocarbon oil such as TDAE.

[0091] Advantageously, the disclosed tire composition - comprising a polymer such as a suitable rubber or elastomer, a parting agent, and a nanocellulose dispersion composition (NDC) comprising nanocellulose, and a carbon black additive - is excellent in the dispersion of both the carbon black additive and the nanocellulose. In one embodiment, for example, the tire composition disclosed herein can be characterized by an area ratio of undispersed material of about 8% or less, about 6% or less, about 4% or less, about 3% or less, or about 2% or less as determined by interference microscopy (IFM). Additionally or alternatively, the tire composition disclosed herein can be characterized by a dispersion index of at least about 90%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, or at least about 98% as determined by interference microscopy (IFM).

[0092] Unexpectedly, the tire composition containing NDC has fatigue life values comparable to those of similar tire formulations without NDC. For example, the tire composition can be characterized by a fatigue life (ASTM D4482) at 100% tensile strain of at least about 300,000 cycles, at least about 325,000 cycles, at least about 350,000 cycles, at least about 375,000 cycles, or at least about 400,000 cycles.

[0093] The foregoing description of the specific embodiments has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teachings. Modifications and variations suitable for specific applications are contemplated. Examples of embodiments of the present invention are listed in the following items [Embodiment 1] to [Embodiment 24]. [Embodiment 1] (I) Polymer; (II) (i) A parting agent containing carbon black filler, elastomer latex, wax, or any combination thereof; and (ii) Nanocellulose, A nanocellulose dispersion composition (NDC) containing; and (III) Carbon black additive; A tire composition containing, The tire composition is characterized by a dispersion index of at least about 90% determined by interference microscopy (IFM). [Embodiment 2] (I) Polymer; (II) (i) A parting agent containing carbon black filler, elastomer latex, wax, or any combination thereof; and (ii) Nanocellulose, A nanocellulose dispersion composition (NDC) containing; and (III) Carbon black additive; A tire composition containing, The tire composition is characterized by a fatigue life at 100% tensile strain of at least about 300,000 cycles. [Embodiment 3] The weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) is in the range of 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, about 90:1 to about 15:1, about 75:1 to about 1.5:1, or about 50:1 to about 2:1. The tire composition according to Embodiment 1 or 2. [Embodiment 4] The polymer contains an elastomer. The tire composition according to any one of Embodiments 1 to 3. [Embodiment 5] The nanocellulose dispersion composition has a nanocellulose dispersibility in the polymer composition that is greater than the dispersibility of the nanocellulose without the parting agent. The tire composition according to any one of Embodiments 1 to 4. [Embodiment 6] The tire composition according to any one of Embodiments 1 to 5, wherein the nanocellulose contains nanocellulose crystal (NC), nanocellulose fibril (NF), or a combination thereof. [Embodiment 7] The tire composition according to any one of Embodiments 1 to 6, wherein the nanocellulose contains lignin-coated nanocellulose crystal (LCNC), lignin-coated nanocellulose fibril (LCNF), or a combination thereof. [Embodiment 8] The tire composition according to any one of Embodiments 1 to 7, wherein the nanocellulose contains hydrophilic cellulose nanocellulose crystal (CNC), hydrophilic cellulose nanocellulose fibril (CNF), or a combination thereof. [Embodiment 9] The tire composition according to any one of Embodiments 1 to 8, wherein the nanocellulose dispersion composition (NDC) further contains a hydrocarbon oil. [Embodiment 10] The tire composition according to any one of Embodiments 1 to 9, wherein the polymer contains natural rubber (NR), isoprene rubber (IR), polybutadiene rubber (BR), emulsion styrene-butadiene rubber (ESBR), or a combination of any of these. [Embodiment 11] The tire composition according to any one of Embodiments 1 to 10, wherein the wax contains unbranched alkane paraffin wax; branched paraffin wax or ceresin wax of natural mineral, petroleum refining, or lignin refining; polyethylene wax; functionalized polyethylene wax; or a combination of any of these. [Embodiment 12] The tire composition according to any one of Embodiments 1 to 11, wherein the carbon black filler and the carbon black additive independently contain furnace carbon black and / or surface-modified furnace carbon black. [Embodiment 13] The carbon black filler and the carbon black additive are about 90 m 2 / g to about 140 m 2 / g of nitrogen surface area; about 80 m 2 / g to about 125 m 2 / g of external surface area; about 2.5 to about 9 of pH; about 55 cm 3 / 100 g to about 67 cm 3 / 100 g of 50GM void volume; about 50 cm 3 / 100 g to about 60 cm 3 / 100 g of 75GM void volume; about 45 cm 3 / 100 g to about 55 cm 3 / 100 g of 100GM void volume; about 2.5 wt% to about 4.5 wt% of moisture content; about 4.5 wt% to about 6.5 wt% of volatile component content; An oxygen content of from about 2.5 wt% to about 5.5 wt%; or any combination thereof, The tire composition according to any one of Embodiments 1 to 12, independently characterized by. [Embodiment 14] The tire composition according to any one of Embodiments 1 to 13, wherein the dispersing agent includes at least two of the carbon black filler, the elastomer latex, and the wax. [Embodiment 15] The weight ratio of the dispersing agent to the nanocellulose is in the range of about 0.1:1 to about 25:1, about 0.1:1 to about 10:1, about 0.1:1 to about 5:1, about 0.1:1 to about 1:1, 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 0.75:1 to about 15:1, or about 1:1 to about 10:1. The tire composition according to any one of Embodiments 1 to 14. [Embodiment 16] The nanocellulose dispersion composition (NDC) is (a) combining an aqueous dispersion of the nanocellulose with the dispersing agent to form a mixture; and (b) drying the mixture to form the nanocellulose dispersion composition (NDC), The tire composition according to any one of Embodiments 1 to 15, produced by a process comprising. [Embodiment 17] The nanocellulose dispersion composition (NDC) is (A) combining an aqueous dispersion of the nanocellulose with the dispersing agent to form a mixture; and (B) drying the mixture to form the nanocellulose dispersion composition (NDC), produced by a process comprising The dispersing agent is stable in the NDC, spacing the nanocellulose particles apart, and reducing or preventing aggregation of the nanocellulose particles in the NDC. The tire composition according to any one of Embodiments 1 to 15. [Embodiment 18] The tire composition is about 20 to about 150 phr of carbon black, about 1 to about 15 phr of nanocellulose, and about 1 to about 15 phr of hydrocarbon oil; or about 30 to about 100 phr of carbon black, about 2 to about 10 phr of nanocellulose, and about 2 to about 10 phr of hydrocarbon oil; or about 40 to about 80 phr of carbon black, about 2 to about 7.5 phr of nanocellulose, and about 3 to about 9 phr of hydrocarbon oil, The tire composition according to any one of Embodiments 1 to 17, comprising. [Embodiment 19] The tire composition according to any one of Embodiments 1 to 18, characterized by a dispersion index of at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, or at least about 98% as determined by interference microscopy (IFM). [Embodiment 20] The tire composition according to any one of Embodiments 1 to 19, characterized by an area ratio of undispersed material of about 8% or less, about 6% or less, about 4% or less, about 3% or less, or about 2% or less as determined by interference microscopy (IFM). [Embodiment 21] The tire composition according to any one of Embodiments 1 to 20, characterized by a fatigue life at 100% tensile strain of at least about 325,000 cycles, at least about 350,000 cycles, at least about 375,000 cycles, or at least about 400,000 cycles. [Embodiment 22] An article of manufacture comprising the tire composition according to any one of Embodiments 1 to 21. [Embodiment 23] The article according to Embodiment 22, wherein the article is a pneumatic tire, a passenger car tire, or a radial tire for trucks and buses. [Embodiment 24] The article according to Embodiment 22, wherein the article is a tire tread.

[0094] Manufactured articles can be formed from and / or can include the tire formulations (tire compositions, tire compounds) of the present invention and are thus encompassed herein. For example, articles that can include the formulations of the present invention can include, but are not limited to, pneumatic tires, passenger vehicle tires, truck and bus radial (TBR) tires, or tire treads. In one aspect, any of the compositions described herein can be used in one or more tire compounds. In various aspects, such tire compounds can be uncured elastomer compounds or cured elastomer compounds. In other aspects, any of the compositions described herein can be used in one or more parts of a tire, including, for example, a tire tread, sidewall, subtread, bead, inner liner, etc. In a further aspect, such tires can include passenger vehicle tires, truck or bus radial tires, or other tires suitable for including the compositions described herein. It should be understood that the individual components of the compositions described herein can be added to an elastomer formulation in addition to or instead of one or more conventional components of such a formulation. It should also be understood that such individual components of the composition can interact with other components of a conventional elastomer formulation.

Examples

[0095] The present invention is further illustrated by the following examples, which should in no way be construed as imposing a limitation on the scope of the present invention. Various other aspects, embodiments, modifications, and their equivalents can be suggested to those skilled in the art after reading the description herein without departing from the spirit of the present invention or the appended claims.

[0096] Furthermore, these examples are not intended to limit in any way the scope or range of available dispersants or available nanocellulose materials that can be used to prepare nanocellulose dispersion compositions for use in polymer formulations, but are presented merely as examples for the purpose of illustrating the concept of combining a dispersant and nanocellulose into highly dispersible NDC.

[0097] The nanocellulose crystals or nanocellulose fibrils in these examples were produced using the AVAP® method described above and a unique method of depositing lignin on the surface of the fibrils or crystals to increase hydrophobicity and enhance compatibility with polymers and elastomers.

[0098] In Example 1, a model passenger vehicle tire tread compound was mixed using N234, a reference carbon black grade. This compound was included as a reference to show typical carbon black dispersion levels. N234 constituted 100% of the filler in this compound, which corresponds to 75 phr in the compound formulation. A detailed description (phr values) of a representative compound formulation and standard mixing procedures are summarized in Table 1-2. As shown in the SEM images of FIGS. 1A and 1B, the N234 carbon black had excellent dispersibility. FIG. 1A is a backscattered electron image of the leather cut compound surface, and FIG. 1B is a secondary electron image of the same area. The degree of dispersion quantified by interference microscopy (IFM) was generally in the range of a dispersion index of 98-100%, and the area fraction of undispersed carbon black was 0.8%.

[0099] Example 2 was manufactured using the same mixing procedure as Example 1, except that a very small portion (6.7 wt%) of N234 was replaced with dried lignin-coated nanocellulose fibrils (LCNF). The LCNF included 6.7 wt% of the total filler loading, which corresponds to 5 phr of the compound formulation. The remaining filler loading included N234 (93.3 wt%), which corresponds to 70 phr of the compound formulation. Figures 2A and 2B demonstrate, by means of a backscattered SEM image (Figure 2A) and a secondary SEM image (Figure 2B), that the dispersion of the nanocellulose was very poor because there were large aggregates of nanocellulose fibrils throughout the compound cross-section. The area ratio of the undispersed material was quantified by interference microscopy (IFM) and was 9.11%.

[0100] Example 3 was manufactured using the same procedure as Example 2. Instead of adding the free-standing dried LCNF as in Example 2, in Example 3, NDC containing LCNF treated with surface-modified carbon black (SMCB, N234) as a dispersant, together with TDAE oil and natural rubber latex, was used. The weight ratio of LCNF: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 less than 1.5 wt% water. The total filler loading of the NDC was 20 phr, and the LCNF added to the final compound was 6.7 wt% relative to the total filler loading, which corresponds to 5 phr in the compound formulation.

[0101] Figures 3A and 3B show the nanocellulose dispersion achieved when LCNF / SMCB / TDAE / NR NDC was added to the rubber compound mixer. Figure 3A is a backscattered electron image of the leather cut compound surface, and Figure 3B is a secondary electron image of the same region. The area ratio of the undispersed material is 2.78% (quantified by IFM), which is significantly improved compared to Example 2 (Figures 2A and 2B), and there are fewer and smaller nanocellulose aggregates present in the cross-section. The dispersibility is more similar to that of the N234 carbon black in Example 1 (Figures 1A and 1B), with only a small amount of undispersed regions.

[0102] In Example 4, the N234, which is a reference carbon black grade, was used to mix the tire tread compound of the model track. This compound is included as a reference to show a typical carbon black dispersion level. N234 contains 100% of the filler in this compound, which corresponds to 50 phr in the compound formulation. The detailed description (phr values) of the representative compound formulation and the standard mixing procedure are summarized in Tables 1 and 3. As shown in Figures 4A and 4B, the N234 carbon black had excellent dispersibility. Figure 4A is a backscattered electron image of the leather cut compound surface, and Figure 4B is a secondary electron image of the same region. The degree of dispersion quantified by interference microscopy (IFM) was generally in the range of 98 - 100% of the dispersion index, and the area ratio of the undispersed carbon black was 0.15%.

[0103] Example 5 was manufactured using the same mixing procedure as Example 4, except that a very small portion (10 wt%) of N234 was replaced with dried lignin-coated nanocellulose fibrils (LCNF). The LCNF comprised 10 wt% of the total filler loading, which corresponds to 5 phr in the compound formulation. The remaining filler loading comprised N234 (90 wt%), which corresponds to 45 phr in the compound formulation. Figures 5A and 5B demonstrate, by means of backscattered SEM images (Figure 5A) and secondary SEM images (Figure 5B), that the dispersion of the nanocellulose was very poor due to large aggregates of nanocellulose fibrils throughout the compound cross-section. The area fraction of the undispersed material was quantified by interference microscopy (IFM) and was 11.52%.

[0104] Example 6 was manufactured using the same mixing procedure as Example 1. Instead of adding the free-standing dried LCNF as in Example 5, in Example 6 the same NDC as in Example 3 was used. In this particular example, the NR latex was used in the NDC since it is a common material in the tread recipe, although other latex elastomer materials may be used. The weight ratio of LCNF:SMCB:TDAE oil:NR was 1:1:1:1. The NDC was prepared in the same manner as in Example 3. The total filler loading of the NDC was 20 phr and the LCNF added to the final compound was 10 wt% of the total filler loading, which corresponds to 5 phr in the compound formulation. Figures 6A and 6B show the nanocellulose dispersion achieved when LCNF / SMCB / TDAE / NR NDC was added to the rubber compound. Figure 6A is a backscattered electron image of the surface of the razor-cut compound and Figure 6B is a secondary electron image of the same area. The area fraction of the undispersed material was 2.44% as quantified by IFM, which is a significant improvement compared to Example 5 (Figures 5A and 5B). Note that the few undispersed regions in the SEM cross-section are significantly smaller than those in Figures 5A and 5B. The measured dispersion level of the nanocellulose in this compound is similar to that of Example 4.

[0105] In Examples 7 to 11, as summarized in Table 4, model TBR (truck and bus radial) tire tread compounds were manufactured regardless of the presence or absence of N234, which is a reference carbon black grade, and LCNF. Example 7 is a reference formulation to show typical carbon black performance, and N234 contains 100% of the filler, which corresponds to 50 phr in the compound formulation. Example 8 contains 2.5 phr less carbon black than Example 7, and Example 9 contains 5 phr less carbon black than Example 7. In Examples 10 - 11, part of the carbon black was replaced with LCNF, but the same NDC described in Examples 3 and 6 was used. The amount of LCNF was 2.5 phr in Example 10 and 5 phr in Example 11. Standard mixing procedures are summarized in Tables 5 and 6. Examples 7 - 11 utilize representative TBR tire tread formulations, but the disclosed NDC can be incorporated into various non-tread formulations (e.g., sidewalls, subtreads, beads / apices, etc.) using appropriate elastomers.

[0106] Upon shearing, LCNF typically aligns in the direction of grinding, so the properties of the polymer formulation and the LCNF dispersion can vary, for example, based on the direction along or against the grain. Regarding the dispersion of carbon black, ASTM D3053 defines macrodispersion as the degree of distribution of the filler into the compound on a scale of approximately 2 μm to 100 μm. Macrodispersion can be analyzed by IFM (interference microscopy, ASTM D2663 Method D), which measures surface roughness by IFM to quantify the macrodispersion of fillers having a diameter of at least 5 μm. Although this test method was developed for carbon black, the analysis data can be used to evaluate the macrodispersion of LCNF. The dispersion results of Examples 7 - 11 are summarized in Table 7 for scans along the grain and against the grain. The macrodispersion by IFM is calibrated for carbon black, while the data in Table 7 can be used to estimate the relative change in the amount of undispersed filler. The measurement of the area ratio is considered to most accurately represent the amount of undispersed filler. Example 11 contains 5 phr of LCNF and obtained unexpectedly good dispersion results in that the area ratios of the undispersed filler in Example 11 (0.51 along the grain and 0.83 against the grain) are similar to those of Examples 7 - 9 containing only carbon black.

[0107] Figures 7A - 7C are backscattered SEM images of the leather cut surface along the grain showing excellent dispersion of both N234 carbon black and LCNF in Example 11. Evidence of aligned discrete fibers is shown at high magnification, and overall unexpectedly good macrodispersion is shown at all magnifications. Figures 8A and 8B show similar results for Example 11 in backscattered SEM images of the leather cut surface against the grain.

[0108] Figure 9-25 compares various properties of each carbon black formulation of Examples 7-11. The T90 curing time was not affected by the presence of LCNF in Examples 10-11 as shown in Figure 9, but the scorch time was slightly longer for Examples 10-11 as shown in Figure 10. Figure 11 demonstrates a slight decrease in Mooney viscosity for the formulations of Examples 10-11 using NDC containing LCNF. The Shore A hardness in Figure 12 decreased due to the removal of N234 carbon black and increased slightly with the addition of LCNF.

[0109] Due to the high aspect ratio and anisotropy of LCNF, the stress-strain behavior showed different results based on tests along or against the grain. Figure 13 illustrates the static modulus of elasticity for the median values of five tests of Examples 7-11 at 100%, 200%, and 300% elongation. Generally, the removal of carbon black resulted in a lower modulus of elasticity, and the addition of LCNF resulted in an increase in the modulus of elasticity (especially at moderate strains). There was no significant decrease in the high-strain modulus of elasticity due to the addition of LCNF. Similarly, Figure 14 shows similar results in the comparison of tensile stress for Examples 7 and 11, with the LCNF formulations slightly improving the moderate strain stiffness (and this can be translated into potential tire handling advantages) and equivalent high strain stiffness.

[0110] Figure 15 illustrates the grinding directions along and against the grain, as well as the tensile tests along and against the grain. Figure 16 includes the data from Figure 13 (along the grain) and adds data for the modulus of elasticity against the grain. Based on the median values of five tests of Examples 7-11 at 100%, 200%, and 300% elongation, there was some evidence of more pronounced mechanical anisotropy for the LCNF-containing formulations. This is more clearly illustrated in Figure 17, which shows the mechanical anisotropy introduced by the addition of LCNF, especially at low and moderate strains.

[0111] Figures 18 and 19 illustrate the tensile strength and elongation at break for both the along-eye and against-eye states, respectively, for the median values of the five tests in Examples 7 - 11. The along-eye tensile strength was always greater than the against-eye tensile strength, and the LCNF-containing samples generally matched the control sample of Example 7. In the elongation at break data, no clear anisotropic trend was seen, and the LCNF-containing samples generally had slightly lower elongation at break values.

[0112] The critical tearing energy (Tc) data of Figure 20 for the median values of the five tests in Examples 7 - 11 showed no anisotropy for the control samples of Examples 7 - 9, but for the LCNF-containing samples, showed surprisingly large (~40% larger) Tc values for the tearing direction against the eye.

[0113] Figures 21, 22, and 23 summarize the DIN wear, rebound at 60 °C, and flexometer heat generation, respectively, for the average of two tests in Examples 7 - 11. The DIN wear data demonstrated a slight increase in DIN wear loss with the addition of LCNF. The rebound increased approximately linearly with the removal of carbon black, and these benefits were maintained by the addition of LCNF to the formulation. The heat generation data showed the same trend as the rebound data.

[0114] Figures 24 and 25 illustrate the tanδ MAX and ΔG’ from the ARES strain sweep data at 60 °C for the average of two tests in Examples 7 - 11. Generally, the strain sweep data showed the same trend as the rebound data and the heat generation data. There was a small but consistent improvement in the hysteresis of Examples 10 - 11 compared to the control sample of Example 7.

[0115] In summary, these results demonstrate that the disclosed NDC enables the effective incorporation and dispersion of sustainable filler (LCNF) with little to no apparent sacrifice in the properties resulting from carbon black and rubber-based formulations. Unexpectedly, the NR-based formulations containing -LCNF introduced by -NDC maintained or improved static stiffness, maintained or improved tear resistance, and improved (reduced) hysteresis compared to the N234 carbon black control without LCNF.

[0116] In Examples 12 - 15, as summarized in Table 8, model inner liner compounds were produced regardless of the presence or absence of the reference carbon black grade, N660, and LCNF. Examples 12 - 13 are reference formulations to show typical carbon black performance, with N660 containing 100% of the filler, which corresponds to 60 phr in the compound formulation. Example 14 contained 5 phr less carbon black than Examples 12 - 13, and Example 15 contained 10 phr less carbon black than Examples 12 - 13. In Examples 14 - 15, a portion of the carbon black was replaced with LCNF, but the same NDC described in Examples 3 and 6 was used except that N234 carbon black was replaced with N660 carbon black. The amount of LCNF was 5 phr in Example 14 and 10 phr in Example 15. Since NDC was an NR-based composition, two control samples were used to mimic the replacement of NR with butyl rubber (Example 12 contained 5 phr of NR while Example 13 contained 10 phr of FR). Table 9 summarizes the standard mixing procedure.

[0117] In Table 10, various properties of each carbon black formulation of Examples 12 - 15 are compared. The T90 cure time was generally not affected by the presence of LCNF. The cure time of Example 14 was longer than that of Control Examples 12 - 13, and the cure time of Example 15 was shorter than that of Control Examples 12 - 13. The T5 and T35 scorch times were slightly longer for NDC - containing Examples 14 - 15 compared to Control Examples 12 - 13. Conversely, Table 10 demonstrates a slight decrease in Mooney viscosity for the formulations of Examples 14 - 15 using NDC containing LCNF. The Shore A hardness decreased slightly due to the removal of N660 carbon black and increased slightly with an increase in the addition amount of LCNF.

[0118] The dispersion index (via IFM) typically decreases by replacing carbon black with NDC, and the resulting dispersion index can depend on the carbon black grade and the filling level of LCNF. However, and unexpectedly, Example 14 - having 5 phr LCNF filling - had excellent dispersion (dispersion index of 93.7%).

[0119] Table 10 also summarizes the static modulus for the median of five tests of Examples 12 - 15 at 100%, 200%, and 300% elongation. Equivalent results were obtained at higher strains, while at 100% elongation, the modulus was improved by the addition of LCNF. The tensile strength and elongation were generally not affected by replacing carbon black with NDC. The resilience at 60 °C generally increased step - by - step by replacing N660 carbon black with LCNF.

[0120] Table 10 includes tanδ MAX and ΔG’ from the RPA strain sweep data at 60 °C for the average of two tests of Examples 12 - 15. The replacement of carbon black with LCNF by NDC resulted in a slight beneficial decrease in both tanδ MAX and ΔG’. Beneficially, the fatigue life values at 100% tensile strain for NDC Examples 14 - 15 in Table 10 were equivalent to those of Control Examples 12 - 13.

[0121] As described above, these results demonstrate that the disclosed NDC enables the effective incorporation and dispersion of sustainable filler (LCNF) with little to no apparent sacrifice in the properties resulting from carbon black and rubber-based formulations. Unexpectedly, butyl rubber-based formulations containing -LCNF introduced by -NDC had properties comparable to those of the N660 carbon black control without LCNF.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

[0122] The present invention is described above with reference to numerous aspects 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 within the full intended scope of the appended claims. Other aspects of the present invention include, but are not limited to, the following (the aspects are described as "comprising", but may alternatively "consist essentially of" or "consist of").

[0123] Aspect 1 (I) A polymer; (II) A nanocellulose dispersion composition (NDC) comprising (i) a parting agent containing carbon black filler, an elastomer latex, a wax, or any combination thereof, and (ii) nanocellulose; and (III) A carbon black additive, a tire composition.

[0124] Aspect 2 The tire composition as defined in Aspect 1, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) is in the range of about 100:1 to about 1:1.

[0125] Aspect 3 The tire composition as defined in Aspect 1, wherein the weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) is in the range of about 50:1 to about 2:1.

[0126] Aspect 4 The tire composition as defined in any one of Aspects 1 to 3, wherein the polymer includes thermoplasticity.

[0127] Aspect 5 The tire composition as defined in any one of Aspects 1 to 3, wherein the polymer includes an elastomer.

[0128] Aspect 6 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 any combination thereof, and is a tire composition defined in any one of Aspects 1-3.

[0129] Aspect 7 The parting agent is compatible with the polymer and reduces the aggregation of nanocellulose, and is a tire composition defined in any one of Aspects 1-6.

[0130] Aspect 8 The nanocellulose dispersion composition has a nanocellulose dispersibility in the tire composition that is greater than the dispersibility of nanocellulose without a parting agent, and is a tire composition defined in any one of Aspects 1-7.

[0131] Aspect 9 The nanocellulose comprises nanocellulose crystal (NC), nanocellulose fibril (NF), or a combination thereof, and is a tire composition defined in any one of Aspects 1-8.

[0132] Aspect 10 The nanocellulose comprises lignin-coated nanocellulose crystal (LCNC), lignin-coated nanocellulose fibril (LCNF), or a combination thereof, and is a tire composition defined in any one of Aspects 1-9.

[0133] Aspect 11 The nanocellulose comprises hydrophilic cellulose nanocellulose crystal (CNC), hydrophilic cellulose nanocellulose fibril (CNF), or a combination thereof, and is a tire composition defined in any one of Aspects 1-10.

[0134] Aspect 12 The tire composition defined in any one of Aspects 1-11, wherein the nanocellulose dispersion composition (NDC) further contains a hydrocarbon oil.

[0135] Aspect 13 The tire composition defined in Aspect 12, wherein the hydrocarbon oil contains an aliphatic hydrocarbon, an aromatic hydrocarbon, or a combination thereof.

[0136] Aspect 14 The tire composition defined in Aspect 12, wherein the hydrocarbon oil contains a treated distillate aromatic extract (TDAE) oil.

[0137] Aspect 15 The tire composition defined in any one of Aspects 1-14, wherein the elastomer latex contains natural rubber (NR), isoprene rubber (IR), emulsion styrene butadiene rubber (ESBR), or any combination thereof.

[0138] Aspect 16 The tire composition defined in any one of Aspects 1-15, wherein the wax contains an unbranched alkane paraffin wax; a branched paraffin wax or ceresin wax of natural mineral, petroleum refining, or lignin refining; a polyethylene wax; a functionalized polyethylene wax; or any combination thereof.

[0139] Aspect 17 The tire composition defined in any one of Aspects 1-16, wherein the carbon black filler and the carbon black additive independently contain furnace carbon black and / or surface-modified furnace carbon black. [[ID=II]]

[0140] Aspect 18 The carbon black filler and the carbon black additive independently have a nitrogen surface area of about 90 m 2 / g to about 140 m 2 / g; and a DBP absorption of about 80 m 2 / g to about 125 m 2External surface area per g; pH of about 2.5 to about 9; about 55 cm 3 / 100 g to about 67 cm 3 50GM void volume per 100 g; 50 cm 3 / 100 g to about 60 cm 3 75GM void volume per 100 g; about 45 cm 3 / 100 g to about 55 cm 3 A tire composition according to any one of aspects 1-17, characterized by a 100GM void volume per 100 g; a moisture content of about 2.5 wt% to about 4.5 wt%; a volatile component content of about 4.5 wt% to about 6.5 wt%; an oxygen content of about 2.5 wt% to about 5.5 wt%; or any combination thereof.

[0141] Aspect 19 A tire composition according to any one of aspects 1-18, wherein the parting agent comprises a carbon black filler, an elastomer latex, or a wax.

[0142] Aspect 20 A tire composition according to any one of aspects 1-18, wherein the parting agent comprises at least two of a carbon black filler, an elastomer latex, and a wax.

[0143] Aspect 21 A tire composition according to any one of aspects 1-20, wherein the weight ratio of the parting agent to nanocellulose ranges from about 0.5:1 to about 25:1.

[0144] Aspect 22 A tire composition according to any one of aspects 1-21, wherein the weight ratio of the parting agent to nanocellulose ranges from about 1:1 to about 10:1.

[0145] Aspect 23 A tire composition according to any one of aspects 1-22, wherein the nanocellulose dispersion composition (NDC) is produced by a process comprising (a) combining an aqueous dispersion of nanocellulose with a parting agent to form a mixture, and (b) drying the mixture to form the nanocellulose dispersion composition (NDC).

[0146] Aspect 24 The tire composition is produced by a process comprising (A) forming a mixture by combining an aqueous dispersion of nanocellulose with a separating agent, and (B) drying the mixture to form a nanocellulose dispersion composition (NDC), wherein the separating agent is stable in the NDC and spaces the nanocellulose particles apart to reduce or prevent aggregation of the nanocellulose particles in the NDC, and is a tire composition as defined in any one of Aspects 1-22.

[0147] Aspect 25 The tire composition contains an appropriate amount of carbon black, for example, about 20 to about 150 phr, about 30 to about 100 phr, or about 40 to about 80 phr, and is a tire composition as defined in any one of Aspects 1-24.

[0148] Aspect 26 The tire composition contains an appropriate amount of nanocellulose, for example, about 1 to about 15 phr, about 2 to about 10 phr, or about 2 to about 7.5 phr, and is a tire composition as defined in any one of Aspects 1-25.

[0149] Aspect 27 The tire composition contains an appropriate amount of hydrocarbon oil, for example, about 1 to about 15 phr, about 2 to about 10 phr, or about 3 to about 9 phr, and is a tire composition as defined in any one of Aspects 1-26.

[0150] Aspect 28 An article of manufacture comprising a tire composition as defined in any one of Aspects 1-27.

[0151] Aspect 29 A pneumatic tire comprising a tire composition as defined in any one of Aspects 1-27.

[0152] Aspect 30 A passenger car tire comprising a tire composition as defined in any one of Aspects 1-27.

[0153] Aspect 31 A radial tire for trucks and buses (TBR) comprising a tire composition defined in any one of Aspects 1-27.

[0154] Aspect 32 A tire tread comprising a tire composition defined in any one of Aspects 1-27.

Claims

**Claim 1** (I) A polymer; (II) (i) A parting agent comprising carbon black filler, elastomer latex, wax, or any combination thereof; and (ii) Nanocellulose comprising lignin-coated nanocellulose crystals (LCNC), lignin-coated nanocellulose fibrils (LCNF), or any combination thereof, A nanocellulose dispersion composition (NDC) comprising; and (III) A carbon black additive; A tire composition comprising, The tire composition is characterized by a dispersion index of at least 90% as determined by interference microscopy (IFM). **Claim 2** (I) A polymer; (II) (i) A parting agent comprising carbon black filler, elastomer latex, wax, or any combination thereof; and (ii) Nanocellulose comprising lignin-coated nanocellulose crystals (LCNC), lignin-coated nanocellulose fibrils (LCNF), or any combination thereof, A nanocellulose dispersion composition (NDC) comprising; and (III) A carbon black additive; A tire composition comprising, The tire composition is characterized by a fatigue life at 100% tensile strain of at least 300,000 cycles. **Claim 3** The weight ratio of the polymer to the nanocellulose dispersion composition (polymer:NDC) is in the range of 100:1 to 1:1, 80:1 to 10:1, 75:1 to 2:1, 60:1 to 5:1, 50:1 to 1:1, 40:1 to 4:1, 75:1 to 25:1, 90:1 to 15:1, 75:1 to 1.5:1, or 50:1 to 2:

1. The tire composition according to claim 1 or 2. **Claim 4** The polymer comprises an elastomer. The tire composition according to any one of claims 1 to 3. **Claim 5** The nanocellulose dispersion composition has a nanocellulose dispersibility in the tire composition that is greater than the dispersibility of the nanocellulose without the parting agent. The tire composition according to any one of claims 1 to 4. **Claim 6** The nanocellulose comprises nanocellulose crystals (NC), nanocellulose fibrils (NF), or any combination thereof. The tire composition according to any one of claims 1 to 5. **Claim 7** The tire composition according to any one of claims 1 to 6, wherein the nanocellulose comprises hydrophilic cellulose nanocrystal (CNC), hydrophilic cellulose nanofibril (CNF), or a combination thereof.

8. The tire composition according to any one of claims 1 to 7, wherein the nanocellulose dispersion composition (NDC) further comprises a hydrocarbon oil.

9. The tire composition according to any one of claims 1 to 8, wherein the polymer comprises natural rubber (NR), isoprene rubber (IR), polybutadiene rubber (BR), emulsion styrene butadiene rubber (ESBR), or any combination thereof.

10. The tire composition according to any one of claims 1 to 9, wherein the wax comprises unbranched alkane paraffin wax; branched paraffin wax or ceresin wax of natural mineral, petroleum refining, or lignin refining; polyethylene wax; functionalized polyethylene wax; or any combination thereof.

11. The tire composition according to any one of claims 1 to 10, wherein the carbon black filler and the carbon black additive independently comprise furnace carbon black and / or surface-modified furnace carbon black.

12. The carbon black filler and the carbon black additive are 90 m ２ / g to 140 m ２ / g of nitrogen surface area; 80 m ２ / g to 125 m ２ / g of external surface area; a pH of 2.5 to 9; 55 cm ３ / 100 g to 67 cm ３ 50 GM void volume of / 100 g; 50 cm ３ / 100 g to 60 cm ３ / 100 g of 75 GM void volume; 45 cm ３ / 100 g to 55 cm ３ / 100 g of 100 GM void volume; a moisture content of 2.5 wt% to 4.5 wt%; a volatile component content of 4.5 wt% to 6.5 wt%; an oxygen content of 2.5 wt% to 5.5 wt%; or any combination thereof, and are independently characterized by the tire composition according to any one of claims 1 to 11.

13. The tire composition according to any one of claims 1 to 12, wherein the splitting agent comprises at least two of the carbon black filler, the elastomer latex, and the wax.

14. The weight ratio of the splitting agent to the nanocellulose is in the range of 0.1:1 to 25:1, 0.1:1 to 10:1, 0.1:1 to 5:1, 0.1:1 to 1:1, 0.25:1 to 15:1, 0.3:1 to 10:1, 0.5:1 to 25:1, 0.75:1 to 15:1, or 1:1 to 10:1, and the tire composition according to any one of claims 1 to 13.

15. The tire composition is 20 to 150 phr of carbon black, 1 to 15 phr of nanocellulose, and 1 to 15 phr of hydrocarbon oil; or 30 to 100 phr of carbon black, 2 to 10 phr of nanocellulose, and 2 to 10 phr of hydrocarbon oil; or 40 to 80 phr of carbon black, 2 to 7.5 phr of nanocellulose, and 3 to 9 phr of hydrocarbon oil, The tire composition according to any one of claims 1 to 14, comprising.

16. The tire composition according to any one of claims 1 to 15, wherein the tire composition is characterized by a dispersion index of at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, or at least 98% determined by interference microscopy (IFM).

17. The tire composition according to any one of claims 1 to 16, wherein the tire composition is characterized by an area ratio of undispersed material of 8% or less, 6% or less, 4% or less, 3% or less, or 2% or less determined by interference microscopy (IFM).

18. The tire composition according to any one of claims 1 to 17, wherein the tire composition is characterized by a fatigue life at 100% tensile strain of at least 325,000 cycles, at least 350,000 cycles, at least 375,000 cycles, or at least 400,000 cycles.

19. An article of manufacture comprising the tire composition according to any one of claims 1 to 18.

20. The article according to claim 19, wherein the article is a pneumatic tire, a passenger car tire, or a radial tire for trucks and buses.

21. The article according to claim 19, wherein the article is a tire tread.

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