Elastomer composites with polysaccharide filler

Abstract

Composites, such as elastomeric composites are described that include at least one elastomer, at least one filler that includes at least one polysaccharide and at least one coupling agent. The polysaccharide can be a solvent exchanged polysaccharide, or a milled polysaccharide and / or the coupling agent can utilize certain functional groups beneficial to linking to the elastomer and polysaccharide in the composite. Methods to prepare the composites and the polysaccharide are further described.

Description

2024906 ELASTOMER COMPOSITES WITH POLYSACCHARIDE FILLER FIELD

[0001] Disclosed herein are elastomer composites comprising a filler that is or includes at least one polysaccharide and also relates to articles or parts thereof containing such elastomer composites. BACKGROUND

[0002] Disclosed herein are elastomer composites, which can also be considered composites or elastomer compositions. Also disclosed herein are composites that contain a filler that is or includes at least one polysaccharide and also relates to articles or parts thereof containing the elastomer composites. Methods of making the elastomer composites and / or articles thereof are also disclosed herein.

[0003] Numerous products of commercial significance are formed of elastomeric compositions wherein particulate reinforcing material is dispersed in any of various synthetic elastomers, natural rubber, or elastomer blends. Carbon black and silica, for example, are widely used as reinforcing agents in natural rubber and other elastomers. It is common to produce a masterbatch, that is, a premixture of reinforcing material, elastomer, and various optional additives, such as extender oil. Numerous products of commercial significance are formed of such elastomeric compositions. Such products include, for example, vehicle tires wherein different elastomeric compositions may be used for the tread portion, sidewalls, wire skim and carcass. Other products include, for example, engine mount bushings, conveyor belts, windshield wipers, seals, liners, wheels, bumpers, and the like.

[0004] There is a current desire or goal to use sustainable fillers in composites. However, acceptable sustainable reinforcing fillers have been difficult to find for the elastomer or tire industry. The two main reinforcing fillers as produced today, conventional carbon black and precipitated silica, are not viewed by the industry as sustainable. A significant shift in the next few decades will most likely need to happen in order to meet the targets of industries such as the tire industry, which seeks to use, for instance, tires with 100% sustainable materials by 2050. There are different approaches within the reinforcing2024906 filler industry to meet the 2050 target, such as: sequester the carbon dioxide that is created during the process of filler production, use more sustainable feedstocks, and / or use renewable energy to name a few.

[0005] Accordingly, there is a need in the industry to develop elastomer composites that can effectively use at least portions of sustainable fillers and reinforce to essentially the same extent as fillers like carbon black and silica. SUMMARY

[0006] One aspect is a composite comprising: at least one elastomer; at least one filler in an amount of at least 40 phr, wherein at least 10 wt.% of the filler comprises at least one polysaccharide; and at least one coupling agent, wherein at least one of the following features is present: (a) the at least one polysaccharide has a particle size distribution of 100 nm < d50 < 5000 nm and / or 200 nm < d90 < 7000 nm; (b) the at least one polysaccharide has a BET surface area of at least 25 m2 / g; and / or (c) the at least one coupling agent comprises at least a first functional group and a second functional group, wherein the first functional group is selected from epoxide, amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol, and the second functional group comprises a sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone.

[0007] As an option, at least two of said features a) through c) are present, or features a) through c) are present, or at least said feature a) is present, or at least said feature b) is present, or at least feature c) is present.

[0008] Another feature is a composite comprising: at least one elastomer;2024906 at least one filler in an amount of at least 40 phr, wherein at least 10 wt.% of the filler comprises at least one polysaccharide; and at least one coupling agent comprising at least a first functional group and a second functional group, wherein the first functional group is selected from epoxide, amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol, and the second functional group comprises a sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone.

[0009] As an option, the at least one polysaccharide comprises at least one of the following: a glucan, a cellulose (e.g., nanocellulose), an amylose, inulin, a curdlan, a dextran, a xylan, a pullulan, guar gum, an alginate, a pectin, a chitosan, a chitin, and / or a starch, and / or any combinations thereof, e.g., a starch or a glucan or an alpha-glucan such as alpha- 1,3-glucan. The at least one polysaccharide can be a highly crystalline form comprising insoluble alpha-glucan particles having a degree of crystallinity of at least about 0.65, wherein the insoluble alpha-glucan has a weight-average degree of polymerization (DPw) of at least 10 or at least 15, and at least 50% (by number) of the glycosidic linkages of the insoluble alpha-glucan are alpha-1,3 glycosidic linkages.

[0010] As another option, the at least one polysaccharide is a highly crystalline form. The at least one polysaccharide can have a particle size distribution of 100 nm < d50 < 400 nm and / or a particle size distribution of 200 nm < d90 < 600 nm.

[0011] As an option, the at least one polysaccharide is a wet cake form. The at least one polysaccharide can have a particle size distribution of 250 nm < d50 < 1200 nm and / or a particle size distribution of 350 nm < d90 < 2000 nm.

[0012] As an option, at least 50 wt.% of the filler, or at least 75 wt.% of the filler comprises the at least one polysaccharide.

[0013] As an option, the at least one polysaccharide is a solvent-exchanged polysaccharide.

[0014] As an option, the BET surface area of the at least one polysaccharide is from 25 m2 / g to 500 m2 / g.2024906

[0015] As an option, the BET surface area of the at least one polysaccharide for feature c) is at least 10 m2 / g.

[0016] As an option, the at least one coupling agent is a non-silane coupling agent.

[0017] As an option, the first functional group and second functional group of at least one coupling agent are such that the first functional group interacts with the at least one polysaccharide, and the second functional group interacts with the at least one elastomer. As an option, the first functional group is selected from amine, thiosulfuric acid, hydrazide, phenol, and naphthol, and the second functional group is selected from sulfide, thiosulfuric acid, carboxylic acid, and hydrazide. As an option, the first and second functional group is hydrazide. As an option, the at least one coupling agent has the formula: H2N(H)NC(O)– Rn–C(O)N(H)NH2, wherein R can be substituted or unsubstituted and is selected from (i) a divalent C6-C20aromatic hydrocarbon radical, (ii) a divalent saturated or unsaturated C2-C20aliphatic radical, and (iii) a di(C1-C10)alkyl disulfide; and n is 0 or 1. As an option, the first functional group is amine and the second functional group is carboxylic acid. As an option, the first and second functional group are each thiosulfuric acid. As an option, the at least one coupling agent is selected from isophthalic dihydrazide, 3,3'- dithiobis(propanoic dihydrazide), and sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2- butenoate.

[0018] As an option, the at least one polysaccharide is the sole filler present in said composite. As an option, the at least one filler further comprises at least one of carbon black and silica. As an option, the filler present in the composite can be at least one polysaccharide along with at least one non-polysaccharide filler referred to herein, at times, as a secondary filler(s). As an option, the at least one secondary filler is present and is selected from carbon black, silica, clay, mica, kaolin, calcium carbonate, carbon nanotubes, pyrolysis carbon, graphene, carbon fiber, KEVLAR fiber, glass fiber, glass sphere, nylon fiber, graphite, boron nitride, graphite nanoplatelet, reduced graphene oxide, carbon nanostructures, fragments of carbon nanostructures, or fractured multiwall carbon nanotubes, or any combinations thereof. As an option, the at least one secondary filler is present and is selected from carbonaceous materials, carbon black, silica, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-wall carbon nanotubes, multi-wall carbon2024906 nanotubes, or combinations thereof, and coated and treated materials thereof (e.g., silicon- treated carbon black). As an option, the least one secondary filler is selected from carbon black, silica, clay, mica, kaolin, metal carbonates, carbon nanotubes, pyrolysis carbon, graphene, carbon fiber, glass fiber, glass sphere, nylon fiber, graphite, metal oxides, boron nitride, graphite nanoplatelet, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-wall carbon nanotubes, multi-wall carbon nanotubes, carbon nanostructures, fragments of carbon nanostructures, or fractured multiwall carbon nanotubes, or any combinations thereof.

[0019] As an option, the at least one elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, isobutylene-based elastomers, halogenated butyl rubber, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, silicone elastomers, and blends thereof.

[0020] As an option, the feature a) obtained by taking a starting polysaccharide and wet milling said starting polysaccharide.

[0021] As an option, the feature b) is obtained by taking a starting polysaccharide and conducting a solvent exchange to obtain a higher surface area compared to the surface area of the starting polysaccharide. As an option, the solvent exchange utilizes a solvent that is capable of exchanging with water. s an option, the higher surface area is an increase of at least at least 10% to 4000% or more compared to the surface area of the starting polysaccharide. As an option, the solvent satisfies an equation using Hansen solubility parameters: Ra < 40 MPa1 / 2, where (Ra)2= 4(δD2 – δD1)2 + (δP2 – δP1)2+ (δH2 – δH1)2.

[0022] Another aspect is an article of manufacture comprising the composites disclosed herein. As an option, the article is a tire or a component thereof, e.g., a tire tread or tire sidewall. As an option, the article is selected from o-ring seals, o-ring sealants, gaskets, diaphragms, valves, hydraulic seals, swell packers, blow out preventers, oil resistant hose liners, wire harnesses, battery cables, turbo hoses, molded air ducts, brake parts, grommets, hydraulic and radiator hoses, transmission seals, transmission gaskets, engine or2024906 chassis vibration mounts, constant velocity joint boots, engine seals, or fuel system components.

[0023] Another aspect is a method for preparing the composites disclosed herein. As an option, the method comprises combining the at least one elastomer and the at least one filler and the at least one coupling agent to form said composite. DETAILED DESCRIPTION

[0024] The disclosure will include illustrative embodiments and should not be construed as limiting; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the full scope of the claims to those skilled in the art.

[0025] Generally, disclosed herein is a composite or an elastomeric composition or elastomer composite that, for instance, can be used to form elastomeric and / or polymeric articles, as further described herein. The polymeric article(s) can be thermoplastic or thermoset. The article(s) can be vulcanized.

[0026] As used herein, an “elastomer composite” or “composite” or a masterbatch is an uncured mixture of filler (reinforcing material), elastomer, and optional additives, such as antidegradants. The composite can comprise an amount (e.g., from 30 phr to 250 phr, or from 30 phr to 80 phr, or other amounts disclosed herein) of dispersed filler. As an option, the composite or elastomer composite, as disclosed herein, further includes at least one coupling agent.

[0027] As an option, the composite or elastomer composite, as disclosed herein, can contain further components, such as antioxidant or antidegradants, in minor amounts (e.g., 10 wt % or less of total particulates or other amounts as disclosed herein). In addition, the composite can contain other particulates or rubber chemicals, e.g., one or more of processing aids, oils (e.g., extender oil), retardants, accelerants or any combinations thereof, including other additives as disclosed herein. Other optional components can include one or more of curative(s) such as sulfur, accelerators, and / or retarders.2024906

[0028] Further disclosed herein are articles made from one or more the elastomeric compositions or polymeric compositions disclosed herein, such as a tire or part thereof, and other elastomeric and / or polymeric articles.

[0029] As discussed above, there is a current desire to use sustainable fillers in elastomer composites. One option is to replace at least some or all of known fillers such as carbon black and / or silica with such sustainable fillers. One feature disclosed herein is the incorporation of at least one filler in an amount of at least 30 phr, wherein at least 10 wt.% of the filler (total filler content by weight) comprises at least one polysaccharide.

[0030] Certain sustainable fillers such as polysaccharides, however, currently do not reinforce to the same extent as carbon black and silica, and therefore would not be viewed as a suitable partial or full replacement for carbon black or silica. Without wishing to be bound by any theory, possible hypotheses for why the reinforcement level is not as high as silica and carbon black include: 1) lack of interaction between the filler and the rubber and 2) the hornification process, which leads to reduced surface area.

[0031] Accordingly, disclosed herein are elastomer composites comprising polysaccharides that are suitable sustainable filler replacements for carbon black and / or silica. In one aspect, the composite comprises, consists essentially of, consists of, or includes: at least one elastomer; at least one filler in an amount of at least 30 phr, wherein at least 10 wt.% of the filler (total filler content by weight) comprises at least one polysaccharide; and at least one coupling agent, wherein at least one of the following features is present: (a) the at least one polysaccharide has a particle size distribution of 100 nm < d50 < 5000 nm and / or 200 nm < d90 < 7000 nm; (b) the at least one polysaccharide has a BET surface area of at least 25 m2 / g; and / or (c) the at least one coupling agent comprises at least a first functional group and a second functional group, wherein the first functional group is selected from2024906 epoxide, amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol, and the second functional group comprises a sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone.

[0032] The polysaccharide present in the composite can be one type of polysaccharide or two different types, or three or more different types. The polysaccharide, when more than one type is present, can be the same polysaccharide chemically but have at least one particle or structural difference (e.g., different d50, different d90, different BET surface area, different particle size distribution other than a d50 or d90, and the like), and / or the two or more polysaccharides can be different chemically.

[0033] The polysaccharide can be any type of commercially available polysaccharide. The polysaccharide can be a naturally occurring polysaccharide. The polysaccharides are generally polymeric carbohydrates composed of monosaccharides joined by glycosidic bonds. The polysaccharide can be a storage polysaccharide. The polysaccharide can be a structural polysaccharide. The polysaccharide can be an acidic polysaccharide. The polysaccharide can be a bacterial polysaccharide. The polysaccharide can be enzymatically developed. The polysaccharide can have one or more groups attached thereto, such as alkyl groups, hydroxyalkyl groups (e.g., or carboxyalkyl groups), where “alkyl” can be a C1-C6alkyl (e.g., such as methyl or ethyl).

[0034] The polysaccharide can comprise, consists of, consist essentially of, or include at least one of the following: a glucan, a cellulose, an amylose, inulin, a curdlan, a dextran, a xylan, a pullulan, guar gum, an alginate, a pectin, a chitosan, a chitin, and a starch.

[0035] As an option, the polysaccharide can be a starch. As an option, the polysaccharide can be a starch. The starch can be unmodified or can be a modified starch, e.g., a crosslinked starch. Examples of modified starches are disclosed in U.S. Patent Nos. 6,755,915 B1 and 11,453,798 B2, the disclosures of which are incorporated by reference herein.

[0036] As another option, the polysaccharide can be an engineered polysaccharide. Exemplary engineered polysaccharides include those described in U.S. Patent Nos.11,608,388B2, 11,795,308B2, and 11,608,417B2, the disclosures of which are2024906 incorporated by reference herein. For example, the polysaccharides can be selected from: poly alpha-1,3-glucan; poly alpha-1,3-1,6-glucan; a water insoluble alpha-(1,3-glucan) polymer having 90% or greater α-1,3-glycosidic linkages, less than 1% by weight of alpha- 1,3,6-glycosidic branch points, and a number average degree of polymerization in the range of from 55 to 10,000; dextran; a composition comprising a poly alpha-1,3-glucan ester compound; and water-insoluble cellulose having a weight-average degree of polymerization (DPw) of at least 10, or at least 15, e.g., from about 15 to about 1000 and a cellulose II crystal structure.

[0037] Specific examples of the at least one polysaccharide includes glucans, such as engineered glucans. More specific examples of the at least one polysaccharide include alpha-glucans, e.g., alpha-1,3-glucan.

[0038] Further examples of the at least one polysaccharide include insoluble alpha-glucan particles having a degree of crystallinity of at least about 0.65, wherein the insoluble alpha-glucan has a weight-average degree of polymerization (DPw) of at least 10, or at least 15, and at least 50% (by number) of the glycosidic linkages of the insoluble alpha- glucan are alpha-1,3 glycosidic linkages.

[0039] The polysaccharide can be utilized, in forming the composite, in a liquid dispersion form, such as an aqueous dispersion form.

[0040] The polysaccharide can have a crystalline form (e.g., MCG or microcrystalline glucan).

[0041] The polysaccharide can be present as a wet cake (WC or “wet cake form).

[0042] Polysaccharides that can be used herein in the composite and / or can be further modified, as described herein for use in the composite, include those described in U.S. Patent Nos.11,608,388B2, 11,795,308B2, and 11,608,417B2, the disclosures of which are incorporated by reference herein. At least some of the polysaccharides that can be used herein can be obtained from International Flavors & Fragrances (IFF). One commercial example is NUVOLVE®engineered polysaccharides, either in highly crystalline form or as a wet cake.

[0043] As an option, the filler present in the composite can be solely one or more polysaccharides.2024906

[0044] One aspect provides a composite comprising at least one polysaccharide and at least one coupling agent comprising at least a first functional group and a second functional group, wherein the first functional group is selected from epoxide, amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol, and the second functional group comprises a sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone. The first and second functional groups can be the same or different.

[0045] As an option, the first functional group can be selected from amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol.

[0046] As an option, the second functional group is selected from sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone.

[0047] “Thiosulfuric acid” and “carboxylic acid” also encompasses salts thereof, e.g., Na+, K+, Li+, and ammonium salts. “Sulfide” refers to monosulfide, disulfide, or polysulfide, e.g., Sxwhere x = 1=10. Coupling agents comprising carboxylic acid include those having the formula – C(R1)=C(R2) – CO2H-, wherein R1and R2are independently selected from H and C1-C8alkyl (e.g., C1-C6alkyl or C1-C4alkyl).

[0048] As an option, wherein the first functional group is selected from amine, thiosulfuric acid, hydrazide, phenol, and naphthol, and the second functional group is selected from sulfide, thiosulfuric acid, carboxylic acid, and hydrazide.

[0049] As an option, the coupling agent contains at least one functional group that is a hydrazide. Examples of hydrazide coupling agents are based on benzohydrazide and naphthalene-2-carbohydrazide residues, which can have as additional functional groups one or more of hydroxy, amino, nitro, as disclosed in U.S. Pat. Publ. No.2019 / 0177513, the disclosure of which is incorporated by reference herein, or 2-hydroxy-3-naphthoic hydrazide as disclosed in EP0478274, the disclosure of which is incorporated by reference herein.

[0050] As an option, the first and second functional groups are each hydrazide, i.e., the coupling agent is a dihydrazide. As an option, dihydrazides have the formula: H2N(H)NC(O)– Rn–C(O)N(H)NH2, wherein R can be substituted or unsubstituted and is selected from (i) a divalent C6-C20aromatic hydrocarbon radical, (ii) a divalent saturated or unsaturated C2-C20aliphatic radical, and (iii) a di(C1-C10)alkyl disulfide; and n is 0 or 1.2024906 Exemplary dihydrazides include, among others, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, as disclosed in U.S. Pat. Publ. No. 2012 / 0277359A1, the disclosure of which is incorporated by reference herein, and isophthalic dihydrazide, as disclosed in EP478274, the disclosure of which is incorporated by reference herein.

[0051] As an option, the at least one coupling agent is isophthalic dihydrazide, 3,3'- dithiobis(propanoic dihydrazide).

[0052] As another option, the first functional group is an amine and the second functional group is carboxylic acid. An example includes sodium (2Z)-4-[(4- aminophenyl)amino]-4-oxo-2-butenoate, commercially available as Sumilink®200 coupling agent from Sumitomo Chemical.

[0053] As another option, the first functional group is amine and the second functional group is thiosulfuric acid. An example includes S-(3-aminopropyl)thiosulfuric acid, commercially available as Sumilink®100 coupling agent.

[0054] More specific examples of the coupling agent that can be utilized are isophthalic dihydrazide, 3,3'-dithiobis(propanoic dihydrazide), and / or sodium (2Z)-4-[(4- aminophenyl)amino]-4-oxo-2-butenoate.

[0055] As one option, the coupling agent can be or include or comprise a conventional coupling agent used in elastomer or rubber composites. Further details of coupling agents are provided elsewhere herein.

[0056] Exemplary coupling agents, that are not feature c) coupling agents, e.g., can be used in conjunction with feature (a) and / or (b) include one or more silane coupling agents, one or more zirconate coupling agents, one or more titanate coupling agents, one or more nitro coupling agents, or any combination thereof. Alternatively, the coupling agents can be used with feature (c) and / or (c) as one or more additional coupling agent. The coupling agent can be or include bis(3-triethoxysilylpropyl)tetrasulfane (e.g., Si 69 from Evonik Industries, Struktol SCA98 from Struktol Company), bis(3- triethoxysilylpropyl)disulfane (e.g., Si 75 and Si 266 from Evonik Industries, Struktol SCA985 from Struktol Company), 3-thiocyanatopropyl-triethoxy silane (e.g., Si 264 from Evonik2024906 Industries), gamma-mercaptopropyl-trimethoxy silane (e.g., VP Si 163 from Evonik Industries, Struktol SCA989 from Struktol Company), gamma-mercaptopropyl-triethoxy silane (e.g., VP Si 263 from Evonik Industries), zirconium dineoalkanolatodi(3-mercapto) propionato-O, N,N'-bis(2-methyl-2-nitropropyl)-1,6-diaminohexane, S-(3- (triethoxysilyl)propyl) octanethioate (e.g., NXT coupling agent from Momentive, Friendly, WV), and / or coupling agents that are chemically similar or that have the one or more of the same chemical groups. Additional specific examples of coupling agents, by commercial names, include, but are not limited to, VP Si 363 from Evonik Industries, and NXT Z and NXT Z-50 silanes from Momentive. The coupling agents described herein could be used to provide hydrophobic surface modification of silica (precoupled or pretreated silica) before using it in any of the processes disclosed herein. It is to be appreciated that any combination of elastomers, additives, and additional composite may be added to the elastomer composite, for instance in a compounder.

[0057] The coupling agent can be or include or comprise a non-silane coupling agent, e.g., the filler can be carbon black or silica. For example, the coupling agent can be any disclosed in PCT Publ. No. WO 2022 / 125679 A1, the disclosure of which is incorporated by reference herein.

[0058] The coupling agent(s) can be present in the composite in an amount of 10 phr or less, e.g., 6 phr or less, 5 phr or less, 4 phr or less, 3 phr or less, or 2 phr or less, e.g., an amount ranging from 0.1 phr to 10 phr, from 0.1 phr to 8 phr, from 0.1 phr to 6 phr, from 0.1 phr to 5 phr, from 0.1 phr to 4 phr, from 0.1 phr to 3 phr, from 0.2 phr to 10 phr, from 0.2 phr to 8 phr, from 0.2 phr to 6 phr, from 0.2 phr to 5 phr, from 0.2 phr to 4 phr, from 0.2 phr to 4 phr, from 0.2 phr to 3 phr, from 0.5 phr to 10 phr, from 0.5 phr to 8 phr, from 0.5 phr to 6 phr, from 0.5 phr to 5 phr, from 0.5 phr to 4 phr, from 0.5 phr to 3 phr, from 1 phr to 10 phr, from 1 phr to 8 phr, from 1 phr to 6 phr, from 1 phr to 5 phr, from 1 phr to 4 phr, or from 1 phr to 3 phr.

[0059] Alternatively, the filler present in the composite can be at least one polysaccharide along with at least one non-polysaccharide filler referred to herein, at times, as a secondary filler(s).2024906

[0060] The secondary filler(s) can be any type of conventional filler or conventionally reinforcement filler, including, but not limited to, carbon black, silica, clay, mica, kaolin, calcium carbonate, carbon nanotubes, pyrolysis carbon, graphene, carbon fiber, KEVLAR fiber, glass fiber, glass sphere, nylon fiber, graphite, boron nitride, graphite nanoplatelet, reduced graphene oxide, carbon nanostructures, fragments of carbon nanostructures, or fractured multiwall carbon nanotubes, or any combinations thereof. Other fillers are disclosed herein. As an option, the at least one secondary filler is present and is selected from carbonaceous materials, carbon black, silica, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-wall carbon nanotubes, multi-wall carbon nanotubes, or combinations thereof, and coated and treated materials thereof (e.g., silicon-treated carbon black). As an option, the least one secondary filler is selected from carbon black, silica, clay, mica, kaolin, metal carbonates, carbon nanotubes, pyrolysis carbon, graphene, carbon fiber, glass fiber, glass sphere, nylon fiber, graphite, metal oxides, boron nitride, graphite nanoplatelet, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-wall carbon nanotubes, multi-wall carbon nanotubes, carbon nanostructures, fragments of carbon nanostructures, or fractured multiwall carbon nanotubes, or any combinations thereof.

[0061] More preferred examples of the secondary filler are at least one carbon black and / or at least one silica.

[0062] From 0.01 wt% to 90 wt% of the filler can optionally be one or more secondary fillers, such as from 0.01 wt% to 85 wt%, from 0.01 wt% to 75 wt%, from 0.01 wt% to 70 wt%, from 0.01 wt% to 65 wt%, from 0.01 wt% to 60 wt%, from 0.01 wt% to 55 wt%, from 0.01 wt% to 50 wt%, from 0.01 wt% to 45 wt%, from 0.01 wt% to 40 wt%, from 0.01 wt% to 35 wt%, from 0.01 wt% to 30 wt%, from 0.01 wt% to 25 wt%, from 0.01 wt% to 20 wt%, from 0.01 wt% to 15 wt%, from 0.01 wt% to 10 wt%, from 0.01 wt% to 5 wt%, from 0.01 wt% to 1 wt%, from 0.1 wt% to 90 wt%, from 1 wt% to 90 wt%, from 2 wt% to 90 wt%, from 5 wt% to 90 wt%, from 10 wt% to 90 wt%, from 15 wt% to 90 wt%, from 20 wt% to 90 wt% from 25 wt% to 90 wt%, from 30 wt% to 90 wt%, from 35 wt% to 90 wt%, from 40 wt% to 90 wt%, from 50 wt% to 90 wt%, from 60 wt% to 90 wt%, from 70 wt% to 90 wt%, from2024906 80 wt% to 90 wt%, or any range based upon any two values described herein, where the wt% is based on the total weight of filler added to form the composite.

[0063] More details of the optional secondary filler are provided elsewhere herein.

[0064] As mentioned earlier, the composites disclosed herein have at least one of the following features or characteristics or properties, identified below (which can be referred to as “feature a)” through “feature c)”: (a) the at least one polysaccharide has a particle size distribution of 100 nm < d50 < 5000 nm and / or 200 nm < d90 < 7000 nm; (b) the at least one polysaccharide has a BET surface area of at least 25 m2 / g; and / or (c) the at least one coupling agent comprises at least a first functional group and a second functional group, wherein the first functional group is selected from epoxide, amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol, and the second functional group comprises a sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone.

[0065] As an option, at least feature a) is present.

[0066] As an option, at least feature b) is present.

[0067] As an option, at least feature c) is present.

[0068] As an option, the composites disclosed herein can have at least two of the features a) through c) present. As an option, features a) and b) are present. As an option, features a) and c) are present. As an option, features b) and c) are present.

[0069] As an option, the composites disclosed herein can have all three of the features a) through c) present.

[0070] Regarding feature a), the particle size distribution can be a d50 that is 100 nm < d50 < 5000 nm. Further examples include, but are not limited to, 100 nm < d50 < 4500 nm, 100 nm < d50 < 4000 nm, 100 nm < d50 < 3000 nm, 100 nm < d50 < 2000 nm, 100 nm < d50 < 1000 nm, 100 nm < d50 < 750 nm, 100 nm < d50 < 500 nm, 100 nm < d50 < 400 nm, 100 nm < d50 < 300 nm, 200 nm < d50 < 5000 nm, 300 nm < d50 < 5000 nm,2024906 400 nm < d50 < 5000 nm, 500 nm < d50 < 5000 nm, 600 nm < d50 < 5000 nm, 700 nm < d50 < 5000 nm, 800 nm < d50 < 5000 nm, 900 nm < d50 < 5000 nm, 1000 nm < d50 < 5000 nm, 1250 nm < d50 < 5000 nm, 1500 nm < d50 < 5000 nm, 1750 nm < d50 < 5000 nm, 2000 nm < d50 < 5000 nm, 2250 nm < d50 < 5000 nm, 2500 nm < d50 < 5000 nm, 2750 nm < d50 < 5000 nm, 3000 nm < d50 < 5000 nm, 3250 nm < d50 < 5000 nm, 3500 nm < d50 < 5000 nm, 3750 nm < d50 < 5000 nm, 4000 nm < d50 < 5000 nm, 4250 nm < d50 < 5000 nm, 4500 nm < d50 < 5000 nm, 4750 nm < d50 < 5000 nm, or 125 nm < d50 < 5000 nm, or any range based upon any two values described herein.

[0071] As an option, more than one type of polysaccharide having feature a) can be used in the same composite. For instance, a first polysaccharide can have the d50 limitation of feature a) and a second polysaccharide can have the d90 limitation of feature a). As another example, the first polysaccharide can have a d50 value that is different from a d50 value of a second polysaccharide used in the same composite. The difference in d50 (or d90) can be 10% or more, such as 20% or more, or 50% or more.

[0072] This option of using more than one type of polysaccharide would be applicable to a first polysaccharide having a feature a) and a second polysaccharide having feature b) or c) or d). Thus, more than one type of polysaccharide can be present with each polysaccharide having a different feature a)-d) and / or having a different sub-feature within the same feature a)-d), as exemplified above.

[0073] Regarding feature a), the particle size distribution can be a d90 that is 200 nm < d90 < 7000 nm. Further examples include, but are not limited to, 200 nm < d90 < 6775 nm, 200 nm < d90 < 6500 nm, 200 nm < d90 < 6000 nm, 200 nm < d90 < 5500 nm, 200 nm < d90 < 5000 nm, 200 nm < d90 < 4500 nm, 200 nm < d90 < 4000 nm, 200 nm < d90 < 3500 nm, 200 nm < d90 < 3000 nm, 200 nm < d90 < 2500 nm, 200 nm < d90 < 2000 nm, 200 nm < d90 < 1500 nm, 200 nm < d90 < 1000 nm, 200 nm < d90 < 750 nm, 200 nm < d90 < 500 nm, 200 nm < d90 < 400 nm, 200 nm < d90 < 300 nm, 250 nm < d90 < 7000 nm, 300 nm < d90 < 7000 nm, 350 nm < d90 < 7000 nm, 400 nm < d90 < 7000 nm, 450 nm < d90 < 7000 nm, 500 nm < d90 < 7000 nm, 600 nm < d90 < 7000 nm, 700 nm < d90 < 7000 nm, 800 nm < d90 < 7000 nm, 900 nm < d90 < 7000 nm, 1000 nm < d90 < 7000 nm, 1500 nm < d90 < 7000 nm, 2000 nm < d90 < 7000 nm, 2500 nm < d90 < 7000 nm, 3000 nm < d90 < 7000 nm, 3500 nm < d90 < 7000 nm, 4000 nm < d90 < 7000 nm, 4500 nm < d90 <2024906 7000 nm, 5000 nm < d90 < 7000 nm, 5500 nm < d90 < 7000 nm, 6000 nm < d90 < 7000 nm, 6500 nm < d90 < 7000 nm, 225 nm < d90 < 600 nm, or 225 nm < d90 < 500 nm, or any range based upon any two values described herein.

[0074] Regarding feature a), the at least one polysaccharide can be a highly crystalline form and can have the particle size distribution of 100 nm < d50 < 400 nm.

[0075] Regarding feature a), the at least one polysaccharide can be a highly crystalline form and can have the particle size distribution of 150 nm < d50 < 350 nm.

[0076] Regarding feature a), the at least one polysaccharide can be a highly crystalline form and can have the particle size distribution of 200 nm < d90 < 600 nm.

[0077] Regarding feature a), the at least one polysaccharide can be a highly crystalline form and can have the particle size distribution of 250 nm < d90 < 500 nm.

[0078] Regarding feature a), the at least one polysaccharide can be a wet cake form and can have the particle size distribution of 250 nm < d50 < 1200 nm.

[0079] Regarding feature a), the at least one polysaccharide can be a wet cake form and can have the particle size distribution of 350 nm < d90 < 2000 nm.

[0080] Regarding feature a), the at least one polysaccharide can be a wet cake form and can have the particle size distribution of 1000 nm < d90 < 7000 nm.

[0081] As an option, the feature a) can be obtained by taking a starting polysaccharide and subjecting the starting polysaccharide to particle size reduction step(s). Particle size reduction can be performed by a number of methods that subject the polysaccharide to high shear conditions, including high shear mixing, grinding, impact, or similar impingement actions. Particle size reduction can be performed with any equipment known in the art, e.g., vertical media mills such as attritors, ball mills, hammer mills, pin disk mills, fluid energy mills, jet mills, fluid jet mills, impingement jet mills, rotor-stators, pelletizers, homogenizers, sonicators, cavitators, classifiers (e.g., air classifiers), air classifier mills, and the like.

[0082] For instance, the starting particle saccharide can be subjected to a milling step(s), such as a wet milling step(s) or a media milling step(s) or a wet media milling step(s). The wet milling can be achieved using an organic solvent(s). The media for the milling can be2024906 any suitable commercially available media, such as, but not limited to, metal media (e.g., zirconia balls). The media mill can be, for instance, a Netzch Minicer media mill.

[0083] The method to create the milled polysaccharide is a further aspect disclosed herein, and further can be incorporated into an integrated facility or production set up where the milled polysaccharide is formed and then utilized in a process of making the composite. (such as including or incorporating one or more of the steps of making the composite as described elsewhere here).

[0084] The milling includes at least one milling step that utilizes media milling. If more than one media milling step is used, the type of media milling with respect to the media or type of milling or milling time, or number or size of media can be the same or different.

[0085] The media milling can be or include agitated ball milling, planetary ball milling, or centrifugal ball milling. One preferred media milling is agitated ball milling.

[0086] The media (which can be considered grinding media), as one option, utilizes a media that is solid balls. The solid balls, for examples, can have an average size that is from about 0.25 mm to 1 mm or greater. The average size can be from 0.3 mm to 1 mm, or 0.4 mm to 1 mm, or from 0.5 mm to 1 mm or from 0.6 mm to 1 mm or from 0.7 mm to 1 mm, or from 0.8 mm to 1 mm.

[0087] As an option, the media for the milling can be a size such that the particle size of the starting polysaccharide is about 3 times to about 10 times smaller or about 5 times to 10 times smaller (e.g., 4 times to 5 times smaller) than the media size utilized (e.g., average media size utilized).

[0088] The solid balls can metal balls, glass balls, ceramic balls, or polymeric balls. Specific examples include, but are not limited to, steel (e.g., chrome steel, or stainless steel such as 304SS and 316SS) or ceramics (e.g., agate, alumina, yttria stabilized zirconia, zirconium silicate, zirconia toughened alumina, and tungsten carbide).

[0089] The milling media can be loaded into the mill so that the volume loading is from 50% to 98% in a mill. The volume loading can be below 50% or higher than 90% if needed or desired. The volume loading can be from 50% to 95%, or from 60% to 90%, from 70% to 90%, from 80% to 90%, from 50% to 80%, from 50% to 70%, from 50% to 60%, or any2024906 range based upon any two values described herein. The volume loading is based on the total volume (space) available in the mill for milling.

[0090] The residence time of the milling in the mill can be for at least 15 seconds or at least 30 seconds, or at least 45 seconds, or at least 1 minute or at least 5 min. The residence time can be from about 15 seconds to 75 minutes, or from 30 seconds to 75 minutes, or from 1 minute to 75 minutes, such as from 2 minutes to 30 minutes or from 2 minutes to 10 minutes or from 2 minutes to 5 minutes. The residence time is based on the time that actual milling is occurring in the mill.

[0091] If performing wet milling, an amount of solvent / water used for wet milling results in 5 to 50 wt.% solids, e.g., from 5 to 30 wt.% solids, from 10 to 50 wt.% solids, or from 10-30 wt.% solids.

[0092] The milling temperature can range from 10°C to 60°C, e.g., from 10°C to 60°C, from 10°C to 50°C, from 10°C to 40°C, from 10°C to 30°C, from 15°C to 60°C, from 15°C to 50°C, from 15°C to 40°C, or from 15°C to 30°C.

[0093] The media milling is operated such that the milling expends a power of at least 0.5 kWh / kg, or at least 0.75 kWh / kg, or at least 1 kWh / kg, or at least 1.5 kWh / kg of dry milled reclaimed carbon. This power can be from 0.5 kWh / kg to 12 kWh / kg, or from 1 kWh / kg to 12 kWh / kg, or from 1.5 kWh / kg to 12 kWh / kg or from 2.5 kWh / kg to 12 kWh / kg, or from 4 kWh / kg to 10 kWh / kg, or from 5 kWh / kg to 12 kWh / kg, or from 6 kWh / kg to 12 kWh / kg, or from 7 kWh / kg to 12 kWh / kg, or from 8 kWh / kg to 12 kWh / kg, or from 2.5 kWh / kg to 10 kWh / kg, or from 2.5 kWh / kg to 8 kWh / kg, or from 2.5 kWh / kg to 6 kWh / kg, or any range based upon any two values described herein.

[0094] As an option, the at least one polysaccharide can be a solvent-exchanged polysaccharide. The mixing of elastomer and filler is typically performed as a dry mixing process, which is standard in the industry. Therefore, many previous attempts to incorporate polysaccharides in an elastomer requires drying of the polysaccharide. It has been discovered, however, that drying polysaccharides lowers the surface area compared to a polysaccharide that is dispersed in water. Without wishing to be bound by any theory, it has been hypothesized that this low surface area is a factor in the low reinforcement level afforded by polysaccharides due to reduced interaction between elastomer and filler.2024906

[0095] It has also been discovered that exposing polysaccharides to organic solvents can increase the surface area beyond that achieved with water. However, polysaccharide solutions or dispersions are often dried, typically by freeze drying or spray drying, which can cause some reduction in surface area.

[0096] It has been discovered that a polysaccharide with high surface areas can be attained by maintaining the polysaccharide in a liquid media comprising at least one organic solvent. As used herein, a “solvent-exchanged” polysaccharide refers to a polysaccharide that is wetted with or dispersed in or dissolved in a liquid media comprising an organic solvent. Upon mixing the solvent-exchanged polysaccharide with at least one elastomer, higher surface area of the polysaccharide allows a stronger interaction with the elastomer and can lead to increased reinforcement properties in a resulting elastomer composition.

[0097] The solvent-exchanged polysaccharide has a higher surface area compared to the surface area of a polysaccharide that has been exposed to a liquid medium and then dried (“dried polysaccharide). As an option, the increase in surface area of the solvent- exchanged polysaccharide can be an increase of at least 10%, at least 50%, at least 100%, at least 200%, at least 300%, at least 500%, at least 1000%, at least 10% to 5000% or more, e.g., at least 10% to 4000% or more, at least 10% to 3000% or more, at least 10% to 2000% or more, at least 10% to 1000% or more, at least 10% to 500% or more, at least 50% to 5000% or more, e.g., at least 50% to 4000% or more, at least 50% to 3000% or more, at least 50% to 2000% or more, at least 50% to 1000% or more, at least 50% to 500% or more, at least 100% to 5000% or more, e.g., at least 100% to 4000% or more, at least 100% to 3000% or more, at least 100% to 2000% or more, at least 100% to 1000% or more, at least 100% to 500% or more, at least 200% to 5000% or more, e.g., at least 200% to 4000% or more, at least 200% to 3000% or more, at least 200% to 2000% or more, at least 200% to 1000% or more, at least 200% to 500% or more, at least 500% to 5000% or more, e.g., at least 500% to 4000% or more, at least 500% to 3000% or more, at least 500% to 2000% or more, at least 500% to 1000% or more, or at least 10% to 300% or more (e.g., at least 20% to 300% or more, at least 30% to 300% or more, at least 40% to 300% or more, at least 50% to 300% or more, at least 60% to 300% or more, at least 70% to 300% or more, at least 80% to 300% or more, at least 90% to 300% or more, at least 100% to 300%) compared to the surface area of the starting polysaccharide or a dried polysaccharide.2024906

[0098] As an option, the liquid media contains at least one organic solvent (“solvent media”). The solvent media can be a mixture of water and organic solvent or can be 100% organic solvent. As an option, the solvent media comprises at least 50 wt.% organic solvent, e.g., at least 60 wt.%, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.% or is 100 wt.% organic solvent. As another option, the solvent media comprises 50-100 wt.% organic solvent, e.g., 60-100 wt.% organic solvent, 70-100 wt.% organic solvent, 80-100 wt.% organic solvent, 90-100 wt.% organic solvent, 95-100 wt.% organic solvent, 50-99 wt.% organic solvent, 60-99 wt.% organic solvent, 70-99 wt.% organic solvent, 80-99 wt.% organic solvent, 90-99 wt.% organic solvent, 95-99 wt.% organic solvent, 50-95 wt.% organic solvent, 60-95 wt.% organic solvent, 70-95 wt.% organic solvent, 80-95 wt.% organic solvent, or 90-95 wt.% organic solvent.

[0099] For the solvent exchange, at least one solvent is utilized that is capable of exchanging with water. As an option, the at least one solvent is miscible with water, including alcohols such as diols, triols, glycols, amides such as dimethyl formaldehyde and dimethyl acetamide; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; ethylene or diethylene glycol monomethyl ether and ethylene glycol monoethyl ether; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone; acids such as acetic acid; dimethyl sulfoxide; ethyl acetate; and other miscible solvents well known in the art.

[0100] As another option, water miscibility can be indicated with Hansen solubility parameters. As an option, the at least one organic solvent satisfies an equation using Hansen solubility parameters: Ra < 40 MPa1 / 2, where (Ra)2= 4(δD2– δD1)2 + (δP2– δP1)2+ (δH2– δH1)2. Exemplary solvents satisfying this equation include, acetic acid, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide, dioxane, ethanol, ethyl acetate, isopropanol, methanol, 1-propanol, tetrahydrofuran, 1-butanol, t-butanol (2-butanol), and the like.

[0101] Typically, for the solvent exchange process, the starting polysaccharide is a wet cake, a dispersion, or a slurry. The water content prior to solvent exchange can range from 20% to 90% by weight, e.g., from 20% to 80% by weight, from 20% to 70% by weight, from 20% to 60% by weight, from 30% to 90% by weight, from 30% to 80% by weight, from2024906 30% to 70% by weight, from 30% to 60% by weight, from 40% to 90% by weight, from 40% to 80% by weight, from 40% to 70% by weight, from 40% to 60% by weight, from 50% to 90% by weight, from 50% to 80% by weight, or from 50% to 70% by weight relative to the total weight of the wetcake, dispersion, or slurry. The polysaccharide can then be combined with any solvent disclosed herein (e.g., suspended in or stirred into, etc.), to form a wet polysaccharide in the form of a powder, paste, pellet, or cake, or slurry. As an option, the resulting wet polysaccharide can be further purified to remove water or reduce water content by methods known in the art, e.g., filtering. The polysaccharide that is solvent- exchanged to form the wet polysaccharide can be subsequently mixed with the at least one elastomer without any drying steps.

[0102] As an option, the solvent media can be present in the wet polysaccharide in an amount of at least 15 wt.% relative to the total weight of the wet polysaccharide, e.g., at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 40 wt.%, at least 45 wt.%, at least 50 wt.%, at least 55 wt.%, at least 60 wt.%, at least 70 wt.% or at least 80 wt.% relative to the total weight of the wet polysaccharide. As another option, the polysaccharide is a dispersion or slurry and is present in an amount ranging from 5 wt.% to 50 wt.% solids, e.g., from 5 wt.% to 40 wt.% solids, from 5 wt.% to 35 wt.% solids, from 5 wt.% to 30 wt.% solids, from 5 wt.% to 25 wt.% solids, from 5 wt.% to 20 wt.% solids, from 5 wt.% to 15 wt.% solids, from 10 wt.% to 50 wt.% solids, from 10 wt.% to 40 wt.% solids, from 10 wt.% to 35 wt.% solids, from 10 to 30 wt.% solids, from 10 to 25 wt.% solids, or from 10 to 20 wt.% solids (with the wt.% solids referring to the amount of polysaccharide in the slurry based on total weight of slurry).

[0103] Conditions for solvent exchange may depend on the solvent being used. In general, solvent exchange can be performed at temperatures ranging from 0°C to 60°C, from 0°C to 50°C, from 0°C to 40°C, from 0°C to 30°C, from 10°C to 60°C, from 10°C to 50°C, from 10°C to 40°C, from 10°C to 30°C, from 15°C to 60°C, from 15°C to 50°C, from 15°C to 40°C, or from 15°C to 30°C. The residence time in the solvent can be at least 1 min. or at least 5 min., e.g., ranging from 5 min. to 24 h, from 5 min. to 12 h, from 5 min. to 6 h, from 5 min. to 1 h, from 5 min. to 30 min., from 5 min. to 15 min., from 10 min. to 24 h, from 10 min. to 12 h, from 10 min. to 6 h, from 10 min. to 1 h, from 10 min. to 30 min., 15 min. to 24 h, from 15 min. to 12 h, from 15 min. to 6 h, or from 15 min. to 1 h.2024906

[0104] The method to create the solvent exchanged polysaccharide is a further aspect disclosed herein, and further can be incorporated into an integrated facility or production set up where the solvent exchanged polysaccharide is formed and then utilized in a process of making the composite (such as including or incorporating one or more of the steps of making the composite as described elsewhere here).

[0105] A solvent-exchanged polysaccharide can be mixed with the at elastomer in with any method known in the art. For example, the mixing can be performed in the solvent media where the elastomer is in solution and the solvent-exchanged polysaccharide is a slurry. As another example, the solvent-exchanged polysaccharide is in powder, cake, or paste form and can be mixed with solid elastomer as described in PCT Publ. No. WO 2020 / 247663, the disclosure of which is incorporated by reference herein.

[0106] Regarding feature b), the BET surface of the at least one polysaccharide (e.g., the solvent-exchanged polysaccharide) can be from 25 m2 / g to 500 m2 / g or higher. Further examples include, but are not limited to, 25 m2 / g to 475 m2 / g, 25 m2 / g to 450 m2 / g, 25 m2 / g to 425 m2 / g, 25 m2 / g to 400 m2 / g, 25 m2 / g to 375 m2 / g, 25 m2 / g to 350 m2 / g, 25 m2 / g to 325 m2 / g, 25 m2 / g to 300 m2 / g, 25 m2 / g to 275 m2 / g, 25 m2 / g to 250 m2 / g, 25 m2 / g to 225 m2 / g, 25 m2 / g to 200 m2 / g, 25 m2 / g to 175 m2 / g, 25 m2 / g to 150 m2 / g, 25 m2 / g to 125 m2 / g, 25 m2 / g to 100 m2 / g, 25 m2 / g to 75 m2 / g, 25 m2 / g to 50 m2 / g, 30 m2 / g to 500 m2 / g, 40 m2 / g to 500 m2 / g, 50 m2 / g to 60 m2 / g, 70 m2 / g to 500 m2 / g, 80 m2 / g to 500 m2 / g, 90 m2 / g to 500 m2 / g, 100 m2 / g to 500 m2 / g, 125 m2 / g to 150 m2 / g, 175 m2 / g to 500 m2 / g, 200 m2 / g to 500 m2 / g, 225 m2 / g to 500 m2 / g, 250 m2 / g to 500 m2 / g, 275 m2 / g to 500 m2 / g, 300 m2 / g to 500 m2 / g, 325 m2 / g to 500 m2 / g, 350 m2 / g to 500 m2 / g, 375 m2 / g to 500 m2 / g, 400 m2 / g to 500 m2 / g, 425 m2 / g to 500 m2 / g, 450 m2 / g to 500 m2 / g, 25 m2 / g to 200 m2 / g, or 475 m2 / g to 500 m2 / g, or any range based upon any two values described herein.

[0107] The BET surface area of the at least one polysaccharide for any of features a), c), or d) can be at least 10 m2 / g, such as, but not limited to, at least 10 m2 / g, at least 20 m2 / g, at least 30 m2 / g, at least 40 m2 / g, at least 50 m2 / g, at least 60 m2 / g, at least 70 m2 / g, at least 80 m2 / g, at least 90 m2 / g, at least 100 m2 / g, at least 125 m2 / g, at least 150 m2 / g, at least 175 m2 / g, at least 200 m2 / g, at least 225 m2 / g, at least 250 m2 / g, at least 275 m2 / g, at least 300 m2 / g, or can be from 10 m2 / g to 500 m2 / g, 25 m2 / g to 475 m2 / g, 25 m2 / g to 450 m2 / g, 25 m2 / g to 425 m2 / g, 25 m2 / g to 400 m2 / g, 25 m2 / g to 375 m2 / g,2024906 25 m2 / g to 350 m2 / g, 25 m2 / g to 325 m2 / g, 25 m2 / g to 300 m2 / g, 25 m2 / g to 275 m2 / g, 25 m2 / g to 250 m2 / g, 25 m2 / g to 225 m2 / g, 25 m2 / g to 200 m2 / g, 25 m2 / g to 175 m2 / g, 25 m2 / g to 150 m2 / g, 25 m2 / g to 125 m2 / g, 25 m2 / g to 100 m2 / g, 25 m2 / g to 75 m2 / g, 25 m2 / g to 50 m2 / g, 30 m2 / g to 500 m2 / g, 40 m2 / g to 500 m2 / g, 50 m2 / g to 60 m2 / g, 70 m2 / g to 500 m2 / g, 80 m2 / g to 500 m2 / g, 90 m2 / g to 500 m2 / g, 100 m2 / g to 500 m2 / g, 125 m2 / g to 150 m2 / g, 175 m2 / g to 500 m2 / g, 200 m2 / g to 500 m2 / g, 225 m2 / g to 500 m2 / g, 250 m2 / g to 500 m2 / g, 275 m2 / g to 500 m2 / g, 300 m2 / g to 500 m2 / g, 325 m2 / g to 500 m2 / g, 350 m2 / g to 500 m2 / g, 375 m2 / g to 500 m2 / g, 400 m2 / g to 500 m2 / g, 425 m2 / g to 500 m2 / g, 450 m2 / g to 500 m2 / g, 25 m2 / g to 200 m2 / g, or 475 m2 / g to 500 m2 / g, or any range based upon any two values described herein.

[0108] As disclosed herein, the filler (e.g., at least the polysaccharide) can be, and preferably is, uniformly or substantially uniformly distributed in the composite or the at least one elastomer or in the composite. This uniform or substantial uniform distribution can be determined by SEM. As used herein, the terms “uniform” and “uniformly” are intended to mean, conventionally for those skilled in the art, that the concentration of a component, for example, particulate filler, in any given fraction or percentage (e.g., 5%) of a volume is the same (e.g., within 2%) as the concentration of that component in the total volume of the material in question, e.g., elastomer composite or dispersion. Those skilled in the art will be able to verify the statistical uniformity of the material, if required, by means of measurements of concentration of the component using several samples taken from various locations (for example near the surface or deeper in the bulk). A filler concentration that does not satisfy this definition would be considered non-uniformly distributed in the elastomer, which may be desired in certain embodiments or applications. For instance, as an option, a polysaccharide filler can be non-uniformly distributed in the composite or the elastomer or matrix, such as in the form of random regions or pockets of filler that are non- uniformly distributed in the composite or elastomer or matrix.

[0109] As an option, the polysaccharide filler can be the sole or only filler present in the composite or elastomeric composition. Thus, in this option, there is no other filler present except for the polysaccharide filler(s).

[0110] As an option, one or more secondary fillers can be additionally present in the composite or elastomeric composition along with the polysaccharide filler. One2024906 additional secondary filler can be present in the composite or elastomeric composition. Or, as an option, two additional secondary fillers, or three or more additional secondary fillers can be present in the composite or elastomeric composition.

[0111] The secondary filler(s) can be any filler other than a polysaccharide filler, as defined herein. Examples of secondary fillers include, but are not limited to, carbon black (e.g., a furnace black, a gas black, a thermal black, an acetylene black, a plasma black, a reclaimed black, and / or a lamp black), reclaimed carbon, silica-coated carbon black, silica- treated carbon black (dual phase carbon-silica filler), silica, clay, mica, kaolin, chalk, calcium carbonate, carbon nanotubes, graphenes, pyrolysis carbon, carbon fibers, KEVLAR fibers, glass fibers, glass spheres, nylon fibers, graphite, boron nitride, graphite nanoplatelets, or any combinations thereof. The secondary filler can be or include individualized, pristine CNTs, i.e., CNTs that are not generated or derived from CNSs, e.g., during processing. Another example of a secondary filler is reduced graphene oxides, such as densified reduced graphene oxides, as described in U.S. Provisional Patent Application No.62 / 857,296 filed June 5, 2019, and incorporated in its entirety by reference herein.

[0112] As an option, the secondary filler(s) can be selected from carbonaceous materials, carbon black, silica, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, reclaimed carbon, recovered carbon black (e.g., as defined in ASTM D8178-19, rCB), graphenes, graphene oxides, reduced graphene oxide (e.g., reduced graphene oxide worms as disclosed in PCT Publ. No. WO 2019 / 070514A1, the disclosure of which is incorporated by reference herein), or densified reduced graphene oxide granules (as disclosed in U.S. Prov. Appl. No.62 / 857,296, filed June 5, 2019, and PCT Publ. No.2020 / 247681, the disclosures of which are incorporated by reference herein), carbon nanotubes, single-wall carbon nanotubes, multi-wall carbon nanotubes, or combinations thereof, or corresponding coated materials (e.g., silicon-treated carbon black) or chemically-treated materials thereof (e.g., chemically-treated carbon black). Other suitable fillers include carbon nanostructures (CNSs, singular CNS), a plurality of carbon nanotubes (CNTs) that are crosslinked in a polymeric structure by being branched, e.g., in a dendrimeric fashion, interdigitated, entangled and / or sharing common walls with one another. CNS fillers are described in U.S. Pat. No.9,447,259, and PCT Appl. No. PCT / US2021 / 027814, the disclosures of which are incorporated by reference herein. Blends of additional fillers can also be used, e.g., blends2024906 of silica and carbon black, silica and silicon-treated carbon black, and carbon black and silicon-treated carbon black. The filler can be chemically treated (e.g. chemically treated carbon black, chemically treated silica, silicon-treated carbon black) and / or chemically modified. The filler can be or include carbon black having an attached organic group(s). The filler can have one or more coatings present on the filler (e.g. silicon-coated materials, silica- coated material, carbon-coated material). The filler can be oxidized and / or have other surface treatments. There is no limitation with respect to the type of filler (e.g., silica, carbon black, or other filler) that can be used.

[0113] The secondary filler(s) can comprise a fibrous filler including natural fibers, semi-synthetic fibers, and / or synthetic fibers (e.g., nanosized carbon filaments), such as short fibers disclosed in PCT Publ. No. WO 2021 / 153643, the disclosure of which is incorporated by reference herein. Other fibrous fillers include poly(p-phenylene terephthalamide) pulp, commercially available as Kevlar®pulp (Du Pont).

[0114] Other suitable secondary filler(s) include bio-sourced or bio-based materials (derived from biological sources), recycled materials, or other fillers considered to be renewable or sustainable include hydrothermal carbon (HTC, where the filler comprises lignin that has been treated by hydrothermal carbonization as described in U.S. Pat. Nos. 10,035,957, and 10,428,218, the disclosures of which are incorporated by reference, herein), rice husk silica, carbon from methane pyrolysis, siliceous earth, crumb rubber, and functionalized crumb rubber.

[0115] The total loading level of the filler (at least one polysaccharide and optionally one or more secondary fillers) can be at least 30 phr, e.g., the total loading level of the filler can range from 30 phr to 250 phr, from 30 phr to 200 phr, from 30 phr to 180 phr, from 30 phr to 150 phr, from 30 phr to 100 phr, from 30 phr to 90 phr, from 30 phr to 80 phr, from 30 phr to 70 phr, from 30 phr to 65 phr, from 30phr to 60 phr, from 30phr to 50 phr, from 40 phr to 250 phr, from 40 phr to 200 phr, from 40 phr to 180 phr, from 40 phr to 150 phr, from 40 phr to 100 phr, from 40 phr to 90 phr, from 40 phr to 80 phr, from 40 phr to 70 phr, from 40 phr to 65 phr, or from 40phr to 60 phr. If a secondary filler is present, the loading level of the secondary filler can be from about 1 phr to about 200 phr, or from about 5 phr to about 150 phr, or from about 10 phr to about 100 phr, or from about 15 phr to about 90 phr, from about 20 phr to about 80 phr, from about 30 phr to about 802024906 phr, from about 40 phr to about 80 phr, from about 50 phr to about 80 phr, from about 5 phr to 50 phr, from about 5 phr to about 40 phr, from about 5 phr to about 30 phr, from about 5 phr to about 20 phr, or from about 5 phr to about 10 phr and any amounts within any one or more of these ranges.

[0116] In the composites disclosed herein, at least 10 wt%, or at least 50 wt%, or at least 75 wt%, or at least 90 wt% of the filler comprises or is at least one polysaccharide. From 10 wt% to 100 wt% of the filler can be the polysaccharide(s) (based on total weight of all fillers present in the composite, dry basis), such as from 10 wt% to 99 wt%, from 10 wt% to 95 wt%, from 10 wt% to 90 wt%, from 10 wt% to 85 wt%, from 10 wt% to 80 wt%, from 10 wt% to 75 wt%, from 10 wt% to 70 wt%, from 10 wt% to 65 wt%, from 10 wt% to 60 wt%, from 10 wt% to 55 wt%, from 10 wt% to 50 wt%, from 10 wt% to 45 wt%, from 10 wt% to 40 wt%, from 10 wt% to 35 wt%, from 15 wt% to 100 wt%, from 20 wt% to 100 wt%, from 25 wt% to 100 wt%, from 30 wt% to 100 wt%, from 35 wt% to 100 wt%, from 40 wt% to 100 wt%, from 45 wt% to 100 wt%, from 50 wt% to 100 wt%, from 55 wt% to 100 wt%, from 60 wt% to 100 wt% from 60 wt% to 100 wt%, from 70 wt% to 100 wt%, from 75 wt% to 100 wt%, from 80 wt% to 100 wt%, or any range based upon any two values described herein, where the wt% is based on the total weight of filler added to form the composite (or the total weight of filler present in the composite).

[0117] If the polysaccharide is the sole filler, the loading level of the filler can be at least 30 phr, e.g., from 30 phr to 200 phr, from 30 phr to 150 phr, from 30 phr to 100 phr, from 30 phr to 90 phr, from 30 phr to 80 phr, from 30 phr to 70 phr, from 30 phr to 60 phr, from 30 phr to 55 phr, or from 30 phr to 50 phr.

[0118] With regard to silica, if used, one or more types of silica, or any combination of silica(s). The silica suitable for reinforcing elastomer composites can be characterized by a surface area (BET) of about 20 m2 / g to about 450 m2 / g; about 30 m2 / g to about 450 m2 / g; about 30 m2 / g to about 400 m2 / g; or about 60 m2 / g to about 250 m2 / g; and for heavy vehicle tire treads a BET surface area of about 60 m2 / g to about 250 m2 / g or for example from about 80 m2 / g to about 200 m2 / g. Highly dispersible precipitated silica can be used as the filler in the present methods. Highly dispersible precipitated silica (“HDS") is understood to mean any silica having a substantial ability to dis-agglomerate and disperse in an elastomeric matrix. Such determinations may be observed in known manner by electron2024906 or optical microscopy on thin sections of elastomer composite. Examples of commercial grades of HDS include, Perkasil®GT 3000GRAN silica from WR Grace & Co, Ultrasil®7000 silica from Evonik Industries, Zeosil®1165 MP and 1115 MP silica from Solvay S.A., Hi-Sil® EZ 160G silica from PPG Industries, Inc., and Zeopol®8741 or 8745 silica from Evonik. Conventional non-HDS precipitated silica may be used as well. Examples of commercial grades of conventional precipitated silica include, Perkasil®KS 408 silica from WR Grace & Co, Zeosil®175GR silica from Solvay S.A., Ultrasil®VN3 silica from Evonik Industries, Hi-Sil® 243 silica from PPG Industries, Inc. and the Hubersil®161 silica from Evonik. Hydrophobic precipitated silica with surface attached silane coupling agents may also be used. Examples of commercial grades of hydrophobic precipitated silica include Agilon®400, 454, or 458 silica from PPG Industries, Inc. and Coupsil silicas from Evonik Industries, for example Coupsil 6109 silica.

[0119] As a secondary filler, a silica-containing filler can be used. Such a filler can have a silica content of at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, or almost 100 wt% or 100 wt%, or from about 1 wt% to about 100 wt%, all based on the total weight of the particle.

[0120] Any of the silica(s) or silica-containing filler can be chemically functionalized, such as to have attached or adsorbed chemical groups, such as attached or adsorbed organic groups. Any combination of silica(s) and / or silica-containing filler can be used. The silica can be in part or entirely a silica having a hydrophobic surface, which can be a silica that is hydrophobic or a silica that becomes hydrophobic by rendering the surface of the silica hydrophobic by treatment (e.g., chemical treatment). The hydrophobic surface may be obtained by chemically modifying the silica particle with hydrophobizing silanes without ionic groups, e.g., bis-triethoxysilylpropyltetrasulfide. Such a surface reaction on silica may be carried out in a separate process step before dispersion, or performed in-situ in a silica dispersion. The surface reaction reduces silanol density on the silica surface, thus reducing ionic charge density of the silica particle in the slurry. Suitable hydrophobic surface-treated silica particles for use in dispersions may be obtained from commercial sources, such as Agilon®454 silica and Agilon®400 silica, from PPG Industries. Silica2024906 dispersions and destabilized silica dispersions may be made using silica particles having low surface silanol density. Such silica may be obtained through dehydroxylation at temperatures over 150°C via, for example, a calcination process.

[0121] With respect to the carbon black, if used, any reinforcing or non-reinforcing grade of carbon black may be selected to yield the desired property in the final rubber composition. Examples of reinforcing grades are N110, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, and N375. Examples of semi-reinforcing grades are N539, N550, N650, N660, N683, N762, N765, N774, N787, and / or N990.

[0122] The carbon black can have any STSA such as ranging from 5 m2 / g to 250 m2 / g, 11 m2 / g to 250 m2 / g, 20 m2 / g to 250 m2 / g or higher, for instance, at least 70 m2 / g, such as from 70 m2 / g to 250 m2 / g , or 80 m2 / g to 200 m2 / g or from 90 m2 / g to 200 m2 / g, or from 100 m2 / g to 180 m2 / g, from 110 m2 / g to 150 m2 / g, from 120 m2 / g to 150 m2 / g and the like. As an option, the carbon black can have an Iodine Number (I2No) of from about 5 to about 35 mg I2 / g carbon black (per ASTM D1510). The carbon black can be a furnace black or a carbon product containing silicon-containing species, and / or metal containing species and the like. The carbon black can be, e.g., a multi-phase aggregate comprising at least one carbon phase and at least one metal-containing species phase or silicon-containing species phase (also known as silicon-treated carbon black, such as ECOBLACK™ materials from Cabot Corporation). As stated, the carbon black can be a rubber black, and especially a reinforcing grade of carbon black or a semi-reinforcing grade of carbon black. Iodine number (I2No.) is determined according to ASTM Test Procedure D1510. STSA (statistical thickness surface area) is determined based on ASTM Test Procedure D-5816 (measured by nitrogen adsorption). OAN is determined based on ASTM D1765-10. Carbon blacks sold under the Regal®, Black Pearls®, Spheron®, Sterling®, Emperor®, Monarch®, Shoblack™, Propel®, Endure®, and Vulcan®trademarks available from Cabot Corporation, the Raven®, Statex®, Furnex®, and Neotex®trademarks and the CD and HV lines available from Birla, and the Corax®, Durax®, Ecorax®, and Purex®trademarks and the CK line available from Evonik (Degussa) Industries, and other fillers suitable for use in rubber or tire applications, may also be exploited for use with various implementations. Suitable chemically functionalized carbon blacks include those disclosed in WO 96 / 18688 and US2013 / 0165560, the2024906 disclosures of which are hereby incorporated by reference. Mixtures of any of these carbon blacks may be employed.

[0123] The carbon black can be an oxidized carbon black, such as pre-oxidized using an oxidizing agent. Oxidizing agents include, but are not limited to, air, oxygen gas, ozone, NO2(including mixtures of NO2and air), peroxides such as hydrogen peroxide, persulfates, including sodium, potassium, or ammonium persulfate, hypohalites such a sodium hypochlorite, halites, halates, or perhalates (such as sodium chlorite, sodium chlorate, or sodium perchlorate), oxidizing acids such a nitric acid, and transition metal containing oxidants, such as permanganate salts, osmium tetroxide, chromium oxides, or ceric ammonium nitrate. Mixtures of oxidants may be used, particularly mixtures of gaseous oxidants such as oxygen and ozone. In addition, carbon blacks prepared using other surface modification methods to introduce ionic or ionizable groups onto a pigment surface, such as chlorination and sulfonation, may also be used. Processes that can be employed to generate pre-oxidized carbon blacks are known in the art and several types of oxidized carbon black are commercially available.

[0124] Further, as an option, an amount, such as a minor amount (10 wt% or less, based on a total weight of filler or particulate material), of any non-polysaccharide filler, non-silica and non-carbon black particles, such as zinc oxide, or calcium carbonate, or other particulate materials useful in rubber compositions, can be present in the composite.

[0125] As an option, the filler, such as the polysaccharide filler, can be provided as a liquid dispersion for purposes of combining with at least one elastomer. In general, the liquid medium can be any liquid, a solvent, for instance, that is suitable for use with the constituents of the compositions described herein and capable of being used to manufacture the intended elastomeric composition. The solvent can be anhydrous, polar and / or aprotic. In some embodiments, the solvent has a high volatility so that, during manufacturing, it can be easily removed (e.g., evaporated), thereby reducing drying time and production costs. Suitable examples include but are not limited to acetone, a suitable alcohol, water or any combination thereof.

[0126] With respect to the one or more elastomers that can be present, any conventional elastomer can be present along with the filler. The elastomeric compositions2024906 can be considered elastomeric composites or considered rubber compositions or rubber composites.

[0127] Exemplary elastomers include natural rubber (NR), functionalized natural rubber (e.g., epoxidized natural rubber (ENR)), synthetic elastomers such as styrene- butadiene rubber (SBR, e.g., solution SBR (SSBR), emulsion SBR (ESBR), or oil-extended SSBR (OESSBR)), functionalized styrene-butadiene rubber, polybutadiene rubber (BR), functionalized polybutadiene rubber, polyisoprene rubber (IR), ethylene-propylene rubber (EPDM), isobutylene-based elastomers (e.g., butyl rubber), halogenated butyl rubber (e.g., chlorinated butyl rubber (CIIR), brominated butyl rubber (BIIR)), polychloroprene rubber (CR), nitrile rubbers (NBR), hydrogenated nitrile rubber (HNBR), fluoroelastomers, perfluoroelastomers, and silicone rubber. As an option, the elastomer can be selected from at least one of natural rubber, styrene-butadiene rubber, and polybutadiene rubber, including blends thereof.

[0128] Other synthetic polymers that can be used in the present methods (whether alone or as blends) include hydrogenated SBR, and thermoplastic block copolymers (e.g., such as those that are recyclable). Synthetic polymers include copolymers of ethylene, propylene, styrene, butadiene and isoprene. Other synthetic elastomers include those synthesized with metallocene chemistry in which the metal is selected from Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Co, Ni, and Ti. Polymers made from bio-based monomers can also be used, such as monomers containing modern carbon as defined by ASTM D6866, e.g., polymers made from bio-based styrene monomers disclosed in U.S. Pat. No.9,868,853, the disclosure of which is incorporated by reference herein, or polymers made from bio-based monomers such as butadiene, isoprene, ethylene, propylene, farnesene, and comonomers thereof.

[0129] If two or more elastomers are used, the two or more elastomers can be charged into the mixer as a blend at the same time (as one charge or two or more charges) or the elastomers can be added separately in any sequence and amount. For example, the elastomer can comprise natural rubber blended with one or more of the elastomers disclosed herein, e.g., butadiene rubber and / or styrene-butadiene rubber, or SBR blended with BR, etc. For instance, the additional elastomer can be added separately to the mixer and the natural rubber can be added separately to the mixer.2024906

[0130] The elastomer can be or include natural rubber. If the elastomer is a blend, it can include at least 50 wt.% or at least 70 wt.% or at least 90 wt.% natural rubber. The blend can further comprise synthetic elastomers such as one or more of styrene-butadiene rubber, functionalized styrene-butadiene rubber, and polybutadiene rubber, and / or any other elastomers disclosed herein.

[0131] The natural rubber may also be chemically modified in some manner. For example, it may be treated to chemically or enzymatically modify or reduce various non- rubber components, or the rubber molecules themselves may be modified with various monomers or other chemical groups such as chlorine. Other examples include epoxidized natural rubber and natural rubber having a nitrogen content of at most 0.3 wt.%, as described in PCT Publ. No. WO 2017 / 207912.

[0132] Other exemplary elastomers include, but are not limited to, rubbers, polymers (e.g., homopolymers, copolymers and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene, where alkyl may be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propylene and the like.

[0133] Other applicable elastomers that can be used in the presently disclosed methods are disclosed in PCT Publ. No. WO 2020 / 247663, the disclosure of which is incorporated by reference herein.

[0134] Other exemplary elastomers include, but are not limited to, rubbers, polymers (e.g., homopolymers, copolymers and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene, where alkyl may be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propylene and the like.

[0135] As an option, the elastomers include, but are not limited to, natural rubber, solution styrene butadiene rubber (sSBR), emulsion styrene butadiene rubber (ESBR), polybutadiene rubber (BR), butyl rubber, chlorinated butyl rubber (CIIR), brominated butyl ruber (BIIR), polychloroprene rubber, acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), fluoroelastomer (FKM), or perfluoroelastomers (FFKM), Aflas®TFE / P rubber, ethylene propylene diene monomer rubber (EPDM), ethylene / acrylic elastomers (AEM), polyacrylates (ACM), polyisoprene, ethylene-propylene rubber, or any combinations thereof.2024906

[0136] Further examples of elastomers include, but are not limited to derivatives of SBR, natural rubber, such as chlorinated rubber, polybutadiene, polyisoprene, poly(styrene-co-butadiene) and the oil extended derivatives of any of them.

[0137] As an option, the at least one elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, and blends thereof.

[0138] The elastomer may have a glass transition temperature (Tg), as measured by differential scanning calorimetry (DSC), ranging from about -120°C. to about 0°C.

[0139] The composites prepared by any of the methods disclosed herein can consist of elastomer and filler, i.e., no rubber chemicals are present. Alternatively, in addition to filler and elastomer, the composite can comprise at least one additive selected from antidegradants and coupling agents. Alternatively, the composites can include one or more rubber chemicals. In another alternative, the composite can be curative-bearing compositions.

[0140] In a typical mixing process (solid elastomer and dry filler), it is often necessary to add certain additives; typical additives include anti-degradants, coupling agents, and one or more rubber chemicals. Rubber chemicals, as defined herein, include one or more of: processing aids (to provide ease in rubber mixing and processing, e.g. various oils and plasticizers, wax), activators (to activate the vulcanization process, e.g. zinc oxide and fatty acids), accelerators (to accelerate the vulcanization process, e.g. sulphenamides, thiazoles, amines, guanidines, thioureas, thiurams, sulfenamides, thiocarbamates, xanthates, benzothiazoles, and the like), vulcanizing agents (or curatives, to crosslink rubbers, e.g. sulfur, peroxides), and other rubber additives, such as, but not limit to, retarders, co-agents, peptizers, adhesion promoters, tackifiers, resins, flame retardants, colorants, and blowing agents. As an option, the rubber chemicals can comprise processing aids (plasticizers, tackifiers, extenders, chemical conditioners, homogenizing agents, and peptizers such as mercaptans, synthetic oil, petroleum and vegetable oils, resins, rosins, and the like) and activators. As another option, the one or more other rubber chemicals are selected from zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, processing oil, cross-linking and curing agents (peroxides, sulfur, sulfur donors, accelerators,2024906 zinc oxide, and fatty acids), antioxidants, antiozonants, secondary filler(s), additional elastomers, and resins. In addition to the secondary fillers disclosed herein, clay, bentonite, titanium dioxide, talc, calcium sulfate, silica, and / or silicates, etc. and / or mixtures thereof can also be added with the rubber chemicals.

[0141] One or more antidegradants or antioxidants can be used in any of the processes disclosed herein. The antioxidant (an example of an antidegradant) can be an amine type antioxidant, phenol type antioxidant, imidazole type antioxidant, metal salt of carbamate, para-phenylene diamine(s) and / or dihydrotrimethylquinoline(s), polymerized quinine antioxidant, and / or wax and / or other antioxidants used in elastomer formulations. Specific examples include, but are not limited to, N-(1,3-dimethylbutyl)-N'-phenyl-p- phenylenediamine (6-PPD, e.g., ANTIGENE 6C , available from Sumitomo Chemical Co., Ltd. and NOCLAC 6C, available from Ouchi Shinko Chemical Industrial Co., Ltd.), "Ozonon" 6C from Seiko Chemical Co., Ltd., polymerized 1,2-dihydro-2,2,4-trimethyl quinoline, Agerite Resin D, available from R. T. Vanderbilt, butylhydroxytoluene (BHT), and butylhydroxyanisole (BHA), and the like. Other antioxidants are listed in PCT Publ. No. and those listed in WO2012 / 037244, the disclosure of which is incorporated by reference herein. The antidegradant can be introduced in an amount ranging from 0% to 5%, from 0.5% to 5%, from 1% to 5%, from 0% to 3%, from 0.5% to 3%, from 1% to 3%, from 0% to 2%, from 0.5% to 2%, or from 1% to 2% based on the weight of the composite that is formed.

[0142] Any conventional mixing procedure can be used to combine the filler with other components of an elastomer composite. Typical procedures used for rubber compounding are described in Maurice Morton, RUBBER TECHNOLOGY 3rdEdition, Van Norstrand Reinhold Company, New York 1987, and 2ndEdition, Van Nordstrand Reinhold Company, New York 1973 (incorporated in its entirety by reference herein). The mixture of components can be thermomechanically mixed together at a temperature between 120 °C and 180 °C.

[0143] Elastomeric composites, as disclosed herein, can be obtained by suitable techniques that employ, for instance, mixing in a single step or in multiple steps in an internal mixer, such as a Banbury, Intermesh mixers, extruder, on a mill or by utilizing other suitable equipment, to produce a homogenized blend. Specific implementations use2024906 techniques such as those described in U.S. Patent No.5,559,169, published September 24, 1996 which is incorporated herein by reference in its entirety.

[0144] Conventional techniques that are well known to those skilled in the art can be used to prepare the elastomeric compositions and to incorporate the filler. Any conventional dry mixing or liquid mixing technique (e.g. liquid masterbatch technique). The mixing of the rubber or elastomer compound can be accomplished by methods known to those having skill in the rubber mixing art. For example, the ingredients are typically mixed in at least two stages, namely at least one non-productive stage followed by a productive mix stage. The final curatives are typically mixed in the final stage which is conventionally called the "productive" mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) of the preceding non-productive mix stage(s). The terms "non-productive" and "productive" mix stages are well known to those having skill in the rubber mixing art. Wet masterbatch methods for producing filled elastomeric compositions, such as those disclosed in U.S. Patent Nos.5,763,388, 6,048,923, 6,841,606, 6,646,028, 6,929,783, 7,101,922, and 7,105,595 may also be employed to produce elastomeric compositions according to various embodiments disclosed herein, and these patents are incorporated in their entirety by reference herein.

[0145] Any suitable mixer, such as a Banbury or Brabender mixer or other internal or closed mixer, or an open mixer, or an extruder or a continuous compounder or a kneading mixer or a combination thereof, may be employed to combine wet pellets with elastomer. Other mixers include a kneading type internal mixer. Commercially available internal mixers from Farrel-Pomini, Harburg Freudenberger Maschinenbau GmbH (HF), Kobelco, or Pelmar Eng'r Ltd can be used. Besides the option to use inner circuits of steam or water or other fluid in the rotors, in addition or alternatively, the internal mixer can have cooling or heating jackets at one region or part or more than one region or part of the mixing chamber to control the temperature of the components being mixed therein. This can create one or more heating / cooling zones in a wall or portion of a wall of a mixer. The mixer can be a single stage mixer or a multi-stage mixer (e.g., two stages or more). Examples of mixers and designs that can be utilized are described in European Patent No.2423253B1 and U.S. Pat. No.7,556,419, the disclosures of which are incorporated herein by reference.2024906

[0146] As another option, the mixer can be a continuous mixer. For example, the elastomer and filler may be mechanically worked by using one or more of a continuous internal mixer, a twin screw extruder, a single screw extruder, or a roll mill, such as those described in U.S. Pat. No.9,855,686 B2, the disclosure of which is incorporated herein by reference. Suitable kneading and masticating devices are well known and commercially available, including for example, a Unimix Continuous Mixer and MVX (Mixing, Venting, eXtruding) Machine from Farrel Pomini Corporation of Ansonia, Conn., an FCM™ Farrel Continuous Mixer, a long continuous mixer from Pomini, Inc., a Pomini Continuous Mixer, twin rotor corotating intermeshing extruders, twin rotor counterrotating non-intermeshing extruders, continuous compounding extruders, the biaxial milling extruder produced by Kobe Steel, Ltd., and a Kobe Continuous Mixer. Alternative masticating apparatus suitable for use with one or more embodiments disclosed herein will be familiar to those of skill in the art.

[0147] The mixing can be performed with a mixer(s) having at least one rotor and the mixer can be one or more of the following: a kneader, a roll mill, a screw extruder, a twin-screw extruder, a multiple-screw extruder, a continuous compounder, and / or a twin- screw extruder. The mixing can be performed with a mixer(s) having at least one rotor and the mixer can have two-wing rotors, four-wing rotors, six-wing rotors, and / or one or more screw rotors.

[0148] As an option, a continuously-fed latex and the filler such as in the form of a filler slurry, can be introduced and agitated in a coagulation tank. This is also known as a "wet mix" technique. The latex and filler slurry can be mixed and coagulated in the coagulation tank into small beads, referred to as "wet crumb." The various general processes and techniques described in U.S. Patent Nos.4,029,633; 3,048,559; 6,048,923; 6,929,783; 6,908,961; 4,271,213; 5,753,742; and 6,521,691 can be used for this combination of filler with elastomer and coagulation of the latex. Each of these patents are incorporated in their entirety by reference herein. This type of elastomeric formulation can be used with the filler using the various techniques, formulations, and other parameters described in these patents and processes, except that the filler, as described herein, is used.

[0149] Exemplary natural rubber latices include, but are not limited to, field latex, latex concentrate (produced, for example, by evaporation, centrifugation or creaming), skim2024906 latex (e.g., the supernatant remaining after production of latex concentrate by centrifugation) and blends of any two or more of these in any proportion. The latex should be appropriate for the wet masterbatch process selected and the intended purpose or application of the final rubber product. The latex is provided typically in an aqueous carrier liquid. Selection of a suitable latex or blend of latices will be well within the ability of those skilled in the art given the benefit of the present disclosure and the knowledge of selection criteria generally well recognized in the industry.

[0150] As described herein, the present composites can be prepared by mixing at least one filler with at least one elastomer. PCT Publ. No. WO 2020 / 247663, the disclosure of which is incorporated by reference herein, describes mixing processes with solid elastomer and a wet filler (e.g., comprising a filler and a liquid) to enable the batch time and temperature to be controlled beyond that attainable with known dry mixing processes. As an option, the composite can be prepared by a method comprising: (a) charging a mixer having one or more rotors with at least a solid elastomer and a wet filler comprising a filler and a liquid present in an amount of at least 15% by weight based on total weight of wet filler; (b) in one or more mixing steps, mixing the at least the solid elastomer and the wet filler to form a mixture and removing at least a portion of the liquid from the mixture by evaporation, and in at least one of said mixing steps conducting said mixing wherein at least one of the following applies: (i) the mixer has at least one temperature-control means that is set to a temperature, Tz, of 65°C or higher, and (ii) the one or more rotors operate, for at least 50% the mixing time, at a tip speed of at least 0.6 m / s; and (c) discharging, from the mixer, the composite comprising the filler dispersed in the elastomer at a loading of at least 20 phr comprising least 15 phr of at least one silica, wherein the composite has a liquid content of no more than 10% by weight based on total weight of said composite. The mixing can be performed in one, two, three, or more mixing steps.

[0151] The wet filler can comprise the liquid present in an amount of at least 15% by weight based on total weight of wet filler (e.g., liquid present in an amount of at least2024906 20% at least 30%, at least 40%, or ranging from 15% to 80%, ranging from 20% to 70%, ranging from 30% to 60%, or ranging from 40% to 60% by weight based on total weight of wet filler, e.g., wet silica). The wet filler can be in the form of a powder paste, pellet, cake, or slurry. As an option, the mixing of the at least a solid elastomer and wet filler is performed in a mixer having at least one temperature-control means that is set to a temperature, Tz, of 50°C or higher, or 55°C or higher, or 60°C or higher, or 65°C or higher, or 70°C or higher and optionally up to 110°C or 100°C, up to 95°C or up to 90°C. As an alternative or an additional option, the mixing of the at least a solid elastomer and wet filler (e.g., wet silica) is performed in a mixer with one or more rotors of the mixer operating at a tip speed of at least 0.6 m / s for at least 50% of mixing time.

[0152] Further details of mixing solid elastomer with wet filler are disclosed in PCT Publ. No. WO 2020 / 247663, the disclosure of which is incorporated by reference herein.

[0153] As another option, one or more rotors can be mechanically coupled to a mixer motor and at least a portion of the mixing in step (b) is performed under power control in which the rotational speed of the one or more rotors is controlled by a controller that (i) calculates a difference (e.g., automatically calculates the difference) between a measured mixer motor power and a power set point and (ii) adjusts the rotational speed of the one or more rotors if the measured mixer motor power deviates from the power set point, as described in PCT Publ. No. WO 2023 / 034575, the disclosure of which is incorporated by reference herein. As a further option, the mixing can be performed under PID power control. The controller can continuously calculate the difference between the measured mixer motor power and the power set point, e.g., at time intervals ranging from 0.05 s to 5 so or from 0.05 s to 1 s. As an option, one or more stages of the mixing (e.g., first and second stages of the mixing) can be performed under power control.

[0154] The mixing process to combine the components together may be a one stage (single stage) or multi-stage (multi-step) process. In a multi-stage process, one or more mixers or mixer types may be employed.

[0155] Curing can be conducted by techniques known in the art. The elastomeric composition can be a cured elastomeric composition, such as sulfur-cured, peroxide-cured and so forth.2024906

[0156] In any method of producing an elastomer composite, the method can further include one or more of the following steps, after the initial step of combining the elastomer with filler: - one or more holding steps or further solidification or coagulation steps to develop further elasticity; - one or more dewatering steps can be used to de-water the composite to obtain a de-watered composite; - one or more extruding steps; - one or more calendaring steps; - one or more milling steps to obtain a milled composite; - one or more granulating steps; - one or more baling steps to obtain a bailed product or mixture; - the baled mixture or product can be broken apart to form a granulated mixture; - one or more mixing or compounding steps to obtain a compounded composite.

[0157] As a further example, the following sequence of steps can occur and each step can be repeated any number of times (with the same or different settings), after the initial step of combining the elastomer with filler: - one or more holding steps or further coagulation steps to develop further elasticity - dewatering the composite (e.g., the elastomer composite exiting the reaction zone) to obtain a dewatered composite; - mixing or compounding the dewatered composite to obtain a compounded mixture; - milling the compounded mixture to obtain a milled mixture (e.g., roll milling); - granulating or mixing the milled mixture; - optionally baling the mixture after the granulating or mixing to obtain a baled mixture;2024906 - optionally breaking apart the baled mixture and mixing.

[0158] Further disclosed herein are article of manufacture comprising the composite as disclosed herein.

[0159] The article can be a tire or a component thereof. The article can be a tire tread or tire sidewall. The article can be o-ring seals, o-ring sealants, gaskets, diaphragms, valves, hydraulic seals, swell packers, blow out preventers, oil resistant hose liners, wire harnesses, battery cables, turbo hoses, molded air ducts, brake parts, grommets, hydraulic and radiator hoses, transmission seals, transmission gaskets, engine or chassis vibration mounts, constant velocity joint boots, engine seals, or fuel system components.

[0160] The elastomer composite may be used to produce an elastomer or rubber containing product. The elastomeric composition or rubber composition can be for tire or tire parts. Various articles of manufacture, including tires and industrial products, may contain at least one component comprised of an elastomeric composition as disclosed herein. For example, the elastomeric compositions as disclosed herein may be used in forming a composite with reinforcing material such as in the manufacture of tires, belts or hoses. As an option, the composition is incorporated in a tire and more specially as a component of a tire, including, for example, one or more of the tire's tread, wirecoat, beadcoat, sidewall, apex, chafer and plycoat.

[0161] As an option, the elastomer composite may be used in or produced for use in various parts of a tire, for example, tires, tire treads, tire sidewalls, wire-skim for tires, and cushion gum for retread tires. Alternatively or in addition, elastomer composite may be used for hoses, seals, gaskets, anti-vibration articles, tracks, track pads for track-propelled equipment such as bulldozers, etc., engine mounts, earthquake stabilizers, mining equipment such as screens, mining equipment linings, conveyor belts, chute liners, slurry pump liners, mud pump components such as impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, impellers for various applications such as mixing slurries and slurry pump impellers, grinding mill liners, cyclones and hydrocyclones, expansion joints, marine equipment such as linings for pumps (e.g., dredge pumps and outboard motor pumps), hoses (e.g., dredging hoses and outboard motor hoses), and other marine equipment, shaft seals for marine, oil, aerospace, and other applications, propeller shafts,2024906 linings for piping to convey, e.g., oil sands and / or tar sands, and other applications where abrasion resistance and / or enhanced dynamic properties are desired. The vulcanized elastomer composite may be used in rollers, cams, shafts, pipes, tread bushings for vehicles, or other applications where abrasion resistance and / or enhanced dynamic properties are desired.

[0162] Traditional compounding techniques may be used to combine vulcanization agents and other additives known in the art, including the additives discussed above in connection with the dewatered product, with the dried elastomer composite, depending on the desired use.

[0163] As disclosed herein, one or more elastomer and / or reinforcement properties can be obtained that are comparable to or better than composites made using only conventional fillers, such as silica and carbon black.

[0164] As disclosed herein, one or more of the following properties can be achieved which are within acceptable ranges for a composite and / or are comparable or better than composites made using only conventional fillers, such as silica and / or carbon black: a. Elongation at break (e.g., at 23°C), b. Tensile strength (e.g., at 23°C), c. Stress at 100% (e.g., at 23°C), d. Stress at 300% (e.g., at 23°C), e. Rebound % (e.g., at 60°C), f. Shore A hardness (e.g., at 23°C), g. Shore A hardness (e.g., at 60°C), h. Hysteresis (e.g., at 60°C and 10 Hz.

[0165] The particles sizes and / or particle size distributions, including the d50 and d90, can be measured based on laser diffraction, dynamic light scattering, and / or image analysis. The techniques can describe results using standard statistical calculations such as the mean and standard deviation. The laser diffraction technique is preferred for obtaining2024906 d50 and d90 measurements, and this is preferably based on a volume distribution. A Horiba Scientific device can be used, which includes software for such calculations and measurements. Another common approach to define the distribution width is to cite three values on the x-axis, the D10, D50, and D90 in a particle distribution graph. The D50, the median, has been defined above as the diameter where half of the population lies below this value. Similarly, 90 percent of the distribution lies below the D90, and 10 percent of the population lies below the D10.

[0166] The number of particles in the initially prepared product or composite can be determined by imaging the samples using electron microscopy and counting the individual particles using detailed image analysis techniques. Sophisticated programs are widely available for the computer-assisted analysis of electron micrographs that use shape, curvature of the particle surface, edge effects, etc., to discriminate between primary particle and associated particles These results can be treated by well-established statistical methods to yield representative particle numbers, distance between particles, particle size and the number of neighbors, and other particle characteristics.

[0167] Unless otherwise specified, all material proportions described as a percent herein are in weight percent.

[0168] The claims will be further clarified by the following examples which are intended to be only exemplary in nature. EXAMPLES

[0169] The polysaccharide filler used was alpha-1,3-glucan, commercially available as Nuvolve®engineered polysaccharide (International Flavors & Fragrances Inc.). The alpha- 1,3-glucan was provided as highly microcrystalline alpha-1,3-glucan (“MCG”; 10 wt.% solids) or as a wetcake (26 wt.% solids; “WC”).

[0170] The elastomers used were standard grade SMR5 and SMR20 natural rubber ([Hokson Rubber, Malaysia]). Technical descriptions of these natural rubbers are widely available, such as in Rubber World Magazine's Blue Book published by Lippincott and Peto, Inc. (Akron, Ohio, USA).2024906

[0171] The coupling agents used were sodium (2Z)-4-[(4-aminophenyl)amino]-4- oxo-2-butenoate, available as Sumilink®200 coupling agent (“S200”; Sumitomo), 3,3'- dithiobis(propanoic dihydrazide) (Fisher Scientific) and isophthalic dihydrazide (Sigma Aldrich).

[0172] Other additives in include N-(1,3-dimethylbutyl)-N'-phenyl-p- phenylenediamine (“6PPD”), an antioxidant, and N-tert-butyl-2 benzothiazole sulfenamide) (“BBTS”; Akrochem), an accelerator.

[0173] Mixing was performed with the following mixers: Brabender Prep mixer equipped with two cam rotors (“Prep); Brabender Type Six mixer (“Type Six”); a BR-1600 Banbury®mixer (“BR1600”; Manufacturer: Farrell) with a ram pressure of 2.8 bar, fitted with two 2-wing, tangential rotors (2WL), providing a capacity of 1.6L.

[0174] For all samples, curing was carried out in a heated press (150°C) for a time determined by a conventional rubber rheometer, e.g., T90+50% of T90, where T90 is the time to achieve 90% vulcanization (pressure = 2500 lbs).

[0175] The following tests were used to obtain performance data on each of the vulcanizates: ^ Tensile stress at 100% elongation (M100) and tensile stress at 300% elongation (M300) were evaluated by ASTM D412 (Test Method A, Die C) at 23°C, 50% relative humidity and at crosshead speed of 500 mm / min. Extensometers were used to measure tensile strain. Elongation at break and tensile strength were also determined according to ASTM D412. ^ Max tan δ was measured with an ARES-G2 rheometer (Manufacturer: TA Instruments) using 8 mm diameter parallel plate geometry in torsional mode. The vulcanizate specimen diameter size was 8mm diameter and about 2mm in thickness. The rheometer was operated at a constant temperature of 60°C and at constant frequency of 10 Hz. Strain sweeps were run from 0.1-68% strain amplitude. Measurements were taken at ten points per decade and the maximum measured tan δ (“max tan δ”) was reported, also referred to as “tan δ” unless specified otherwise.2024906 ^ Shore A Hardness was measured on vulcanized rubber samples having a thickness of 12.7 mm and diameter of 25.4 mm at 60°C according to ASTM D2240 (1997). ^ Rebound was measured on vulcanized rubber samples having a thickness of 12.7 mm and diameter of 25.4 mm at 60°C according to ASTM D7121 ^ Specific Gravity was measured according to ASTM D792. Examples 1-3 and Comparative Examples 1-4

[0176] This Example describes natural rubber composites and compounds made by mixing a alpha-1,3-glucan (MCG) with elastomer and a coupling agent. The Comparative Examples either do not include a coupling agent or include an additive that is not one of the disclosed coupling agents. Formulations and properties are listed in Table 1. Table 1 Formulation (phr) Comp 1 Comp 2 Comp 3 Comp 4 Ex.1 Ex.2 Ex.3 SMR20 100 100 100 100 100 1 52024906 Examples 1-3

[0177] Stage 1 mixing was performed with the Brabender Prep and the protocol of Table 2 at settings of 120°C and 80 rpm, and a fill factor of 70%. Table 2 Time (s) Temperature (°C) Description 0 Add polymerprotocol of Table 3 at settings of 50°C and 60 rpm, and a fill factor of 63%. Table 3 Time (s) Description 0 Add ½ sta e 1 com osite then the sulfur and accelerator and then theComparative Examples 1-4

[0179] The fillers and additives (if any) for the Comparative formulations are listed below: - Comparative Example 1: no filler; - Comparative Example 2: MCG + polyethylene glycol 3350 (“PEG”; Sigma Aldrich);2024906 - Comparative Example 3: MCG + Jeffamine®D-2000 polyetheramine (from Sigma Aldrich); and - Comparative Example 4: silica with no silane coupling agent (ZEOSIL®Z1165 MP precipitated silica, Solvay USA, Inc).

[0180] Comp 1 (no filler) was mixed in one stage with the Brabender Prep and the protocol of Table 4 at settings of 40°C and 60 rpm, and a fill factor of 60%. Table 4 Time (s) Temperature (°C) Description 0 Add polymer and switch cooling flow water on hng to the protocols of Table 5 (nonproductive) at settings of 110°C and 60 rpm, and a fill factor of 65%. Productive mixing was performed according to the protocol of Table 6 at settings of 70°C and 60 rpm, and a fill factor of 65%. Table 5 Time (s) Temperature (°C) Description 0 Add polymer d.Table 6 Time (s) Description t 1 it th th lf d l t d th th i i

[0182] Nonproductive mixing of Comp 4 (silica filler, no silane) was performed with a Banbury 1.6 L mixer according to the protocol of Table 7, at settings of 60°C and 80 rpm, and a fill factor of 70%. The productive mixing was performed according to the protocol of Table 3.2024906 Table 7 Time (s) Temperature (°C) Description 0 Add 100% masterbatch 30 Add 75% iliincorporated polysaccharide filler and coupling agents S200, 3,3’- dithiobis(propanioic dihydrazide), or isophthalic dihydrazide resulted in properties exceeding that of uncoupled silica filler with the exception of the stress at 300%, which significantly increased from 1.86 MPa to greater than 7.8 MPa by incorporation of the coupling agents. The tanδmax values were noticeably reduced compared to the filled comparative samples. Examples 1-3 provided low specific gravity and high rebound while maintaining similar filler volume fraction. Examples 4 and 5 and Comparative Examples 5 and 6

[0184] The following Examples describe the preparation of natural rubber composites and compounds made by mixing a polysaccharide filler with elastomer and a coupling agent in which a glucan filler wetcake was a solvent-exchanged filler. Formulations and properties are listed in Table 8.2024906 Table 8 Elong Tensil Stre Stres G' at G' at tan R ShorSpecific Gravity, g / mL 0.947 1 1.1517 1.092 1.118 1.0571 1.089 -2024906

[0185] All mixing involving glucan, including blending of glucan and carbon black composites, was performed with a Prep mixer equipped with two cam rotors, with the exception of Example 5, in which mixing was performed with a Type Six mixer. Stage 1 mixing with carbon black or silica filler was performed with a BR-1600 mixer. Example 4

[0186] This Example describes the preparation of a composite comprising a glucan / carbon black filler blend and a coupling agent S200. The glucan filler used was the wetcake form (“WC”; 9.8 vol.% glucan) and the carbon black used was N234 VULCAN®7H carbon black from Cabot Corporation (“V7H”; 9.5 vol.%). The carbon black as mixed was a wet carbon black obtained by jet milling V7H carbon black pellets, followed by re-pelletizing and wetting the dry, milled carbon black with reverse osmosis treated water in a pin pelletizer. The water content of the wet carbon black was in the range of 45-60 % , by weight of wet carbon black.

[0187] In this Example, separate glucan and carbon black composites were prepared initially followed by blending of the composites. Stage 1 mixing of the glucan composite was performed with the protocol of Table 9 at settings of 110°C and 80 rpm, and a fill factor of 70%. Table 9 Time (s) Temperature (°C) Description 0 Add polymer t,

[0188] Stage 1 preparation of the carbon black composite was performed with the protocol of Table 10 at settings of 90°C and 105 rpm, and a fill factor of 70%.2024906 Table 10 Time (s) Temperature (°C) Description 0 Add polymer 30 R d t d t 50 dd 75% fill it 15 dck composites along with rubber chemicals according to the protocol of Table 11 at settings of 70°C and 70 rpm, and a fill factor of 70%. Table 11 Temperature (°C) Description Add glucan and CB compositesle 3. Example 5

[0191] This Example describes the preparation of a composite comprising a glucan- carbon black filler (“V7H”) blend and a coupling agent, S200, in which the glucan was a solvent-exchanged glucan. Separate glucan and carbon black composites were prepared initially followed by blending of the composites.

[0192] Prior to forming the initial glucan composite, a glucan wetcake was subjected to a solvent-exchange process to form a solvent-exchanged wetcake (“WC-SE”). The glucan wetcake was solvent-exchanged with 100 mL of acetone and coupling agent per gram of wetcake BD. This mixture was stirred for 3 h and vacuum filtered with a No.2 filter paper. The residue was not fully dried and quickly resuspended within acetone to produce a 15 wt.% slurry (9.2 vol% glucan).

[0193] A 5 wt.% natural rubber solution was prepared by dissolving SMR20 pieces (less than ¼ in) in a solvent blend of 90 wt.% n-hexane and 10 wt.% acetone, followed by placing this mixture on a roll mill rotating at 26 rpm for 24 h. The resulting solution was2024906 combined with the solvent-exchanged glucan wetcake slurry and mixed for 20 min. with a paddle mixer. Equal volume of acetone was added to coagulate the composite. The coagulated composite was cut into ~ ½ in. pieces and left in a fume hood overnight. The composite was further dried in a 70°C oven for 24 h to complete the removal of solvent.

[0194] A carbon black-containing composite was prepared according to the protocol of Table 10. The solvent-exchanged glucan-natural rubber composite was then combined with the carbon black composite according to the protocol of Table 11. Productive mixing was performed according to the protocol of Table 3. Comparative Examples 5 and 6

[0195] The fillers and additives (if any) for the Comparative Examples 5 and 6 are listed below: - Comparative Example 5: VULCAN®3H carbon black filler from Cabot Corporation at loading of 45 phr (“V3H-45”); and - Comparative Example 6: VULCAN®3H carbon black filler from Cabot Corporation at loading of 55 phr (“V3H-55”).

[0196] Comparative Examples Comp 5 and 6 (45 phr and 55 phr of carbon black) were prepared according to the protocol of Table 12 at settings of 70°C and 70 rpm, and a fill factor of 70%. Productive mixing was performed according to the protocol and settings of Table 3. Table 12 Time (s) Temperature (°C) Description 0 Add ol mer g

[0197] As can be seen from the properties listed in Table 8, rubber reinforcement was noticeably improved when mixing solvent exchanged glucan with natural rubber in organic solvents. Comparative Example 3 containing MCG + PEG reinforces like uncoupled silica, Comparative Example 4. Adding a coupling agent, S200 as in Example 1, results in2024906 some improvement in the reinforcement with a stress at 300% strain increasing from 4.83 MPa to 7.82 MPa.

[0198] The reinforcement level improved with the use of the wetcake form, as demonstrated in Example 5. Example 5, which is the composite with the solvent-exchanged form, provides the highest level of reinforcement with only a small effect on ultimate tensile properties. The reinforcement level approaches that of Comparative Example 5, which has a similar overall loading (~45 phr). This demonstrates that organic solvent exchange of sustainable fillers is a promising approach for the production of rubber compounds. Examples 6-11 and Comparative Examples 7 and 8

[0199] This set of Examples demonstrates the effect on rubber compound properties when the polysaccharide was milled. Specifically, milled versus unmilled glucan composites are prepared in which the glucan was used in its highly crystalline form (“MCG”) or its wetcake form (“WC”). Milling Processes

[0200] An aqueous dispersion of MCG or WC (10 wt.%) was subjected to high shear mixing for 8 min. at 800 rpm with a Dispermat®stirrer fitted with a Cowles blade. The aqueous dispersion was then subjected to a Minicer®Media Mill (NETZSCH Premier Technologies, LLC) containing 0.5 mm yittria stabilized zirconia media with a media charge of 85 vol.%. A residence time of 4.9 min (or 30 minutes of milling time). was applied for both the MCG and wetcake samples to produce sub-micron dispersions. The data of Table 13 demonstrates the filler size that can be achieved depending on the form and the milling time.2024906 Table 13 Volume Weighted D10, μm Form Solvent 1 Pass 5 min. 30 min. 60 min.

[0201] es were achieved with the MCG form whereas the largest particle sizes were achieved with the solvent- exchanged. Time of milling had little effect on size after milling for 5 min. Because of the difficulty in measuring the particle size of MCG (unmilled), it was assumed that the particle size of MCG was greater than the particle size after 1 pass.

[0202] Formulations and properties are shown in Table 14.2024906 Table 14 Formu Glucan Glucan MCG WC MCG, WC, m V3H (p V7H, d V7H, w SMR 2 NR Lat S200 Isopht 6PPDElongaTensileStressStressG' at 6G' at 6tanδmRebouShoreSpecific Gravity, g / mL1.092 1.118 1.112 1.111 1.083 1.081.0891.089 1.090 1.1022024906

[0203] All mixing involving glucan, including blending of glucan and carbon black composites, was performed with a Brabender Prep mixer. Stage 1 mixing with carbon black or silica filler was performed with a BR-1600 mixer. Examples 6-8

[0204] This Example describes the preparation of composites comprising a glucan- carbon black filler (“V7H”) blend, in which a glucan composite is formed from a highly crystalline form (MCG) or wetcake (WC) and blended with a carbon black composite. The composites were formed with or without coupling agent, as listed below. - Example 6: a 1:1 filler blend of WC:carbon black (V7H); - Example 7: a 1:1 filler blend of MCG / carbon black (V7H) filler blend; - Example 8: a 1:1 MCG:carbon black (V7H) filler blend + coupling agent (S200).

[0205] MCG or WC composites were prepared according to the protocol of Table 9 at settings of 110°C and 80 rpm, and a fill factor of 70%. A carbon black composite was performed with the protocol of Table 10 at settings of 90°C and 105 rpm, and a fill factor of 70%, in which the wet carbon black was prepared as described for Example 4. Stage 2 mixing was performed by combining the glucan and carbon black composites along with rubber chemicals according to the protocol of Table 11 at settings of 70°C and 70 rpm, and a fill factor of 70%. Productive mixing was performed with the protocol of Table 3 at settings of 50°C and 60 rpm, and a fill factor of 63%. Examples 9 and 10

[0206] This Example describes the preparation of composites comprising glucan in which the glucan was milled. - Example 9: a 1:1 milled WC:carbon black (V7H) filler blend + coupling agent (S200); and - Example 10: a 1:1 milled MCG:carbon black (V7H) filler blend + coupling agent (S200)2024906

[0207] The glucan forms MCG or WC were milled according to the aqueous milling process described above. To prepare the composite, approximately 400 g of the milled 10 wt.% glucan dispersions were added to 120 g of concentrated latex to produce a 50 phr NR / glucan composite. These two materials were mixed with an overhead stirrer for 10 min., after which 90 mL of 10 vol.% glacial acetic acid was added slowly over the course of 2 minutes to coagulate the natural rubber latex / glucan composite. The coagulated material was kneaded by hand until nearly all the material coagulated and the remaining fluid was devoid of natural rubber latex particles. A hydraulic press was used to remove the remaining water. The sample was cut into small pieces (less than 1 in.) and left to dry in a fume hood overnight. The sample was then placed in an oven at 70°C for 24 h to remove the remaining water present, thereby forming the glucan-based composite.

[0208] A carbon black composite was prepared according to the protocol of Table 12 at settings of 70°C and 70 rpm, and a fill factor of 70%. The resulting glucan-natural rubber composite was combined with the carbon black composite according to the protocol of Table 11 and productive mixing was performed according to the protocol of Table 3. Comparative Examples 7 and 8

[0209] The comparative samples contained VULCAN®3H carbon black filler (“V3H”) from Cabot Corporation, with or without coupling agents as listed below: - Comparative Example 7: 50 phr V3H carbon black + coupling agent (“S200”); - Comparative Example 8: 50 phr V3H carbon black + coupling agent isophthalic dihydrazide.

[0210] All comparative carbon black composites were prepared according to the protocol of Table 12. Productive mixing was performed according to the protocol of Table 3.

[0211] Rubber properties of all compounds are shown in Table 14. Examples 6-8, in addition to Example 4, demonstrate that suitable composites can be made with glucan / carbon black filler blends while providing superior hysteresis compared to the carbon black. Examples 9 and 10 show the benefits of milled engineered polysaccharides including higher reinforcement; see, in particular, Comparative Example 3. The hysteresis and rebound is significantly lower for Examples 4 and 6-10, which can provide advantages in2024906 rolling resistance and fuel economy. Due to the low density of the polysaccharide, the specific gravity of the cured rubber article is comparable or lower, which can help with lightweighting the tire and vehicle. Example 11

[0212] This Example describe the effect of milling on elastomer compositions dispersed with solvent-exchanged glucan. Example 11 is a natural rubber (SMR20) composition comprising a glucan / carbon black filler blend in which the glucan is milled and solvent-exchanged. For Example 11, separate glucan and carbon black composites were prepared initially followed by blending of the composites. Formulations and corresponding rubber properties of Example 11 including those of Example 5 are shown in Table 15. Table 15 Ex.5 Ex.11 Slurry D50, μm > 2.39 1.34

[0213] Nuvolve wetcake was solvent-exchanged with 100 mL of acetone per gram of glucan. This mixture was stirred for 3 h and vacuum filtered with a No.2 filter paper. The residue was not fully dried and quickly resuspended within absolute ethanol. A 15 wt.% solvent exchanged Nuvolve, wetcake was subjected to high shear mixing for 8 min. at 8002024906 rpm with a Dispermat®stirrer fitted with a Cowles blade. The dispersion was subjected to a Minicer®Media Mill (NETZSCH Premier Technologies, LLC) containing 0.5 mm yittria stabilized zirconia media. A residence time of 4.9 minutes was applied to produce sub- micron dispersions.

[0214] A 5 wt.% organic natural rubber solution was prepared by dissolving SMR20 pieces (less than ¼ in) in a solvent blend of 90 wt.% n-hexane and 10 wt.% acetone, followed by placing this mixture on a roll mill rotating at 26 rpm for 24 h. The resulting solution was combined with the solvent-exchanged and milled glucan and mixed for 20 min. with a paddle mixer. Equal volume of acetone was added to coagulate the composite. The coagulated composite was cut into ~ ½ in. pieces and left in a fume hood overnight. The composite was further dried in a 70°C oven for 24 h to complete the removal of solvent.

[0215] From the rubber properties of Table 15, it can be seen that incorporating a milled glucan results in a compound having improved reinforcement properties, particularly stress at 300%, even when compared to a compound containing solvent-exchanged glucan. Examples 12-17 and Comparative Examples 9 and 10

[0216] These Examples describe the preparation of elastomer compounds containing glucan filler in which the elastomer is epoxidized natural rubber (“ENR)”). All formulations and corresponding rubber properties are shown in Table 16.2024906 Table 16 Formu SlurrySlurryENR25ENR25WC (phMCG (Carbon CarbonS2006PPD Zinc Ox Stearic Sulfur BBTSElongaTensileStressStressG' at 6G' at 6tanδmRebouShoreSpecific Gravity, g / mL1.145 1.151 1.127 1.131 1.129 1.134 1.128 1.1442024906

[0217] The composites are listed below. - Example 12: 1:1 filler blend of milled WC:carbon black (V7H); - Example 13: 1:1 filler blend of milled MCG:carbon black (V7H); - Example 14: 1:1 filler blend of milled WC:carbon black (V7H) + coupling agent S200; - Example 15: 1:1 filler blend of milled MCG:carbon black (V7H) + coupling agent S200; - Example 16: 1:1 filler blend of milled MCG:carbon black (V7H) + coupling agent S200; and - Example 17: (2?)1:1 filler blend of milled WC:carbon black (V7H) + coupling agent S200. Examples 12-15

[0218] Separate glucan and carbon black composites were prepared initially followed by blending and compounding of the composites. The glucan composites were prepared according to the protocol of Table 9, and the carbon black composites were prepared according to the protocol of Table 10. The glucan and carbon black composites were blended and compounded according to the protocol of Table 11 and productive mixing was performed according to the protocol of Table 3. Examples 16 and 17

[0219] The aqueous dispersions of MCG and WC glucan were milled according to the process described under “Milling Processes” above to produce milled 10 wt.% dispersions. To prepare the composite, approximately 400 g of the milled glucan dispersions were added to 120 g of concentrated epoxidized natural rubber latex (ENR Latex) with 25 mol.% epoxide groups (Malaysian Rubber Board) to produce a 50 phr glucan composite. These two materials were mixed with an overhead stirrer for 10 min. An equal volume of absolute ethanol was then added slowly over the course of 2 min. to coagulate the composite. A hydraulic press was used to remove the remaining water and solvent. The2024906 sample was cut into small pieces (less than 1 in.) and left to dry in a fume hood overnight. The sample was then placed in an oven at 70°C for 24 h to remove the remaining water present, thereby forming the glucan-based composite.

[0220] Stage 2 mixing was performed by adding free carbon black to the composite in a Brabender Prep mixer according to the protocol of Table 17 at settings of 70°C and 70 rpm, and a fill factor of 70%. Productive mixing was performed according to the protocol of Table 3. Table 17 Time (s) Temperature, °C Description 0 Add composite / sincorporating a milled glucan in an epoxidized natural rubber composite provides beneficial reinforcement properties, particularly stress at 300%.

[0222] The use of the terms “a” and “an” and “the” are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

Claims

2024906 CLAIMS 1. A composite comprising: at least one elastomer; at least one filler in an amount of at least 40 phr, wherein at least 10 wt.% of the filler comprises at least one polysaccharide; and at least one coupling agent, wherein at least one of the following features is present: (a) the at least one polysaccharide has a particle size distribution of 100 nm < d50 < 5000 nm and / or 200 nm < d90 < 7000 nm; (b) the at least one polysaccharide has a BET surface area of at least 25 m2 / g; and / or (c) the at least one coupling agent comprises at least a first functional group and a second functional group, wherein the first functional group is selected from epoxide, amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol, and the second functional group comprises a sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone.

2. The composite of any preceding claim, wherein the at least one polysaccharide comprises at least one of the following: a glucan, a cellulose, an amylose, inulin, a curdlan, a dextran, a xylan, a pullulan, guar gum, an alginate, a pectin, a chitosan, a chitin, and / or a starch, and / or any combinations thereof.

3. The composite of any preceding claim, wherein the at least one polysaccharide comprises a starch.

4. The composite of any preceding claim, wherein the at least one polysaccharide comprises a glucan.

5. The composite of any preceding claim, wherein the at least one polysaccharide comprises alpha-glucan.2024906 6. The composite of any preceding claim, wherein the at least one polysaccharide comprises alpha-glucan alpha-1,3-glucan.

7. The composite of any preceding claim, wherein the at least one polysaccharide is a highly crystalline form comprising insoluble alpha-glucan particles having a degree of crystallinity of at least about 0.65, wherein the insoluble alpha-glucan has a weight-average degree of polymerization (DPw) of at least 10, and at least 50% (by number) of the glycosidic linkages of the insoluble alpha-glucan are alpha-1,3 glycosidic linkages.

8. The composite of any preceding claim, wherein the at least one polysaccharide is a wet cake form.

9. The composite of any preceding claim, wherein the at least one polysaccharide is a highly crystalline form and has the particle size distribution of 100 nm < d50 < 400 nm.

10. The composite of any preceding claim, wherein the at least one polysaccharide is a highly crystalline form and has the particle size distribution of 200 nm < d90 < 600 nm.

11. The composite of any preceding claim, wherein the at least one polysaccharide is a wet cake form and has the particle size distribution of 250 nm < d50 < 1200 nm.

12. The composite of any preceding claim, wherein the at least one polysaccharide is a wet cake form and has the particle size distribution of 350 nm < d90 < 2000 nm.

13. The composite of any preceding claim, wherein at least 50 wt.% of the filler comprises the at least one polysaccharide.

14. The composite of any preceding claim, wherein at least 75 wt.% of the filler comprises the at least one polysaccharide.

15. The composite of any preceding claim, wherein the at least one polysaccharide is a solvent-exchanged polysaccharide.

16. The composite of any preceding claim, wherein the BET surface area of the at least one polysaccharide is from 25 m2 / g to 500 m2 / g.2024906 17. The composite of any preceding claim, wherein a BET surface area of the at least one polysaccharide for feature c) is at least 10 m2 / g.

18. The composite of any preceding claim, wherein the at least one coupling agent is a non-silane coupling agent.

19. The composite of any preceding claim, wherein the first functional group and second functional group of at least one coupling agent are such that the first functional group interacts with the at least one polysaccharide, and the second functional group interacts with the at least one elastomer.

20. The composite of any preceding claim, wherein the first functional group is selected from amine, thiosulfuric acid, hydrazide, phenol, and naphthol, and the second functional group is selected from sulfide, thiosulfuric acid, carboxylic acid, and hydrazide.

21. The composite of any preceding claim, wherein the first and second functional group is hydrazide.

22. The composite of any preceding claim, wherein the at least one coupling agent has the formula: H2N(H)NC(O)– Rn–C(O)N(H)NH2, wherein R can be substituted or unsubstituted and is selected from (i) a divalent C6-C20aromatic hydrocarbon radical, (ii) a divalent saturated or unsaturated C2-C20aliphatic radical, and (iii) a di(C1-C10)alkyl disulfide; and n is 0 or 1.

23. The composite of any one of claims 1-20, wherein the first functional group is amine and the second functional group is carboxylic acid.

24. The composite of any one of claims 1-20, wherein the first and second functional group are each thiosulfuric acid.

25. The composite of any one of claims 1-20, wherein the at least one coupling agent is selected from isophthalic dihydrazide, 3,3'-dithiobis(propanoic dihydrazide), and sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate.

26. The composite of any preceding claim, wherein the at least one coupling agent is present in an amount ranging from 0.1 phr to 10 phr.

27. The composite of any preceding claim, wherein the at least one filler further comprises at least one of carbon black and silica.2024906 28. The composite of any preceding claim, wherein said at least one elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, polyisoprene rubber, ethylene-propylene rubber, isobutylene-based elastomers, halogenated butyl rubber, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, silicone elastomers, and blends thereof.

29. The composite of any preceding claim, wherein the at least one polysaccharide is the sole filler present in said composite.

30. The composite of any one of claims 1-29, wherein at least one secondary filler is present.

31. The composite of claim 30, wherein the least one secondary filler is selected from carbon black, silica, clay, mica, kaolin, metal carbonates, carbon nanotubes, pyrolysis carbon, graphene, carbon fiber, glass fiber, glass sphere, nylon fiber, graphite, metal oxides, boron nitride, graphite nanoplatelet, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-wall carbon nanotubes, multi-wall carbon nanotubes, carbon nanostructures, fragments of carbon nanostructures, or fractured multiwall carbon nanotubes, or any combinations thereof.

32. The composite of claim 1, wherein: (i) at least two of said features a) through c) are present, or (ii) features a) through c) are present, or (iii) at least said feature a) is present, or (iv) at least said feature b) is present, or (v) at least feature c) is present.

33. The composite of any preceding claim, wherein the feature a) obtained by taking a starting polysaccharide and wet milling said starting polysaccharide.

34. The composite of any preceding claim, wherein the feature b) is obtained by taking a starting polysaccharide and conducting a solvent exchange to obtain a higher surface area compared to the surface area of the starting polysaccharide.2024906 35. The composite of claim 34, wherein the higher surface area is an increase of at least 10% to 4000% or more compared to the surface area of the starting polysaccharide.

36. The composite of claim 34 or 35, wherein the solvent exchange utilizes a solvent that is capable of exchanging with water.

37. The composite of any one of claims 34-36, wherein the solvent satisfies an equation using Hansen solubility parameters: Ra < 40 MPa1 / 2, where (Ra)2= 4(δD2– δD1)2 + (δP2– δP1)2+ (δH2– δH1)2.

38. A composite comprising: at least one elastomer; at least one filler in an amount of at least 40 phr, wherein at least 10 wt.% of the filler comprises at least one polysaccharide; and at least one coupling agent comprising at least a first functional group and a second functional group, wherein the first functional group is selected from epoxide, amine, pyridine, benzimidazole, thiosulfuric acid, hydrazide, phenol, naphthol, and catechol, and the second functional group comprises a sulfide, thiosulfuric acid, carboxylic acid, azide, hydrazide, tetrazine, nitrile oxide, and nitrone.

39. An article of manufacture comprising the composite of any preceding claim.

40. The article of claim 39, wherein said article is a tire or a component thereof.

41. The article of claim 39, wherein said article is a tire tread or tire sidewall.

42. The article of claim 39, wherein said article is a o-ring seals, o-ring sealants, gaskets, diaphragms, valves, hydraulic seals, swell packers, blow out preventers, oil resistant hose liners, wire harnesses, battery cables, turbo hoses, molded air ducts, brake parts, grommets, hydraulic and radiator hoses, transmission seals, transmission gaskets, engine or chassis vibration mounts, constant velocity joint boots, engine seals, or fuel system components.

43. A method for preparing the composite of any one of claims 1-38, said method comprising combining the at least one elastomer and the at least one filler and the at least one coupling agent to form said composite.

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