Method of making a composite material having an elastomer, a filler, and a linking agent

Abstract

Disclosed herein are methods of mixing at least a solid elastomer, a wet filler comprising carbon black and a liquid, the liquid being present in an amount of at least 20 weight percent based on the total weight of the wet filler, and a linking agent. In one or more mixing steps, the methods further comprise mixing the at least solid elastomer, wet filler, and linking agent to form a mixture, and removing at least a portion of the liquid from the mixture by evaporation. The methods further comprise discharging from the mixer a composite material comprising a filler dispersed in the elastomer at a loading of at least 20 phr. Also disclosed are composite materials, vulcanized products, and articles formed therefrom.

Description

[0001] This application is a divisional application of Chinese invention patent application (invention title: method for preparing composite material having elastomer, filler and binder, application date: December 8, 2021; application number: 2021800824353). Technical Field

[0002] This document discloses a method for preparing composite materials by combining solid elastomers, wet fillers, and binders. It also discloses composite materials manufactured by the method of the present invention and corresponding vulcanizates derived from these composite materials. Background Technology

[0003] In the rubber industry, there has always been a desire to develop methods for dispersing fillers in elastomers, and in particular, a desire to develop methods that can be achieved efficiently in terms of filler dispersion quality, time, effort, and / or cost.

[0004] Many commercially viable products are formed from elastomer compositions in which reinforcing fillers are dispersed in any of a variety of synthetic elastomers, natural rubbers, or elastomer blends. For example, carbon black and silica are widely used to reinforce natural rubber and other elastomers. Masterbatches are typically produced, which are premixes of reinforcing fillers, elastomers, and various optional additives (e.g., extender oils). Such masterbatches are then compounded with processing and curing additives, and upon curing, a variety of commercially viable products are generated. Such products include, for example, pneumatic and non-pneumatic or solid tires for vehicles, including tread portions (including the crown (driving surface) and base), bottom tread, airtight layer, sidewalls, wire skim, carcass, and others. Other products include, for example, engine mounts, bushings, conveyor belts, windshield wipers, rubber components for aerospace and marine equipment, vehicle track elements, seals, liners, gaskets, wheels, bumpers, vibration damping systems, and the like.

[0005] While there are many methods for incorporating fillers into solid elastomers, there remains a continued need for new methods to achieve acceptable or enhanced elastomer composite dispersion quality and functionality from elastomer composite masterbatches, which can translate into acceptable or enhanced properties in the corresponding vulcanized rubber blends and rubber products. Summary of the Invention

[0006] One aspect is a method for preparing composite materials, the method comprising:

[0007] (a) Loading a mixer with at least a solid elastomer, a wet filler comprising carbon black and liquid, and a binder, wherein the liquid is present in an amount of at least 20% by weight based on the total weight of the wet filler;

[0008] (b) In one or more mixing steps, at least a solid elastomer, a wet filler, and a binder are mixed to form a mixture, and at least a portion of the liquid is removed from the mixture by evaporation; and

[0009] (c) Discharging from the mixer a composite material comprising filler dispersed in an elastomer at a load of at least 20 phr, wherein the composite material has a liquid content of no more than 10% by weight based on the total weight of the composite material.

[0010] The linker is selected from compounds having at least two functional groups, wherein:

[0011] The first functional group is selected from -N(R) 1 (R) 2 ), -N(R 1 (R) 2 (R) 3 ) + A - -S-SO3M 1 and the structures represented by equations (I) and (II),

[0012] (I) (II)

[0013] Where A - The ions are chloride, bromide, iodide, hydroxide, nitrate, or acetate, where X = NH, O, or S, and Y = H or OR. 4 NR 4 R 5 -S n R 4 And n is an integer selected from 1 to 6, and

[0014] The second functional group is selected from thiocarbonyl, nitriles, nitrile ketones, nitrile imines, and -S-SO3M. 2 -S x -R 6 -SH, -C(R) 6 )=C(R 7 )-C(O)R 8 , -C(R 6 )=C(R 7 )-CO2R 8 , -C(R 6 )=C(R 7 )-CO2M 2 ,and

[0015] R 1 -R 8 Each is independently selected from H and C1-C8 alkyl groups; M 1 and M 2 Each is independently selected from H and Na. + K + Li + N(Rʹ)4 + Each Rʹ is independently selected from H and C1-C 20 Alkyl group, and x is an integer selected from 1 to 8.

[0016] Another aspect is a method for preparing composite materials, the method comprising:

[0017] (a) Loading a first mixer with at least a solid elastomer and a wet filler comprising carbon black and liquid, wherein the liquid is present in an amount of at least 20% by weight based on the total weight of the wet filler;

[0018] (b) In one or more mixing steps, at least a solid elastomer and a wet filler are mixed to form a mixture, and at least a portion of the liquid is removed from the mixture by evaporation;

[0019] (c) Discharge from the first mixer a mixture comprising filler dispersed in the elastomer at a load of at least 20 phr, wherein the mixture has a liquid content reduced to less than the liquid content at the beginning of step (b), and wherein the mixture has a material temperature ranging from 100°C to 180°C.

[0020] (d) The mixture from (c) is mixed in a second mixer to obtain a composite material; and

[0021] (e) Discharge from the second mixer a composite material having a liquid content of less than 3% by weight based on the total weight of the composite material.

[0022] The linker is loaded into a first mixer, a second mixer, or both the first and second mixers, wherein the linker is selected from compounds having at least two functional groups.

[0023] The first functional group is selected from -N(R) 1 (R) 2 ), -N(R 1 (R) 2 (R) 3 ) + A - -S-SO3M 1 and the structures represented by equations (I) and (II),

[0024] (I) (II)

[0025] Where A - The ions are chloride, bromide, iodide, hydroxide, nitrate, or acetate, where X = NH, O, or S, and Y = H or OR. 4 NR 4 R 5 -S n R 4 And n is an integer selected from 1 to 6, and

[0026] The second functional group is selected from thiocarbonyl, nitriles, nitrile ketones, nitrile imines, and -S-SO3M. 2 -S x -R 6 -SH, -C(R) 6 )=C(R 7 )-C(O)R 8 , -C(R 6 )=C(R 7 )-CO2R 8 , -C(R 6 )=C(R 7 )-CO2M 2 ,and

[0027] R 1 -R 8 Each is independently selected from H and C1-C8 alkyl groups; M 1 and M 2 Each is independently selected from H and Na. + K + Li + N(Rʹ)4 + Each Rʹ is independently selected from H and C1-C 20 Alkyl group, and x is an integer selected from 1 to 8.

[0028] Another aspect is a method for preparing a vulcanized product, said method comprising curing a composite material prepared by any of the methods disclosed herein in the presence of at least one curing agent to form a vulcanized product. Other aspects include composite materials, vulcanized products, and articles formed therefrom.

[0029] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the method may further comprise any one or more of the following embodiments: the binder further comprises at least one spacer between the first and second functional groups, wherein the at least one spacer is selected from -(CH2). n -,-(CH2) y C(O)-, -C(R) 9 )=C(R 10 -, -C(O)-, -N(R)9 )-, and -C6H4-, where R 9 and R 10 Each is independently selected from H and C1-C8 alkyl groups, and y is an integer selected from 1-10; the linker is selected from thiourea, cystamine, and compounds of formula (1), (2), and (3).

[0030]

[0031]

[0032] ,

[0033] Where M 1 and M 2 Each is independently selected from H and Na. + and N(Rʹ)4 + And R 6 and R 7 Independently selected from H and C1-C6 alkyl groups; the linker is selected from compounds of formula (1) and R 6 and R 7 Each is H; the connecting agent is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate.

[0034] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the method may further comprise any one or more of the following embodiments: the loading includes a separate loading of a binder and wet filler into a mixer; the loading includes multiple additions of a solid elastomer, wet filler, and / or binder; the mixing is performed in one mixing step; the mixing is performed in two or more mixing steps; the mixing in (b) is a second mixing step, wherein the first mixing step includes mixing at least a portion of the solid elastomer and at least a portion of the wet filler, followed by loading a binder into the mixer; the loading in (a) includes loading a mixture comprising a binder and wet filler into the mixer; the loading in (a) includes loading a co-pellet comprising a binder and wet filler into the mixer; in at least one of the mixing steps, the method includes performing the mixing, wherein the mixer has at least one temperature control means set to a temperature T of 65°C or higher. z In at least one of the mixing steps, the method includes mixing with one or more rotors of a mixer operating at a tip speed of at least 0.6 m / s for at least 50% of the mixing time; the resulting total specific energy of the mixed composite material is at least 1,300 kJ / kg.

[0035] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the method may further comprise any one or more of the following embodiments: the wet filler further comprises at least one material selected from: carbonaceous materials, silica, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, pyrolytic carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof, and materials thereof coated and treated; the wet filler further comprises silica; the wet filler has a liquid present in an amount ranging from 20% to 80% by weight based on the total weight of the wet filler; the wet filler is in the form of powder, paste, granules, or cake.

[0036] With respect to any aspect, method, or implementation disclosed herein, where applicable, the method may further comprise any one or more of the following implementations: the solid 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, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluorinated elastomers, perfluorinated elastomers, silicone elastomers, and blends thereof; the solid elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, and blends thereof.

[0037] With respect to any aspect, method, or implementation disclosed herein, where applicable, the method may further include any one or more of the following implementations: the one or more mixing steps are a continuous process; the one or more mixing steps are a batch process.

[0038] With respect to any aspect, method, or embodiment disclosed herein, where applicable, the method may further include any one or more of the following embodiments: the method further includes aging the composite material to form an aged composite material; aging the composite material at a temperature of at least 20°C for at least 5 days; aging the composite material at a temperature of at least 40°C for at least 1 day; a vulcanized product prepared from the aged composite material having a maximum tanδ that increases by no more than 10% of the value of a vulcanized product prepared from the unaged composite material; and a Payne effect that increases by no more than 10% of the value of a vulcanized product prepared from the unaged composite material.

[0039] Specifically, the present invention includes:

[0040] 1. A method for preparing composite materials, including:

[0041] (a) Loading a mixer with at least a solid elastomer, a wet filler comprising carbon black and liquid, and a binder, wherein the liquid is present in an amount of at least 20% by weight based on the total weight of the wet filler;

[0042] (b) In one or more mixing steps, the at least solid elastomer, wet filler, and binder are mixed to form a mixture, and at least a portion of the liquid is removed from the mixture by evaporation; and

[0043] (c) Discharging from the mixer a composite material comprising filler dispersed in the elastomer at a load of at least 20 phr, wherein the composite material has a liquid content of no more than 10% by weight based on the total weight of the composite material.

[0044] The linker is selected from compounds having at least two functional groups, wherein:

[0045] The first functional group is selected from -N(R) 1 (R) 2 ), -N(R 1 (R) 2 (R) 3 ) + A - -S-SO3M 1 and the structures represented by equations (I) and (II),

[0046] (I) (II)

[0047] Where A - The ions are chloride, bromide, iodide, hydroxide, nitrate, or acetate, where X = NH, O, or S, and Y = H or OR. 4 NR 4 R 5 -S n R 4 And n is an integer selected from 1 to 6, and

[0048] The second functional group is selected from thiocarbonyl, nitriles, nitrile ketones, nitrile imines, and -S-SO3M. 2 -S x -R 6 -SH, -C(R) 6 )=C(R 7 )-C(O)R 8 , -C(R 6 )=C(R 7 )-CO2R 8 , -C(R 6 )=C(R 7 )-CO2M2 ,and

[0049] R 1 -R 8 Each is independently selected from H and C1-C8 alkyl groups; M 1 and M 2 Each is independently selected from H and Na. + K + Li + N(Rʹ)4 + Each Rʹ is independently selected from H and C1-C 20 Alkyl group, and x is an integer selected from 1 to 8.

[0050] 2. The method of item 1, wherein the linker further comprises at least one spacer between the first and second functional groups, wherein the at least one spacer is selected from -(CH2). n -,-(CH2) y C(O)-, -C(R) 9 )=C(R 10 -, -C(O)-, -N(R) 9 )-, and -C6H4-, where R 9 and R 10 Each is independently selected from H and C1-C8 alkyl groups, and y is an integer selected from 1 to 10.

[0051] 3. The method of item 1, wherein the linker is selected from thiourea, cystamine, and compounds of formula (1), (2), and (3).

[0052]

[0053]

[0054] .

[0055] 4. The method of any one of items 1-3, where M 1 and M 2 Each is independently selected from H and Na. + and N(Rʹ)4 + And R 6 and R 7 Independently selected from H and C1-C6 alkyl groups.

[0056] 5. The method of item 4, wherein the binder is selected from compounds of formula (1) and R 6 and R 7 Each is represented by H.

[0057] 6. The method of any one of items 1-5, wherein the linker is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate.

[0058] 7. The method of any one of items 1-6, wherein the loading includes a separate loading of the binder and the wet filler into the mixer.

[0059] 8. The method of any one of items 1-7, wherein the loading comprises multiple additions of the solid elastomer, wet filler and / or binder.

[0060] 9. The method of any one of items 1-8, wherein the mixing is performed in a mixing step.

[0061] 10. The method of any one of items 1-8, wherein the mixing is performed in two or more mixing steps.

[0062] 11. The method of Item 10, wherein the mixing in (b) is a second mixing step, wherein the first mixing step comprises mixing at least a portion of the solid elastomer and at least a portion of the wet filler, and subsequently loading the binder into the mixer.

[0063] 12. The method of any one of items 1-11, wherein loading in (a) comprises loading a mixture containing the binder and the wet filler into the mixer.

[0064] 13. The method of any one of items 1-11, wherein loading in (a) comprises loading the mixer with co-granules containing the binder and wet filler.

[0065] 14. The method of any one of items 1-13, wherein in at least one of the mixing steps, the method includes performing the mixing, wherein the mixer has at least one temperature control means, the control means being set to a temperature T of 65°C or higher. z .

[0066] 15. The method of any one of items 1-14, wherein in at least one of the mixing steps, the method comprises mixing 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 the mixing time.

[0067] 16. The method of any one of items 1-15, wherein the resulting total specific energy for mixing is at least 1,300 kJ / kg composite material.

[0068] 17. The method of any one of items 1-16, wherein the wet filler further comprises at least one material selected from: carbonaceous materials, silica, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, pyrolytic carbon, graphene, graphene oxide, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof, and materials thereof that have been coated and treated.

[0069] 18. The method of any one of items 1-16, wherein the wet filler further comprises silica.

[0070] 19. The method of any one of items 1-18, wherein the wet packing has a liquid present in an amount ranging from 20% to 80% by weight based on the total weight of the wet packing.

[0071] 20. The method of any one of items 1-19, wherein the wet filler is in the form of powder, paste, granules or cake.

[0072] 21. The method of any one of items 1-20, wherein the solid 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, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluorinated elastomers, perfluorinated elastomers, silicone elastomers, and blends thereof.

[0073] 22. The method of any one of items 1-20, wherein the solid elastomer is selected from natural rubber, functionalized natural rubber, styrene-butadiene rubber, functionalized styrene-butadiene rubber, polybutadiene rubber, functionalized polybutadiene rubber, and blends thereof.

[0074] 23. The method of any one of items 1-22, wherein the one or more mixing steps are a continuous process.

[0075] 24. The method of any one of items 1-22, wherein the one or more mixing steps are batch processes.

[0076] 25. Methods for preparing composite materials, including:

[0077] (a) Loading a first mixer with at least a solid elastomer and a wet filler comprising carbon black and liquid, wherein the liquid is present in an amount of at least 20% by weight based on the total weight of the wet filler;

[0078] (b) In one or more mixing steps, the at least solid elastomer and wet filler are mixed to form a mixture, and at least a portion of the liquid is removed from the mixture by evaporation;

[0079] (c) Discharge from the first mixer a mixture comprising filler dispersed in the elastomer at a load of at least 20 phr, wherein the mixture has a liquid content reduced to less than the liquid content at the beginning of step (b), and wherein the mixture has a material temperature ranging from 100°C to 180°C.

[0080] (d) The mixture from (c) is mixed in a second mixer to obtain a composite material; and

[0081] (e) Discharge from the second mixer a composite material having a liquid content of less than 3% by weight based on the total weight of the composite material.

[0082] A linker is loaded into the first mixer, the second mixer, or both the first and second mixers, wherein the linker is selected from compounds having at least two functional groups.

[0083] The first functional group is selected from -N(R) 1 (R) 2 ), -N(R 1 (R) 2 (R) 3 ) + A - -S-SO3M 1 and the structures represented by equations (I) and (II),

[0084] (I) (II)

[0085] Where A - The ions are chloride, bromide, iodide, hydroxide, nitrate, or acetate, where X = NH, O, or S, and Y = H or OR. 4 NR 4 R 5 -S n R 4 And n is an integer selected from 1 to 6, and

[0086] The second functional group is selected from thiocarbonyl, nitriles, nitrile ketones, nitrile imines, and -S-SO3M. 2 -S x -R 6 -SH, -C(R) 6 )=C(R 7 )-C(O)R 8 , -C(R 6 )=C(R 7 )-CO2R 8 , -C(R 6 )=C(R7 )-CO2M 2 ,and

[0087] R 1 -R 8 Each is independently selected from H and C1-C8 alkyl groups; M 1 and M 2 Each is independently selected from H and Na. + K + Li + N(Rʹ)4 + Each Rʹ is independently selected from H and C1-C 20 Alkyl group, and x is an integer selected from 1 to 8.

[0088] 26. The method of Item 25, wherein the binder is loaded into the first mixer, and step (b) comprises mixing the at least solid elastomer, wet filler and binder to form a mixture.

[0089] 27. The method of Item 25 or 26, wherein the binder is loaded into the second mixer, and step (d) comprises mixing the mixture from (c) and the binder in the second mixer to obtain a composite material.

[0090] 28. The method of any one of items 25-27, wherein the first and second mixers are identical.

[0091] 29. The method of any of 25-27, wherein the first and second mixers are different.

[0092] 30. The method of any one of items 25-29, wherein the second mixer operates under at least one of the following conditions:

[0093] (i) 5 psi or lower plunger pressure;

[0094] (ii) The plunger is raised to at least 75% of its maximum plunger level;

[0095] (iii) The plunger operates in floating mode;

[0096] (iv) The plunger is positioned such that it is essentially not in contact with the mixture;

[0097] (v) The mixer is plungerless; and

[0098] (vi) The fill factor of the mixture ranges from 25% to 70%.

[0099] 31. A method for preparing a vulcanized product, comprising:

[0100] The composite material prepared by any one of the methods in items 1-30 is cured in the presence of at least one curing agent to form a vulcanized product.

[0101] 32. The method of any one of items 1-31, further comprising aging the composite material to form an aged composite material.

[0102] 33. The method of Item 32, wherein the composite material is aged at a temperature of at least 20°C for at least 5 days.

[0103] 34. The method of Item 32, wherein the composite material is aged at a temperature of at least 40°C for at least 1 day.

[0104] 35. The method of Item 32, wherein the vulcanized product prepared from the aged composite material has a maximum tanδ such that the increase in the maximum tanδ does not exceed 10% of the value of the vulcanized product prepared from the unaged composite material.

[0105] 36. The method of Item 32, wherein the vulcanized product prepared from the aged composite material has a Payne effect that increases by no more than 10% of the value of the vulcanized product prepared from the unaged composite material.

[0106] 37. Articles comprising a vulcanized product prepared by any one of the methods in items 31 to 36. Detailed Implementation

[0107] This document discloses in part a method for preparing or forming composite materials by mixing a solid elastomer with a wet filler. It also discloses in part composite materials, vulcanized products, and articles formed therefrom.

[0108] When mixing fillers with elastomers, a challenge is ensuring the mixing time is long enough to allow sufficient filler incorporation and dispersion before the elastomer in the mixture is subjected to high temperatures and degradation. In typical dry mixing methods, controlling mixing time and temperature to avoid such degradation and optimizing filler incorporation and dispersion is often impossible.

[0109] PCT Publication No. WO2020 / 247663 (the disclosure of which is incorporated herein by reference) describes a mixing process with solid elastomers and wet fillers (e.g., containing fillers and liquids) to enable batch times and temperatures to be controlled beyond those achievable with known dry mixing processes. Other benefits are also available, such as enhanced filler dispersion and / or improved rubber-filler interactions and / or improved rubber compound properties compared to conventionally mixed masterbatches during compounding and vulcanization. At least one of two properties can be improved, for example, the ratio of tensile stress at 300% elongation to stress at 100% elongation (M300 / M100), and the tangential increment (tanδ) measured at 60°C. Higher M300 / M100 values ​​are considered to be associated with improved tire abrasion resistance, and lower tanδ values ​​are considered to be associated with improved tire energy efficiency.

[0110] This document discloses a method for incorporating the use of wet fillers and further incorporating binders in a mixing process with solid elastomers. The composite material formed by the methods disclosed herein can be considered an uncured mixture of fillers and elastomers. The formed composite material can be considered a mixture or masterbatch. Alternatively, the formed composite material can be an intermediate product that can be used in subsequent rubber compounding and one or more vulcanization processes. Prior to compounding and vulcanization, the composite material may undergo additional processes, such as one or more holding steps or further mixing steps, one or more additional drying steps, one or more extrusion steps, one or more calendering steps, one or more milling steps, one or more granulation steps, one or more baling steps, one or more twin-screw discharge extrusion steps, or one or more rubber processing steps to obtain a rubber compound or rubber article.

[0111] In one aspect, this document discloses a method for preparing composite materials, the method comprising:

[0112] (a) Loading a mixer with at least a solid elastomer, a wet filler comprising carbon black and liquid, and a binder, wherein the liquid is present in an amount of at least 20% by weight based on the total weight of the wet filler;

[0113] (b) In one or more mixing steps, at least a solid elastomer, a wet filler, and a binder are mixed to form a mixture, and at least a portion of the liquid is removed from the mixture by evaporation; and

[0114] (c) Discharging from the mixer a composite material comprising filler dispersed in an elastomer at a load of at least 20 phr, wherein the composite material has a liquid content of no more than 10% by weight based on the total weight of the composite material.

[0115] The linker is selected from compounds having at least two functional groups, wherein:

[0116] The first sensory group is selected from -NR 1 R 2 -N(R) 1 (R) 2 (R) 3 ) + A - -S-SO3M 1 and the structures represented by equations (I) and (II),

[0117] (I) (II)

[0118] Where A - The ions are chloride, bromide, iodide, hydroxide, nitrate, or acetate, where X = NH, O, or S, and Y = H or OR. 4 NR 4 R 5 -S n R 4 And n is an integer selected from 1 to 6, and

[0119] The second functional group is selected from thiocarbonyl, nitriles, nitrile ketones, nitrile imines, and -S-SO3M. 2 -S x -R 6 -SH, -C(R) 6 )=C(R 7 )-C(O)R 8 , -C(R 6 )=C(R 7 )-CO2R 8 , -C(R 6 )=C(R 7 )-CO2M 2 ,and

[0120] R 1 -R 8 Each is independently selected from H and C1-C8 alkyl groups; M 1 and M 2 Each is independently selected from H and Na. + K + Li + N(Rʹ)4 + Each Rʹ is independently selected from H and C1-C 20 Alkyl group, and x is an integer selected from 1 to 8.

[0121] Without being bound by any theory, it is believed that while mixing with wet fillers can enhance filler dispersion, the binder can interact with the filler and / or elastomer to produce a stronger interaction between the filler and elastomer. Alternatively, the binder may have at least two functional groups, wherein the first and second functional groups can interact with the elastomer and / or filler. The interaction can involve adsorption or chemical bonding, for example, through ionic interactions, dipole-dipole interactions, hydrogen bonds, covalent bonds, etc. In the composite material, the binder can be in the same form as that loaded onto the mixer or in a different form, for example, if it interacts with the filler and / or elastomer through chemical bonding.

[0122] The linker containing at least two functional groups may contain two, three, four, or more functional groups. In any of these embodiments, the linker contains a first functional group, which may be selected from -NR. 1 R 2 -N(R) 1 (R) 2 (R) 3 ) + A - -S-SO3M 1 and the structures represented by equations (I) and (II),

[0123] (I) (II)

[0124] Where A - The ions are chloride, bromide, iodide, hydroxide, nitrate, or acetate, where X = NH, O, or S, and Y = H or OR. 4 NR 4 R 5 or S n R 4 And n is an integer selected from 1 to 6. In some respects, the first functional group can be chosen from -NR. 1 R 2 (For example, -NHR) 1 (or -NH2), -CO2M 1 , and -S-SO3M 1 .

[0125] The linker may further include a second functional group, which may be selected from thiocarbonyl, nitrile oxide, nitrile ketone, nitrile imine, -S-SO3M 2 -S x -R 6 -SH, -C(R) 6 )=C(R 7 )-C(O)R 8 , -C(R 6 )=C(R 7)-CO2R 8 , -C(R 6 )=C(R 7 )-CO2M 2 In some respects, the second functional group can be selected from -S-SO3M. 2 and -CR 6 =CR 7 -CO2M 2 The functional group is -CO2M 1 and -S-SO3M 1 -S-SO3M 2 and -CR 6 =CR 7 -CO2M 2 In such cases, these can be selected from their acids or salts, such as M 1 and M 2 Each is independently selected from H and Na. + K + Li + and N(Rʹ)4 + (For example, ammonium salts, where each Rʹ is independently selected from H and C1-C) 20 Alkyl groups, such as C1-C 12 Alkyl or C1-C6 alkyl or C1-C4 alkyl, for example, monoalkyl, dialkyl, trialkyl, or tetraalkylammonium salts). The linker contains two or more M... 1 or two or more M 2 In the case of groups, each M 1 Or M 2 It can be independently selected from H and Na. + K + Li + and N(Rʹ)4 + .

[0126] In the implementation scheme described herein, R 1 -R 8 Each is independently selected from H and C1-C8 alkyl groups; M 1 and M 2 Each is independently selected from H and Na. + K + Li + N(Rʹ)4 + And x is an integer selected from 1 to 8.

[0127] As an option, the first functional group can interact with carbon black. Carbon black may have one or more types of surface functional groups, such as, but not limited to, oxygen-containing groups such as carboxylic acids (and their salts), hydroxyl groups (e.g., phenols), esters or lactones, ketones, aldehydes, acid anhydrides, and benzoquinones. As another option, the second functional group can interact with a solid elastomer. The solid elastomer may be a natural elastomer, a synthetic elastomer, or a blend thereof. For example, the solid elastomer may be 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, polychloroprene rubber, nitrile rubber, hydrogenated nitrile rubber, polysulfide rubber, polyacrylate elastomers, fluorinated elastomers, perfluorinated elastomers, silicone elastomers, and blends thereof. As an option, the solid elastomer may be selected from natural rubber, styrene-butadiene rubber, and polybutadiene rubber. Solid elastomers may have olefin groups and / or be functionalized with many groups.

[0128] As an option, the first functional group can be selected from -NR 1 R 2 (e.g., -NH2) and -S-SO3M 1 Furthermore, the second functional group can be selected from -S-SO3M. 2 and -CR 3 =CR 4 -CO2M 2 .

[0129] The binder may contain more than two functional groups. For such a binder, each additional functional group (e.g., a third, fourth, etc.) may be selected from the list of first and second functional groups disclosed herein. Alternatively, more than one type of binder may be used to prepare the composite material.

[0130] The linker may further include at least one spacer between the first and second functional groups. For example, one or more spacers may be bonded to each other and ultimately bonded to the first and second functional groups. As an option, the at least one spacer is selected from -(CH2). n -,-(CH2) y C(O)-, -C(R) 9 )=C(R 10 -, -C(O)-, -N(R) 9 )-, and -C6H4-, where y is an integer selected from 1 to 10 and R 9 and R 10 Each is independently selected from H and C. 1 -C 6 alkyl.

[0131] Exemplary binders are selected from compounds of formula (1), formula (2) and formula (3).

[0132]

[0133]

[0134] .

[0135] M 1 and M 2 As defined in this article, R 6 and R 7 Independently selected from H and C1-C8 alkyl groups (e.g., independently selected from H and C1-C6 alkyl groups or independently selected from H and C1-C4 alkyl groups). As an option, M 1 and M 2 Each is independently selected from H and Na. + and N(Rʹ)4 + For example, selected from H and Na + And R 6 and R 7 They are the same, for example, R 6 and R 7 Each is H. An example of a linker for formula (1) is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate, which can be Sumilink ® 200 coupling agents are commercially available, and an example of the linker for formula (2) is S-(3-aminopropyl)thiosulfate, which can be Sumilink. ® 100 coupling agent (Sumitomo) is commercially available. Examples of the coupling agent in formula (3) are... Tire additives (Eastman Chemical Co.) are commercially available. Other binders include cystamine and thiourea.

[0136] One aspect is a method for preparing composite materials, the method comprising:

[0137] (a) Loading a mixer with at least a solid elastomer, a wet filler comprising carbon black and liquid, and a binder, wherein the liquid is present in an amount of at least 20% by weight based on the total weight of the wet filler;

[0138] (b) In one or more mixing steps, at least a solid elastomer, a wet filler, and a binder are mixed to form a mixture, and at least a portion of the liquid is removed from the mixture by evaporation; and

[0139] (c) Discharging from the mixer a composite material comprising filler dispersed in an elastomer at a load of at least 20 phr, wherein the composite material has a liquid content of no more than 10% by weight based on the total weight of the composite material.

[0140] The binder is selected from:

[0141] (i) dihydrazide compounds, such as those disclosed in U.S. Patent Publication No. 2012 / 0277359A1, the disclosure of which is incorporated herein by reference, particularly including phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide, such as those disclosed in EP0478274, the disclosure of which is incorporated herein by reference; and / or

[0142] (ii) Acylhydrazide compounds, such as those disclosed in U.S. Patent Publication No. 2019 / 0177513, the disclosure of which is incorporated herein by reference; and / or

[0143] (iii) Tetraazine compounds, such as those disclosed in U.S. Patent Publication No. 2020 / 0231782, the disclosure of which is incorporated herein by reference; and / or

[0144] (iv) pyrazolinone-based compounds, such as those disclosed in PCT Publication No. WO2020 / 045575, the disclosure of which is incorporated herein by reference (e.g., Compound 1 and Compound 2); and / or

[0145] (v)Ex. 2,2'-bis(benzimidazolyl-2)ethyl disulfide, as disclosed in U.S. Patent No. 9,200,145, the disclosure of which is incorporated herein by reference; and / or

[0146] (vi) N,N'-bis(2-nitropropyl-1,3-diamino-benzene), as disclosed in U.S. Patent No. 5,213,025, the disclosure of which is incorporated herein by reference; and / or

[0147] (vii) Compounds containing a nitroxide radical, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinoxy radical), such as U.S. Patent Nos. 6,084,015, 6,194,509, 8,584,725 and U.S. Publication No. 2009 / 0292044, the disclosure of which is incorporated herein by reference; and / or

[0148] (viii) 1,3-bis(citrimethylene)benzene, which can be Perkalink ®900 Anti-Reduction Agent (RheinChemieAdditives, Germany) was purchased commercially.

[0149] The amount of binder loaded into the mixer can range from 10 phr or less, for example, 6 phr or less, 5 phr or less, 4 phr or less, 3 phr or less, or 2 phr or less, for example, in the following ranges: 0.1 phr to 10 phr, 0.1 phr to 8 phr, 0.1 phr to 6 phr, 0.1 phr to 5 phr, 0.1 phr to 4 phr, 0.1 phr to 3 phr, 0.2 phr to 10 phr, 0.2 phr to 8 phr, 0.2 phr to 6 phr. phr, 0.2 phr to 5 phr, 0.2 phr to 4 phr, 0.2 phr to 4 phr, 0.2 phr to 3 phr, 0.5 phr to 10 phr, 0.5 phr to 8 phr, 0.5 phr to 6 phr, 0.5 phr to 5 phr, 0.5 phr to 4 phr, 0.5 phr to 3 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 6 phr, 1 phr to 5 phr, 1 phr to 4 phr, or 1 phr to 3 phr.

[0150] A method for preparing a composite material includes the following steps: loading or introducing at least a solid elastomer, a wet filler, and a binder into a mixer, for example, a) one or more solid elastomers and b) one or more fillers, wherein at least one filler or a portion thereof has been wetted with a liquid prior to mixing with the solid elastomer (wet filler). During the mixing step, the solid elastomer combines with the wet filler and binder to form a mixture. The method further includes, in one or more mixing steps, performing the mixing, wherein at least a portion of the liquid is removed by evaporation or an evaporation process occurring during mixing. The liquid in the wet filler can be removed by evaporation (and at least a portion can be removed under the claimed mixing conditions) and can be a volatile liquid, for example, volatile at bulk mixing temperatures. For example, volatile liquids can be distinguished from oils (e.g., bulk oils, process oils) that may be present at least a portion of the mixing time, because such oils are meant to be present in the discharged composite material and therefore do not evaporate during most of the mixing time.

[0151] The packing loaded into the mixer comprises wet packing. In its dry state, the packing may contain little or no liquid (e.g., water or moisture) adsorbed onto its surface. For example, carbon black may have 0 wt.% or 0.1 wt.% to 1 wt.% or up to 3 wt.% or up to 4 wt.% liquid, and precipitated silica may have 4 wt.% to 7 wt.% liquid, for example, 4 wt.% to 6 wt.% liquid (e.g., water or moisture) content. Such packing is referred to herein as dry packing or unwetted packing. With the wet packing of the present invention, liquid or other liquid may be added to the packing and present on most or substantially all of the surface of the packing, which may include liquid-accessible internal surfaces or pores. Thus, sufficient liquid is provided to wet most or substantially all of the surface of the packing before mixing with the solid elastomer. During mixing, as the wet packing is dispersed in the solid elastomer, at least a portion of the liquid may also be removed by evaporation, and then the surface of the packing becomes interactive with the solid elastomer. The wet packing may have a liquid content of at least 20% by weight, relative to the total weight of the wet packing, for example, at least 25% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, or 20% to 99% by weight, 20% to 95% by weight, 20% to 90% by weight, 20% to 80% by weight, 20% to 70% by weight, 20% to 60% by weight, 30% to 99% by weight, 30% to 95% by weight, 30% to 90% by weight, 30% to 80% by weight, 30% to 70% by weight, 30% to 60% by weight, 40% to 99% by weight. Liquid content of the packing material, expressed as a percentage by weight, 40% to 95% by weight, 40% to 90% by weight, 40% to 80% by weight, 40% to 70% by weight, 40% to 60% by weight, 45% to 99% by weight, 45% to 95% by weight, 45% to 90% by weight, 45% to 80% by weight, 45% to 70% by weight, 45% to 60% by weight, 50% to 99% by weight, 50% to 95% by weight, 50% to 90% by weight, 50% to 80% by weight, or 50% to 60% by weight, relative to the total weight of the wet packing material. The liquid content of the packing material can be expressed as the following weight percentages: As an alternative, the amount of liquid can be determined based on the oil adsorption number (OAN) of the filler, where the OAN is determined based on ASTM D2414. The OAN is a measure of the filler structure and can be used to determine the amount of liquid used to wet the filler. For example, wet fillers such as wet carbon black, wet silica (e.g., precipitated silica), or wet silica-treated carbon black may have a liquid content determined according to the following equation: In one embodiment, k ranges from 0.3 to 1.1, or 0.5 to 1.05, or 0.6 to 1.1, or 0.7 to 1.1, or 0.8 to 1.1, or 0.9 to 1.1, or 0.6 to 1.0, or 0.7 to 1.0, or 0.8 to 1.0, or 0.8 to 1.05, or 0.9 to 1.0, or 0.95 to 1, or 0.95 to 1, or 1.0 to 1.1. Alternatively, the wet packing has a liquid content ranging from 20% to 80%, 30% to 70%, 30% to 60%, 40% to 70%, or 40% to 60%.

[0152] As an option, the wet filler has a solid consistency. As an option, the dry filler is only wetted to the extent that the resulting wet filler retains the form of a powder, granules, pellets, cake, or paste, or a similar consistency and / or has the appearance of a powder, granules, pellets, cake, or paste. The wet filler does not flow like a liquid (under zero applied stress). As an option, the wet filler can retain its shape at 25°C (when molded into such a shape), whether it is a single particle, agglomerate, pellet, cake, or paste. The wet filler is not a composite material manufactured by a liquid masterbatch process, and is not any other pre-blended composite material in which the filler is dispersed in a solid elastomer (from an elastomer in a liquid state) (where the elastomer is a continuous phase). The wet filler is not a slurry of filler and does not have the consistency of a liquid or slurry.

[0153] The liquid used for wetting the filler may be or include an aqueous liquid, such as, but not limited to, water. The liquid may include at least one other component, such as, but not limited to, a base, acid, salt, solvent, surfactant, coupling agent (e.g., if the filler further comprises silica) and / or processing aids and / or any combination thereof. More specific examples of the components are NaOH, KOH, acetic acid, formic acid, citric acid, phosphoric acid, sulfuric acid, or any combination thereof. For example, the base may be selected from NaOH, KOH, and mixtures thereof, or the acid may be selected from acetic acid, formic acid, citric acid, phosphoric acid, or sulfuric acid, and combinations thereof. The liquid may be or include a solvent (e.g., an alcohol such as ethanol) that is immiscible with the elastomer used. Alternatively, the liquid consists of about 80 wt.% to 100 wt.% or 90 wt.% to 99 wt.% water, based on the total weight of the liquid.

[0154] In the methods disclosed herein, at least a solid elastomer, wet filler, and binder are loaded (e.g., fed, introduced) into a mixer. The loading of the solid elastomer and / or filler and / or binder may occur in one or more steps or additions. Loading may occur in any manner, including but not limited to batch, semi-continuous, or continuous flow delivery, metering addition, unloading, and / or feeding of the solid elastomer and wet filler into the mixer. The solid elastomer and wet filler are not introduced into the mixer as a premix, wherein the premix is ​​prepared by means other than combining the solid elastomer and wet filler. The solid elastomer and wet filler may be added together, but not as a mixture prepared by means other than combining the solid elastomer and wet filler (e.g., not for predispersing the wet filler into the elastomer (where the elastomer is a continuous phase) by means other than combining the solid elastomer and wet filler). Mixtures, premixes, or preblators from the solid elastomer, wet filler, and binder may be loaded into the mixer and may be prepared by any number of known methods, e.g., in a mixer or container.

[0155] The loading of the solid elastomer, wet filler, and binder may occur simultaneously or sequentially, and may occur in any order. Loading may comprise separate charges of binder and wet filler. Alternatively, loading may comprise a mixture comprising wet filler and binder. For example, (a) adding all of the solid elastomer first, (b) adding all of the wet filler first, (c) adding all of the solid elastomer first with a portion of the wet filler and binder, followed by adding one or more remaining portions of the wet filler and binder, (d) adding a portion of the solid elastomer, followed by adding a portion of the wet filler and / or binder, (e) adding at least a portion of the wet filler first, followed by adding at least a portion of the solid elastomer and / or at least a portion of the binder, (f) simultaneously or approximately simultaneously adding a portion of the solid elastomer, a portion of the wet filler, and a portion of the binder as separate charges to a mixer, or (g) adding at least a portion of the solid elastomer and at least a portion of the wet filler in any order and in one or more portions, mixing at least a portion of the solid elastomer and at least a portion of the wet filler, loading at least a portion of the binder into the mixer, and mixing the solid elastomer, wet filler, and binder to form a mixture. Other suitable methods for loading solid elastomers and wet fillers into a mixer are disclosed in PCT Publication No. WO2020 / 247663, the contents of which are incorporated herein by reference.

[0156] Regarding the mixture comprising a wet filler and a binder, the mixture may be a particulate mixture of the wet filler and the binder, such as a powder. If the binder is liquid, it may be applied to or otherwise bonded to the wet filler by any number of methods known in the art (e.g., impregnation, spraying, etc.). If the binder is solid, it may be applied to or bonded to the wet filler by a solution or dispersion (e.g., an aqueous solution or aqueous dispersion). The powder may be loaded into a mixer as is or may be formed into granules, i.e., granules of the mixture comprising the binder. As another option, a solution or dispersion containing the binder may be bonded to bulk carbon black (and optionally silica and / or other filler types). In addition to bonding, the solution may also wet the carbon black (and optionally silica and / or other filler types) to form a wet filler. The resulting wet filler (e.g., which is or contains wet carbon black) may then be fed into a needle granulator and granulated by the methods disclosed herein.

[0157] The wet packings disclosed herein contain carbon black. On a dry basis, the packing contains, for example, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% carbon black relative to the total weight of the packing, or substantially all of the packing is carbon black. In addition to carbon black, the packing may also contain other types of packing, i.e., at least one additional packing. The additional packing may be granular, fibrous, or plate-like. For example, granular packing is made from a discrete material. Such packing may typically have an aspect ratio (e.g., length to diameter) of 3:1 or less, or 2:1 or less, or 1.5:1 or less. Fibrous packing may have an aspect ratio of, for example, 2:1 or greater, 3:1 or greater, 4:1 or greater, or higher.

[0158] As an option, the at least one additional filler is selected from carbonaceous materials, carbon black, silica, nanocellulose, lignin, clay, nanoclay, metal oxides, metal carbonates, pyrolytic carbon, recycled carbon, recycled carbon black (e.g., rCB as defined in ASTM D8178-19), graphene, graphene oxide, reduced graphene oxide (e.g., reduced graphene oxide worms disclosed in PCT Publication No. WO2019 / 070514A1, the disclosure of which is incorporated herein by reference), or densified reduced graphene oxide particles (e.g., disclosed in U.S. Provisional Application No. 62 / 857,296 and PCT Publication No. 2020 / 247681, filed June 5, 2019, the disclosures of which are incorporated herein by reference), carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof, or corresponding coated materials (e.g., silicon-treated carbon black) or chemically treated materials (e.g., chemically treated carbon black). Other suitable fillers include carbon nanostructures (CNSs, singular CNSs), multiple carbon nanotubes (CNTs) that are crosslinked in the polymer structure by branching (e.g., in a dendritic manner), interlacing, entanglement, and / or sharing a common wall. CNS fillers are described in U.S. Patent No. 9,447,259 and PCT Application No. PCT / US2021 / 027814 (the disclosures of which are incorporated herein by reference). Blends of other fillers may also be used, such as blends of silica and carbon black, silica and silicon-treated carbon black, and carbon black and silicon-treated carbon black. The filler may be chemically treated (e.g., chemically treated carbon black, chemically treated silica, silicon-treated carbon black) and / or chemically modified. The filler may be or comprise carbon black with attached organic groups. The filler may have one or more coating layers present on the filler (e.g., silicon-coated materials, silica-coated materials, carbon-coated materials). The filler may be oxidized and / or have other surface treatments. There are no restrictions on the types of fillers that can be used (e.g., silica, carbon black, or other fillers).

[0159] Other fillers may include fibrous fillers, including natural fibers, semi-synthetic fibers, and / or synthetic fibers (e.g., nanoscale carbon filaments), such as short fibers disclosed in PCT Publication No. WO2021 / 153643 (the disclosure of which is incorporated herein by reference). Other fibrous fillers include those that can be Kevlar. ® DuPont is a commercially available poly(terephthalamide) pulp.

[0160] Other suitable fillers include bio-derived or bio-based materials (derived from bio-sources), recycled materials, or other fillers considered renewable or sustainable, including hydrothermal carbon (HTC, where the filler contains lignin that has been hydrothermally carbonized, as described in U.S. Patent Nos. 10,035,957 and 10,428,218, the disclosures of which are incorporated herein by reference), rice husk silica, carbon from methane pyrolysis, engineered polysaccharide particles, starch, silica, fragmented rubber, and functionalized fragmented rubber. Exemplary engineered polysaccharides include those described in U.S. Patent Publications 2020 / 0181370 and 2020 / 0190270 (the disclosures of which are incorporated herein by reference). For example, the polysaccharide may be selected from: poly-α-1,3-glucan; poly-α-1,3-1,6-glucan; water-insoluble α-(1,3-glucan) polymers having 90% or more of α-1,3-glycosidic bonds, less than 1% by weight of α-1,3,6-glycosidic branching points, and a number-average degree of polymerization in the range of 55 to 10,000; dextran; compositions comprising poly-α-1,3-glucan ester compounds; and water-insoluble cellulose having a weight-average degree of polymerization (DPw) of about 10 to about 1000 and a cellulose II crystal structure.

[0161] As an option, the wet filler may be or include a blend of carbon black and at least one other filler (e.g., silica, silicon-treated carbon black, etc.) in any weight ratio, provided that at least 50% (or at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%) of the filler is carbon black on a dry basis. The wet packing may contain liquid in amounts of about 25 wt.% to about 75 wt.%, for example, about 30 wt% to about 75 wt%, about 40 wt% to about 75 wt%, about 45 wt% to about 75 wt%, about 50 wt% to about 75 wt%, about 30 wt% to about 70 wt%, about 40 wt% to about 70 wt%, about 45 wt% to about 70 wt%, about 50 wt% to about 70 wt%, about 30 wt% to about 65 wt%, about 40 wt% to about 65 wt%, about 45 wt% to about 65 wt%, about 50 wt% to about 65 wt%, about 30 wt% to about 60 wt%, about 40 wt% to about 60 wt%, about 45 wt% to about 60 wt%, or about 50 wt% to about 60 wt%, based on the total weight of the wet packing. The at least one additional packing may be wetted such that the blend of packings has a liquid content of at least 20 wt% based on the total weight of the wet packing, or any amount disclosed herein.

[0162] In addition to wet packing, as an option, the mixture may further include one or more unwetted packings (e.g., any packing not wetted as described herein, such as dry packing, such as packing having no more than 10% by weight of liquid). When unwetted packing is present, the total amount of packing may be such that at least 50% or at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% by weight of the total weight of packing are wet packing, for example, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, 90% to 99%, or 95% to 99% of the total amount of packing may be wet packing, with the remainder of packing in an unwetted state or not considered wet packing.

[0163] The amount of packing material (e.g., wet packing material alone or wet packing material together with other packing materials) loaded into the mixture may be target (based on dry weight) at least 20 phr, at least 30 phr, at least 40 phr, or range from 20 phr to 250 phr, 20 phr to 200 phr, 20 phr to 180 phr, 20 phr to 150 phr, 20 phr to 100 phr, 20 phr to 90 phr, 20 phr to 80 phr, 30 phr to 200 phr. r, 30 phr to 180 phr, 30 phr to 150 phr, 30 phr to 100 phr, 30 phr to 80 phr, 30 phr to 70 phr, 40 phr to 200 phr, 40 phr to 180 phr, 40 phr to 150 phr, 40 phr to 100 phr, 40 phr to 80 phr, 35 phr to 65 phr, or 30 phr to 55 phr, or other amounts within or outside one or more of these ranges. The above phr amounts may also be applied to fillers dispersed in elastomers (filler loading). Other filler types, blends, combinations, etc., may be used, such as those disclosed in PCT Publication No. WO2020 / 247663, the disclosure of which is incorporated herein by reference.

[0164] Regarding the solid elastomer used and mixed with wet filler, the solid elastomer can be considered a dry elastomer or a substantially dry elastomer. The solid elastomer may have a liquid content (e.g., solvent or water content) of 5 wt.% or less, based on the total weight of the solid elastomer, such as 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, or 0.1 wt.% to 5 wt.%, 0.5 wt.% to 5 wt.%, 1 wt.% to 5 wt.%, 0.5 wt.% to 4 wt.%, and so on. The solid elastomer (e.g., the starting solid elastomer) may be a completely elastomer (having a starting liquid, such as water, at a content of 5 wt.% or less), or may be an elastomer further comprising one or more fillers and / or other components. For example, the solid elastomer may be 50 wt.% to 99.9 wt.% elastomer, wherein 0.1 wt.% to 50 wt.% filler is pre-dispersed in the elastomer, wherein the pre-dispersed filler is in addition to the wet filler. Such elastomers can be prepared by a dry mixing process between unwetted fillers and solid elastomers. Alternatively, composite materials manufactured by mixing wet fillers and solid elastomers (e.g., according to the methods disclosed herein) can be used as solid elastomers, and further mixed with wet fillers according to the methods disclosed herein. However, solid elastomers are not composite materials, mixtures, or formulations manufactured by liquid masterbatch processes, and are not any other pre-blended composite materials in which fillers are dispersed in an elastomer while the elastomer is in a liquid state (e.g., latex, suspension, or solution).

[0165] Any solid elastomer can be used in the methods of the present invention. Exemplary elastomers include natural rubber (NR), functionalized natural rubber, synthetic elastomers such as styrene-butadiene rubber (SBR, e.g., solution SBR (SSBR), emulsion SBR (ESBR), or oil-increased SSBR (OESSB+R)), 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, polychloroprene rubber (CR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), fluorinated elastomers, perfluorinated elastomers, and silicone rubbers, such as natural rubber, and blends thereof, such as natural rubber, styrene-butadiene rubber, polybutadiene rubber, and blends thereof, such as blends of the first and second solid elastomers. Other synthetic polymers that can be used in the methods of this invention (whether alone or as blends) include hydrogenated SBRs and thermoplastic block copolymers (e.g., those that are recyclable). Synthetic polymers include copolymers of ethylene, propylene, styrene, butadiene, and isoprene. Other synthetic elastomers include elastomers synthesized using metallocene chemistry, wherein 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 may also be used, such as monomers containing modern carbon as defined by ASTM D6866, for example, polymers made from bio-based styrene monomers disclosed in U.S. Patent No. 9,868,853 (the disclosure of which is incorporated herein by reference), or polymers made from bio-based monomers such as butadiene, isoprene, ethylene, propylene, farnesene, and their comonomers. If two or more elastomers are used, they can be loaded into the mixer simultaneously (as a single charge or two or more charges) as a blend, or they can be added individually in any order and amount. For example, the solid elastomer may comprise natural rubber blended with one or more elastomers disclosed herein (e.g., butadiene rubber and / or styrene-butadiene rubber, or SBR blended with BR, etc.). Alternatively, additional solid elastomers may be added individually to the mixer, and natural rubber may be added individually to the mixer.

[0166] The solid elastomer may be or include natural rubber. If the solid elastomer is a blend, it may include at least 50 wt.% or at least 70 wt.% or at least 90 wt.% of natural rubber. The blend may further include a synthetic elastomer, such as one or more of the following: styrene-butadiene rubber, functionalized styrene-butadiene rubber, and polybutadiene rubber, and / or any other elastomer disclosed herein.

[0167] Natural rubber can also be chemically modified in several ways. For example, it can be treated to chemically or enzymatically modify or reduce various non-rubber components, or the rubber molecules themselves can be modified with various monomers or other chemical groups (e.g., chlorine). Other examples include epoxidized natural rubber and natural rubber with a nitrogen content of up to 0.3 wt.%, as described in PCT Publication No. WO2017 / 207912.

[0168] Other exemplary elastomers include, but are not limited to, rubber, 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene (wherein the alkyl group may be methyl, ethyl, propyl, etc.), acrylonitrile, ethylene, propylene, and polymers such as homopolymers, copolymers, and / or terpolymers.

[0169] Other suitable solid elastomers that can be used in the methods disclosed in this invention are disclosed in PCT Publication No. WO2020 / 247663, the contents of which are incorporated herein by reference.

[0170] Regarding the mixers that can be used in any of the methods disclosed herein, any suitable mixer capable of combining fillers with solid elastomers (e.g., mixing or compounding them together) can be utilized. The mixer can be a batch mixer or a continuous mixer. Combinations of mixers and processes can be utilized in any of the methods disclosed herein, and the mixer can be used sequentially, in series, and / or integrated with other processing equipment. The mixer can be an internal or closed mixer or an open mixer, or an extruder or a continuous compounding machine or a kneading mixer, or a combination thereof. The mixer can be capable of incorporating fillers and binders into the solid elastomer and / or capable of dispersing fillers and binders in the elastomer and / or distributing fillers and binders in the elastomer.

[0171] The mixer may have one or more rotors (at least one rotor). The at least one rotor or the one or more rotors may be a helical rotor, a meshing rotor, a tangential rotor, a kneading rotor, a rotor for an extruder, a roller mill that imparts significant total energy, or a creasing mill. Typically, one or more rotors are utilized in a mixer; for example, a mixer may incorporate one rotor (e.g., a helical rotor), two, four, six, eight, or more rotors. In a given mixer configuration, the rotor groups may be positioned in parallel and / or in a sequential orientation.

[0172] Regarding mixing, mixing can be carried out in one or more mixing steps. Mixing begins when at least a solid elastomer and wet filler are loaded into the mixer and energy is applied to a mixing system that drives one or more rotors of the mixer. The one or more mixing steps can occur after the loading step is completed, or can overlap with the loading step for any length of time. For example, a portion of one or more solid elastomers and / or wet fillers can be loaded into the mixer before or after mixing begins. Then, one or more additional portions of the solid elastomers and / or fillers and / or binders can be loaded into the mixer. For batch mixing, the loading step is completed before the mixing step is finished.

[0173] As an option, controlling the mixer surface temperature by any mechanism can provide the opportunity for longer mixing or residence times, which can result in improved filler dispersion and / or improved rubber-filler interaction and / or consistent and / or efficient mixing compared to mixing processes without temperature control of at least one mixer surface.

[0174] Temperature control means may be, but are not limited to, the flow or circulation of a heat transfer fluid through channels in one or more components of the mixer. For example, the heat transfer fluid may be water or heat transfer oil. For example, the heat transfer fluid may flow through a rotor, mixing chamber walls, a ram, and a drop door. In other embodiments, the heat transfer fluid may flow around one or more components of the mixer in a jacket (e.g., a jacket with fluid flow means) or coil. As another option, the temperature control means (e.g., supplying heat) may be electrical components embedded in the mixer. The system for providing temperature control means may further include means for measuring the temperature of the heat transfer fluid or the temperature of one or more components of the mixer. The temperature measurement may be fed to a system for controlling the heating and cooling of the heat transfer fluid. For example, the desired temperature of at least one surface of the mixer can be controlled by setting the temperature of the heat transfer fluid located in a channel adjacent to one or more components of the mixer (e.g., walls, doors, rotors, etc.).

[0175] The temperature of the at least one temperature control means may, as an example, be set and maintained by one or more temperature control units (“TCUs”). This set temperature or TCU temperature is also referred to herein as “T”. z "With the incorporation of temperature control measures for the heat transfer fluid, T" z It indicates the temperature of the fluid itself.

[0176] As an option, the temperature control method can be set to temperature T. zThe temperature range is 30°C to 150°C, 40°C to 150°C, 50°C to 150°C, or 60°C to 150°C, for example, 30°C to 155°C, 30°C to 125°C, 40°C to 125°C, 50°C to 125°C, 60°C to 125°C, 30°C to 110°C, 40°C to 110°C, 50°C to 110°C, 60°C to 110°C, 30°C to 100°C, 40°C to 100°C, 50°C to 100°C. 60°C to 100°C, 30°C to 95°C, 40°C to 95°C, 50°C to 95°C, 50°C to 95°C, 30°C to 90°C, 40°C to 90°C, 50°C to 90°C, 65°C to 95°C, 60°C to 90°C, 70°C to 110°C, 70°C to 100°C, 70°C to 95°C, 70°C to 90°C, 75°C to 110°C, 75°C to 100°C, 75°C to 95°C, or 75°C to 90°C. Other ranges are possible for devices available in the art.

[0177] Compared to dry mixing, the method of the present invention allows for higher energy input under similar conditions regarding filler type, elastomer type, and mixer type. Controlled removal of water from the mixture enables extended mixing times and thus improves filler dispersion. As described herein, the method of the present invention provides operating conditions that balance longer mixing times with water evaporation or removal within a reasonable timeframe.

[0178] Other operating parameters to consider include the maximum usable pressure. Pressure affects the temperature of the filler and rubber mixture. If the mixer is a batch mixer with a plunger, the pressure inside the mixer chamber can be affected by controlling the pressure applied to the plunger cylinder.

[0179] As another option, the rotor tip speed can be optimized. The energy input to the mixing system is at least partially a function of the speed and type of at least one rotor. The tip speed, taking into account the rotor diameter and rotor speed, can be calculated using the following formula:

[0180] Tip speed, m / s = π x (rotor diameter, m) x (rotation speed, rpm) / 60.

[0181] Since the tip velocity can vary during mixing, as an option, a tip velocity of at least 0.5 m / s or at least 0.6 m / s is achieved for at least 50% of the mixing time, for example, at least 60%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or substantially all of the mixing time. For at least 50% of the mixing time, or other portions of the mixing listed above, the tip velocity may be at least 0.6 m / s, at least 0.7 m / s, at least 0.8 m / s, at least 0.9 m / s, at least 1.0 m / s, at least 1.1 m / s, at least 1.2 m / s, at least 1.5 m / s, or at least 2 m / s. Tip speeds can be selected to minimize mixing time, or can be 0.6 m / s to 10 m / s, 0.6 m / s to 8 m / s, 0.6 to 6 m / s, 0.6 m / s to 4 m / s, 0.6 m / s to 3 m / s, 0.6 m / s to 2 m / s, 0.7 m / s to 4 m / s, 0.7 m / s to 3 m / s, 0.7 m / s to 2 m / s, 0.7 m / s to 10 m / s, 0.7 m / s to 8 m / s, 0.7 to 6 m / s, 1 m / s to 10 m / s, 1 m / s to 8 m / s, 1 m / s to 6 m / s, 1 m / s to 4 m / s, 1 m / s to 3 m / s, or 1 m / s to 2 m / s (e.g., for at least 50% of the mixing time or other mixing times described herein).

[0182] Any or a combination of commercial mixers having one or more rotors, temperature control means and other components, as well as related mixing methods for producing rubber compounds, can be used in the methods of this invention, such as those disclosed in PCT Publication No. WO2020 / 247663, the disclosure of which is incorporated herein by reference.

[0183] The phrase "one or more mixing steps" is understood to mean that the steps disclosed herein can be a first mixing step prior to emission, followed by further mixing steps. The one or more mixing steps can be a single mixing step, for example, a one-stage or single-stage mixing step or process, wherein mixing is carried out under one or more of the following conditions: at least one mixer temperature is controlled by a temperature control means, wherein one or more rotors operate at a tip speed of at least 0.6 m / s for at least 50% of the mixing time, and / or at least one temperature control means is set to a temperature T of 65°C or higher. z And / or continuous mixing; each described in further detail herein. In some cases, the composite material may be discharged with a liquid content not exceeding 10% by weight in a single stage or single mixing step. In other embodiments, two or more mixing steps or mixing stages may be performed, provided that one of the mixing steps is carried out under one or more of the specified conditions.

[0184] As indicated, during the one or more mixing steps, in any of the methods disclosed herein, at least some of the liquid present in the introduced mixture and / or wet filler is removed at least partially by evaporation. Alternatively, the one or more mixing steps or stages may further remove a portion of the liquid from the mixture by expression, compaction, and / or wringing, or any combination thereof. Alternatively, a portion of the liquid may be discharged from the mixer after or simultaneously with the discharge of the composite material.

[0185] During the mixing cycle, after most of the liquid has been released from the composite material and incorporated into the filler, the mixture undergoes a temperature rise. Excessive temperature rise is desirable to avoid, as it can degrade the elastomer. Discharge (e.g., "unloading" in batch mixing) may occur based on time or temperature, or specific energy or power parameters chosen to minimize such degradation.

[0186] In any of the methods disclosed herein, a discharge step from a mixer occurs and a composite material comprising filler dispersed in natural rubber with a total load of at least 20 phr, for example, 20 to 250 phr, or other loads disclosed herein. Alternatively, discharge occurs based on a defined mixing time. The mixing time between the start of mixing and discharge can be about 1 minute or longer, for example, about 1 minute to 40 minutes, about 1 minute to 30 minutes, about 1 minute to 20 minutes, or 1 minute to 15 minutes, or 3 minutes to 1 minute, 5 minutes to 30 minutes, or 5 minutes to 20 minutes, or 5 minutes to 15 minutes, or 1 minute to 12 minutes, or 1 minute to 10 minutes, or other times. Alternatively, for batch internal mixers, plunger downtime can be used as a parameter for monitoring batch mixing time, for example, the time the mixer operates with the plunger in its lowest position, such as fully seated, or with the plunger deflected (as described in PCT Publication No. WO2020 / 247663, the disclosure of which is incorporated herein by reference). Plunger downtime can be less than 30 min, less than 15 min, less than 10 min, or range from 3 min to 30 min, or 5 min to 15 min, or 5 min to 10 min. Alternatively, discharge can occur based on unloading or discharge temperature. For example, the mixer may have unloading temperatures ranging from 120°C to 190°C, 130°C to 180°C, such as 140°C to 180°C, 150°C to 180°C, 130°C to 170°C, 140°C to 170°C, 150°C to 170°C, or other temperatures within or outside these ranges.

[0187] The method further includes discharging the resulting composite material from the mixer. Based on the total weight of the composite material, the discharged composite material may have a liquid content of no more than 10% by weight, as described by the following equation:

[0188]

[0189] In any of the methods disclosed herein, the discharged composite material may have the following liquid content: not exceeding 10% by weight, based on the total weight of the composite material; for example, not exceeding 9% by weight, not exceeding 8% by weight, not exceeding 7% by weight, not exceeding 6% by weight, not exceeding 5% by weight, not exceeding 2% by weight, or not exceeding 1% by weight, based on the total weight of the composite material. This amount may range from 0.1% by weight to 10% by weight, 0.5% by weight to 9% by weight, 0.5% by weight to 7% by weight, 0.5% by weight to 5% by weight, or 0.5% by weight to 3% by weight, based on the total weight of the composite material discharged from the mixer at the end of the method. In any of the methods disclosed herein, the liquid content (e.g., “moisture content”) may be measured as the weight percentage of liquid present in the composite material based on the total weight of the composite material.

[0190] In any of the methods disclosed herein, the liquid content in a composite material can be measured as the weight percentage of liquid present in the composite material based on the total weight of the composite material. Many instruments are known in the art for measuring the liquid (e.g., water) content in rubber materials, such as the coulometric Karl Fischer titration system, or moisture balance, for example from Mettler (Toledo International, Inc., Columbus, OH).

[0191] In any of the methods disclosed herein, while the discharged composite material may have a liquid content of 10% by weight or less, liquid (e.g., water) may optionally be present in the mixer, which is not retained in the discharged composite material. This excess liquid is not part of the composite material and is not part of any liquid content calculated for the composite material.

[0192] In any of the methods disclosed herein, the total liquid content (or total water content or total moisture content) of the material loaded into the mixer is higher than the liquid content of the composite material discharged at the end of the method. For example, the liquid content of the discharged composite material may be 10% to 99.9% (wt.% vs. wt.%), 10% to 95%, or 10% to 50% lower than the liquid content of the material loaded into the mixer.

[0193] Optionally, the method further includes adding a binder and optionally an anti-degradation agent during loading or mixing (i.e., during one or more mixing steps). In any embodiment disclosed herein, as another option, after mixing of at least the solid elastomer and the wet filler has begun and before the discharge step, the method may further include adding a binder and optionally at least one anti-degradation agent to the mixer such that the binder and said at least one anti-degradation agent are mixed with the solid elastomer and the wet filler. As an option, the mixture consists essentially of a solid elastomer and a wet filler; the mixture consists essentially of a solid elastomer, a wet filler, and an anti-degradation agent; the composite material consists essentially of filler and an anti-degradation agent dispersed in an elastomer; the composite material consists of filler dispersed in an elastomer; the composite material consists of filler and an anti-degradation agent dispersed in an elastomer. As another option, the addition of the binder and the anti-degradation agent may occur before the composite material is formed and has a water content of 10 wt% or less, or 5 wt% or less.

[0194] The addition of the binder and optional anti-degradation agent can be performed at any time prior to the discharge step, for example, before or after the mixer reaches an indicated mixer temperature of 120°C or higher. This indicated mixer temperature can be measured by a temperature measuring means within the mixing chamber. The indicated mixer temperature may be the same as or differ from the highest temperature of the mixture or composite material reached during the mixing stage by 30°C or less, or 20°C or less, or 10°C or less (or 5°C or less, or 3°C or less, or 2°C or less) (which can be determined by removing the composite material from the mixer and inserting a thermocouple or other temperature measuring means into the composite material). In this mixing method, as an option, the binder and optional anti-degradation agent may be added to the mixer when the mixer reaches a temperature of 120°C or higher. In other embodiments, the indicated temperature may be in the range of 120°C to 190°C, 125°C to 190°C, 130°C to 190°C, 135°C to 190°C, 140°C to 190°C, 145°C to 190°C, 150°C to 190°C, 120°C to 180°C, 125°C to 180°C, 130°C to 180°C. 135°C to 180°C, 140°C to 180°C, 145°C to 180°C, 150°C to 180°C, 120°C to 170°C, 125°C to 170°C, 130°C to 170°C, 135°C to 170°C, 140°C to 170°C, 145°C to 170°C, 150°C to 170°C, and so on.

[0195] Examples of anti-degradation agents that can be introduced include N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), and others are described in other sections of this document. Anti-degradation agents can be introduced in amounts ranging from 1% to 5% by weight, 0.5% to 2% by weight, or 0% to 3% by weight based on the weight of the resulting composite material. Anti-degradation agents added during the effluent or mixing steps can help prevent elastomer degradation during mixing; however, due to the presence of water in the mixture, the degradation rate of the elastomer is lower compared to dry mixing processes, and the addition of anti-degradation agents can be delayed.

[0196] Following the formation and discharge of the composite material, the method may include a further optional step of blending the composite material with an additional elastomer to form a composite material comprising a blend of the elastomer. The "additional elastomer" or second elastomer may be another natural rubber, or may be a non-natural rubber elastomer, such as any elastomer disclosed herein, for example, synthetic elastomers (e.g., styrene-butadiene rubber (SBR, e.g., SSBR, ESBR, etc.), polybutadiene (BR) and polyisoprene rubber (IR), ethylene-propylene rubber (e.g., EPDM), isobutylene-based elastomers (e.g., butyl rubber), polychloroprene rubber (CR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), polysulfide rubber, polyacrylate elastomers, fluororubber, perfluororubber, and silicone elastomers). Blends of two or more types of elastomers (blends of the first and second elastomers) may also be used, including blends of synthetic and natural rubbers or blends with two or more types of synthetic or natural rubbers.

[0197] Two or more charges of different elastomers can be loaded into a mixer to form a composite blend. For example, undried natural rubber and at least one other elastomer can be loaded into the mixer, wherein the at least one other elastomer is also a coagulated or solid elastomer (e.g., having less than 5% water). Alternatively, an elastomer blend can be loaded into the mixer. As another option, the method may include mixing the discharged composite material with another elastomer to form a blend. The discharged composite material (e.g., after single-stage, two-stage, or multi-stage mixing) may have a moisture content of no more than 5% by weight, 3% by weight, or 2% by weight, relative to the weight of the composite material when blended with one or more other elastomers (e.g., a composite material containing carbon black and natural rubber may be blended with a synthetic elastomer such as BR or SBR). Furthermore, both the elastomer and filler (wet or dry, such as wet or dry carbon black and / or silica and / or silicon-treated carbon black) may be incorporated into the composite material.

[0198] As an alternative, composite materials comprising fillers (e.g., carbon black and / or silica) and elastomers (e.g., natural rubber and / or SBR and / or BR) prepared according to the methods disclosed herein can be combined with masterbatches containing natural rubber and / or synthetic polymers prepared by any method known in the art (e.g., by known dry mixing or solvent masterbatch processes). For example, silica / elastomer masterbatches can be prepared as described in U.S. Patent Nos. 9,758,627 and 10,125,229, or masterbatches derived from neodymium-catalyzed polybutadiene, as described in U.S. Patent No. 9,758,646, the disclosure of which is incorporated herein by reference. Masterbatches may have fibrous fillers, such as poly(terephthalamide) slurry, as described in U.S. Patent No. 6,068,922, the disclosure of which is incorporated herein by reference. Masterbatches may contain fillers such as graphene, graphene oxide, reduced graphene oxide, or densified reduced graphene oxide particles, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanostructures, wherein masterbatches of the latter are disclosed in U.S. Patent No. 9,447,259 and PCT Application No. PCT / US2021 / 027814, the disclosures of which are incorporated herein by reference. Other suitable masterbatches may include composite materials prepared from mixed wet fillers and solid elastomers, as described in PCT Publication No. WO2020 / 247663, the disclosure of which is incorporated herein by reference. For example, masterbatches may contain fillers such as carbon black and / or silica and elastomers such as natural rubber and / or SBR and / or butadiene rubber. Commercially available masterbatches may also be used, such as those from... Silica / SBR masterbatch or Commercially available masterbatches for carbon black / SBR (both available from the Dynasol Group).

[0199] Exemplary masterbatches containing elastomer blends (whether the blends are formed by a first or single-stage mixing or by a multi-stage mixing) include: blends of natural rubber with synthetic, biological and / or functionalized elastomers (e.g., SSBR, ESBR, BR), wherein the filler may be selected from one or more of carbon black, silica and silicon-treated carbon black.

[0200] In addition to solid elastomers, wet fillers, and binders, one or more charges of at least one other elastomer may be loaded into the mixer to form a composite blend. Alternatively, the method may include mixing the discharged composite material with another elastomer to form a blend. The at least one other elastomer may be the same as or different from the solid elastomer.

[0201] Alternatively, the composite material may contain at least one additive selected from anti-degradation agents and coupling agents at the time of discharge (e.g., where the wet filler further contains silica, or where dry silica is loaded into the mixer), which may be added at any time during discharge or mixing.

[0202] The carbon black may be untreated carbon black or treated carbon black or a mixture thereof. The filler may be or include wet carbon black in the form of granules, loose powder, particles and / or agglomerates. Wet carbon black may be formed into granules, particles or agglomerates in, for example, a granulator, fluidized bed or other equipment to manufacture wet filler.

[0203] Wet carbon black may be one or more of the following:

[0204] - Never-dried carbon black; and / or

[0205] - Never-dried carbon black granules; and / or

[0206] - Dry carbon black granules that have been re-wetted (e.g., with water in a pelletizer); and / or

[0207] - Dried carbon black granules that have been ground and then re-wetted with water in a granulator; and / or

[0208] - Dry carbon black granules bound to water; and / or

[0209] - Fluffy powder, granules, or agglomerates that are bound to water.

[0210] In typical carbon black manufacturing, carbon black is initially prepared as a dry, finely granulated (fluffy) material. Fluffy carbon black can be densified by conventional granulation processes, for example, by combining the carbon black with a liquid (e.g., adding water) and feeding the mixture into a needle granulator. Alternatively, the liquid can be a solution or dispersion containing a binder. Needle granulators are well known in the art and include those described in U.S. Patent No. 3,528,785. The resulting wet granules are then heated under controlled temperature and time parameters to remove the liquid from the granules, followed by further processing and transport. In an alternative method, carbon black granules can be manufactured by a process that omits the drying step. In such a method, the granulated carbon black contains at least 20% by weight of process water based on the total weight of the wet carbon black, for example, at least 30% by weight, or at least 40% by weight.

[0211] Alternatively, dried carbon black granules (e.g., commercially available carbon black granules) can be re-wetted in a granulator. The granules can be granulated, ground, classified, and / or milled, for example, in an air jet mill. The resulting carbon black is in a fluffy form and can be re-granulated in a granulator, or compressed or agglomerated in the presence of water to wet the carbon black. As an option, the carbon black can be repalletized in a granulator in the presence of a solution or dispersion containing a binder. Alternatively, fluffy carbon black can be compressed into other forms, such as brick form, using equipment known in the art. As another option, carbon black, such as carbon black granules or fluffy carbon black, can be wetted, for example, by using a fluidized bed, sprayer, mixer, or rotary drum and the like. In the case where the liquid is water, carbon black that has never been dried or carbon black that has been re-wetted can have a water content ranging from 20% to 80% by weight, 30% to 70% by weight, or other ranges such as 55% to 60% by weight, relative to the total weight of wet carbon black.

[0212] Carbon black can be furnace black, gas black, thermal black, acetylene black or lamp black, plasma black, recycled carbon black (e.g., as defined in ASTM D8178-19), or carbon products containing silicon and / or metals, and the like.

[0213] The carbon black used in any of the methods disclosed herein can be any grade of reinforced and semi-reinforced carbon black or has a statistical thickness surface area (STSA) (e.g., ranging from 20 μm). 2 / g to 250m 2 Other carbon blacks ( / g or higher). STSA (Statistical Thickness Surface Area) is determined based on ASTM Test Procedure D-5816 (measured by nitrogen adsorption). Examples of ASTM grade reinforced grades are N110, N121, N134, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, and N375 carbon black. Examples of ASTM grade semi-reinforced grades are N539, N550, N650, N660, N683, N762, N765, N774, N787, N990 carbon black, and / or N990 grade thermal black.

[0214] Carbon black can have any statistical thickness surface area (STSA), for example, in the range of 20 m². 2 / g to 250m 2 / g or higher. STSA (Statistical Thickness Surface Area) is determined based on ASTM Test Procedure D-5816 (measured by nitrogen adsorption). Carbon black may have a compression oil absorption value (COAN) ranging from about 30 mL / 100g to about 150 mL / 100g. The compression oil absorption value (COAN) is determined according to ASTM D3493. As an option, carbon black may have a range of 20 mL / g or higher. 2 / g to 180m 2 / g, or a range of 60m 2 / g to 150m 2 / g of STSA, wherein the COAN ranges from 40mL / 100g to 115mL / 100g or from 70mL / 100g to 115mL / 100g.

[0215] As described, carbon black can be rubber black, and more particularly reinforced or semi-reinforced grades of carbon black. Carbon blacks sold under the trademarks Regal®, Black Pearls®, Spheron®, Sterling®, Propel®, Endure®, and Vulcan® from Cabot Corporation; the trademarks Raven®, Statex®, Furnex®, and Neotex® and the CD and HV series from Birla Carbon (formerly Columbia Chemicals); and the trademarks Corax®, Durax®, Ecorax®, and Purex® and the CK series from Orion Engineered Carbons (formerly Evonik and Degussa Industries), as well as other fillers suitable for rubber or tire applications, may also be developed for various implementations. Suitable chemically functionalized carbon blacks include those disclosed in WO96 / 18688 and US2013 / 0165560 (the disclosures of which are incorporated herein by reference). Mixtures of any of these carbon blacks may be used.

[0216] Any method disclosed herein relates in part to a method for preparing composite materials comprising at least two mixing steps or stages. These two (or more) mixing steps can be considered as multi-step or multi-stage mixing having a first mixing step or stage and at least a second mixing step or stage. One or more of the multi-stage mixing processes can be batch, continuous, semi-continuous, or combinations thereof.

[0217] For multi-stage processes, the method for preparing the composite material includes the steps of loading or introducing the following into a first mixer: at least a) one or more solid elastomers, b) one or more fillers, wherein at least one filler or a portion thereof is a wet filler as described herein (e.g., a wet filler comprising filler and a liquid present in an amount of at least 20 wt.% based on the total weight of the wet filler), and optionally, c) a binder. During this mixing step, the combination of the solid elastomer with the wet filler and optionally the binder forms a mixture or composite material, which may be considered the first mixing step or stage. The method further includes, in this first mixing step, mixing the mixture to the extent that at least a portion of the liquid is removed by evaporation or an evaporation process occurring during mixing. This first mixing step (in one or more mixing steps) or stage is carried out using one or more of the methods for forming the composite material described above, wherein it is understood that, after the completion of the first mixing, the mixture discharged from the mixer after the first mixing step (e.g., the discharged mixture) need not have a liquid content of more than 10 wt.%. In other words, through a multi-stage process, the mixture obtained from the first mixer (or the first mixing step) after the first mixing can have a liquid content of more than 10 wt.%, but it does have a reduced liquid content (in wt.%) compared to the liquid content of the combined solid elastomer and wet filler at the beginning of the first mixing step.

[0218] As a further option, prior to the use of a first mixer or other mixer for the second mixing step, a settling time may exist, during which the composite material formed by the first mixer is allowed to stand or cool, or both, in the first mixer or in another container or location (e.g., mixing, stopping, and then further mixing). For example, this settling time may allow the mixture to reach a material temperature below 180°C (also known as a probe temperature) before the commencement of the further mixing step (e.g., the discharged mixture may have a material temperature ranging from about 100°C to about 180°C, about 70°C to 179°C, or about 100°C to about 170°C, or about 120°C to about 160°C). Alternatively, the settling time prior to the commencement of the further or second mixing step may be from about 1 minute to 60 minutes or longer. The material temperature can be obtained by many methods known in the art, for example, by inserting a thermocouple or other temperature measuring means into the mixture or composite material.

[0219] The method then includes mixing or further mixing the mixture in at least a second mixing step or stage using the same mixer (i.e., the first mixer) and / or using a second mixer different from the first mixer. Through a multi-stage mixing process, the binder can be optionally loaded into the first mixer or the second mixer, or both.

[0220] Following the first mixing, further mixing steps for multi-stage mixing may utilize any one or more of the mixing procedures, parameters, or steps used in the first mixing step as described herein. Therefore, in further mixing steps or stages, the same or different mixer design and / or the same or different operating parameters as the first mixer may be used in the further mixing stages. The mixer and its options described above for the first mixing step and / or the operating parameters described above for the mixing step may optionally be used in the further or second mixing steps (e.g., mixing steps, as described herein, including a tip speed of at least 0.5 m / s for at least 50% of the time or at least 0.6 m / s for at least 50% of the time, and / or a T value of 65°C or higher). z And other parameters described herein or in PCT Publication No. WO2020 / 247663, the contents of which are incorporated herein by reference.

[0221] In a multi-stage process, the second mixing step (second stage mixing) may also include loading additional components other than the mixture discharged from the first mixing step into the mixer. For example, without loading a binder into the first mixer, a binder may be loaded into the second mixer, either as a separate charge or as a mixture (particle mixture or co-particle) with fillers (wet or dry fillers, the same or different fillers loaded into the first mixer). Alternatively or as an example, the method may include loading additional fillers, such as dry fillers, wet fillers, or blends thereof, before or during the second mixing step. The additional fillers may be the same as or different from the fillers already present in the mixture, such as any of the other fillers disclosed herein. For example, the mixture discharged from the first mixer may be considered a masterbatch, in which all or part of it is combined with additional fillers. For example, wet or dry carbon black, silica, silicon-treated carbon black (and blends thereof) may be added to the mixture discharged from the first mixing step, such as a mixture containing carbon black and natural rubber.

[0222] For multi-stage mixing processes, in at least one option, at least a second mixer is used in a further mixing step. When this option is used, the second mixer may have the same or different design as the first mixer, and / or may have the same or one or more different operating parameters than the first mixer. Specific examples of the first and second mixer options are provided below, and these examples are not intended to be limiting. For example, the first mixer may be a tangential mixer or a meshing mixer, and the second mixer may be a tangential mixer, a meshing mixer, an extruder, a kneader, or a roller mill. For example, the first mixer may be an internal mixer, and the second mixer may be a kneader, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a continuous compounding mill, or a roller mill. For example, the first mixer may be a first tangential mixer, and the second mixer may be a second (different) tangential mixer. For example, the first mixer operates with a plunger, and the second mixer operates without a plunger. For example, a second mixer is utilized and operated at a fill factor based on a mixture ranging from 25% to 70%, 25% to 60%, 25% to 50%, 30% to 50% by dry weight, or other fill factor amounts described herein.

[0223] As an option, the method includes mixing or further mixing the mixture in at least a second mixing step or stage using the same mixer (i.e., the first mixer) and / or using a second mixer different from the first mixer. Mixing with the second mixer may cause the second mixer or the second mixing to operate as follows: at a plunger pressure of 5 psi or lower and / or with the plunger raised to at least 75% of the highest plunger level (e.g., at least 85%, at least 90%, at least 95%, or at least 99% or 100% of the highest plunger level), and / or with the plunger operating in a floating mode, and / or with the plunger positioned such that it substantially does not contact the mixture; and / or without a plunger mixer; and / or with a fill factor ranging from 25% to 70%. The method then includes discharging the resulting composite material from the last used mixer, such that the composite material has a liquid content of no more than 10% by weight, based on the total weight of the composite material. Suitable methods for operating the second mixer are described in PCT Publication No. WO2020 / 247663, the disclosure of which is incorporated herein by reference.

[0224] Additives may also be incorporated into the mixing and / or compounding steps (e.g., whether in a single-stage mixing process or in the second or third stage of a multi-stage mixing process) and may include anti-degradation agents and one or more rubber chemicals to enable the filler to disperse into the elastomer. Rubber chemicals as defined herein include one or more of the following: processing aids (to provide ease of rubber mixing and processing, such as various oils and plasticizers, waxes), activators (to activate the vulcanization process, such as zinc oxide and fatty acids), accelerators (to accelerate the vulcanization process, such as sulfonamides and thiazoles), vulcanizing agents (or curing agents to crosslink the rubber, such as sulfur, peroxides), and other rubber additives, such as, but not limited to, retarders, auxiliaries, plasticizers, adhesion promoters (e.g., using cobalt salts to promote the adhesion of steel cords to rubber-based elastomers (e.g., as described in U.S. Patent No. 5,221,559 and U.S. Patent Publication No. 2020 / 0361242, the disclosures of which are incorporated herein by reference), resins (e.g., tackifiers, traction resins), and resins (e.g., tackifiers, traction resins). The rubber chemicals include resins, flame retardants, colorants, foaming agents, and additives for reducing heat buildup (HBU). Alternatively, the rubber chemicals may contain processing aids and activators. As another option, the one or more other rubber chemicals are selected from zinc oxide, fatty acids, zinc salts of fatty acids, waxes, accelerators, resins, and processing oils. Exemplary resins include those selected from one or more of the following: C5 resins, C5-C9 resins, C9 resins, rosin resins, terpene resins, aromatic-modified terpene resins, dicyclopentadiene resins, alkylphenol resins, and resins disclosed in U.S. Patent Nos. 10,738,178, 10,745,545 and U.S. Patent Publication No. 2015 / 0283854 (the disclosure of which is incorporated herein by reference).

[0225] In any of the methods for producing composite materials disclosed herein, after the composite material is formed, the method may further include one or more of the following steps:

[0226] - One or more holding steps;

[0227] One or more drying steps may be used to further dry the composite material to obtain a dry composite material;

[0228] - One or more extrusion steps;

[0229] - One or more rolling steps;

[0230] - One or more milling steps to obtain a milled composite material;

[0231] - One or more granulation steps;

[0232] - One or more cutting steps;

[0233] - One or more packaging steps to obtain a baled product or mixture;

[0234] - Packaged mixtures or products may be broken down to form granulated mixtures; and / or

[0235] - One or more mixing or compounding steps; and / or

[0236] - One or more sheeting steps.

[0237] As a further example, after the composite material is formed, the following sequence of steps may occur, and each step may be repeated any number of times (with the same or different settings):

[0238] - One or more maintenance steps to further develop resilience

[0239] - One or more cooling steps

[0240] - Further dry the composite material to obtain a further dried composite material;

[0241] - Mixing or compounding composite materials to obtain compounded mixtures;

[0242] - Milling the compounded mixture to obtain a milled mixture (e.g., roller milling);

[0243] - Granulate the milled mixture;

[0244] - Optionally, the mixture may be packaged after granulation to obtain a packaged mixture;

[0245] - Optionally, the packaged mixture can be broken down and mixed.

[0246] Alternatively, the composite material may be compounded with one or more anti-degradation agents, zinc oxide, fatty acids, zinc salts of fatty acids, waxes, accelerators, resins, processing oils, and / or curing agents, and vulcanized to form a vulcanized product. Such vulcanized compounded materials may have one or more improved properties, such as one or more improved rubber properties, such as, but not limited to, improved hysteresis, abrasion resistance, and / or rolling resistance, for example in tires, or improved mechanical and / or tensile strength, or improved tanδ and / or improved tensile stress ratio, and so on.

[0247] As an example, in the compounding step, the components (other than sulfur or other crosslinking agents and accelerators) are combined with the pure composite material in a mixing device (non-curing agents and / or anti-degradation agents, typically pre-mixed and collectively referred to as "smalls"). The most common mixing device is an internal mixer, such as a Banbury or Brabender mixer, but other mixers, such as continuous mixers (e.g., extruders), may also be used. Subsequently, in a later or second compounding step, crosslinking agents, such as sulfur, and accelerators (if necessary) (collectively referred to as curing agents) are added. As another option, the compounding may include combining the composite material with one or more of the following in a single compounding stage or step: anti-degradation agents, zinc oxide, fatty acids, zinc salts of fatty acids, waxes, accelerators, resins, processing oils, and curing agents; for example, the curing agent may be added along with the smalls in the same compounding stage. The compounding step is typically carried out in the same type of equipment as the mixing step, but may be carried out on different types of mixers or extruders or roller mills. Those skilled in the art will recognize that once the curing agent has been added, vulcanization will begin once the appropriate activation conditions for the crosslinking agent are met. Therefore, when using sulfur, the temperature during mixing should preferably be kept basically below the curing temperature.

[0248] This document also discloses a method for manufacturing a vulcanized product. The method may include the step of curing the composite material in the presence of at least one curing agent. Curing may be accomplished by applying heat, pressure, or both, as known in the art.

[0249] Regarding the vulcanized product, the vulcanized product may have one or more elastomer properties. For example, the vulcanized product may have a tensile stress ratio M300 / M100 of at least 5.9, such as at least 6.0, at least 6.1, or at least 6.2, as evaluated by ASTM D412, where M100 and M300 refer to the tensile stress at 100% and 300% elongation, respectively.

[0250] Alternatively or additionally, the vulcanized product may have the following maximum tanδ (60°C): not greater than 0.22, for example, not greater than 0.21, not greater than 0.2, not greater than 0.19, not greater than 0.18, for example, not greater than 0.16, not greater than 0.15, not greater than 0.14, not greater than 0.13, not greater than 0.12, or not greater than 0.11.

[0251] Vulcanized products prepared from the composite material of the present invention (e.g., in T...) zVulcanized products manufactured by any of the processes disclosed herein for mixing wet fillers, solid elastomers, and binders (whether single-stage or multi-stage) at the disclosed mixing conditions, or at tip speeds, may exhibit improved properties. For example, vulcanized products prepared from the composites of the present invention may have improved properties compared to vulcanized products prepared from composites manufactured by dry mixing of solid elastomers, unwetted fillers, and binders (“dry-mixed composites”), particularly those dry-mixed composites having the same composition (“dry-mixed equivalents”). Thus, a comparison was made between dry mixing and the mixing process of the present invention, among comparable fillers, elastomers, filler loads (e.g., ±5 wt%, ±2 wt.%), and formulations (including binders) and optionally curing additives. Under these conditions, the vulcanized product has a smaller tanδ value than the vulcanized product prepared from dry-mixed composites having the same composition. Alternatively, the vulcanized product has a tensile stress ratio M300 / M100 greater than that of a vulcanized product prepared from a dry-mixed composite material having the same composition, wherein M100 and M300 refer to the tensile stress at 100% and 300% elongation, respectively.

[0252] Elastomers (e.g., diene-based elastomers) are known to degrade in the presence of air / oxygen. Degradation can take the form of polymer chain breakage and / or crosslinking, which can affect rubber properties. Elastomer composites can be cured in the presence of a curing agent (e.g., sulfur) to achieve crosslinking, resulting in a cured (relative to the composite) and more stable vulcanized product in terms of degradation; degradation can still occur, but to a lesser extent, compared to the uncured composite. However, long-term storage (and / or transportation) of uncured elastomer composites may be required (e.g., 3, 6, 9 months, or up to 1 year or even up to 2 years). Furthermore, the temperature rise often present in warehouses or during transportation (trucks, containers) can accelerate the degradation rate. To reduce this rate, the composite can be stored in refrigeration units or under air conditioning. However, such storage solutions require excessive energy expenditure and refrigeration equipment.

[0253] It has been found that composite materials containing binders can exhibit reduced degradation over time at temperatures of at least 20°C, for example, after at least 5 days, at least 1 week, at least 2 weeks, at least 1 month (at least 30 days), at least 2 months, at least 30 months, and even at least 6 months (at least 180 days) up to a maximum of 1 year (12 months) or even up to a maximum of 2 years. Such composite materials that have been stored or aged are referred to as "aged composite materials". Alternatively, aged composite materials can be those that have been stored or aged at elevated temperatures for at least 1 day. The degradation of aged composite materials can be observed by monitoring the rubber properties of the composite material or the vulcanized product. For example, according to the methods disclosed herein, vulcanized products prepared from composite materials made with binders retain certain properties over time. Aging the composite materials disclosed herein for a period of at least 1 day, 5 days, or up to 1 year yields enhanced hysteretic properties in vulcanized products prepared from the aged composite materials, as indicated by the following: the maximum tanδ, Payne effect, and / or Payne ratio values ​​increase by no more than 10% of the values ​​of vulcanized products prepared from unaged composite materials (e.g., aged for no more than 2 days or no more than 1 day). This can, for example, enhance the rheological properties of the composite materials (and blends formed from such composite materials). An example of such properties is the Payne effect of the vulcanized product, which can be indicated by the Payne ratio or Payne difference. The Payne ratio is defined by G'(0.1%) / G'(50%), where G'(0.1%) is the dynamic storage modulus measured at a strain amplitude of 0.1% and G'(50%) is the dynamic storage modulus measured at a strain amplitude of 50%. The Payne difference is the difference between G'(0.1%) and G'(50%).

[0254] At room temperature (e.g., 20°C), the aged composite material may be stored or aged for at least 5 days or other time periods disclosed herein. The aging period may be determined from the date of manufacture (day 0). Alternatively, the aged composite material is a composite material that has been stored or aged at a temperature of at least 20°C (e.g., 20°C to 200°C) or under environmental conditions (e.g., temperatures ranging from 20°C to 40°C or 20°C to 30°C), whether in a climate-controlled environment or in an area without climate control (e.g., a warehouse, a truck). The aging period may be at least 7 days, at least 2 weeks, at least 1 month, at least 3 months, at least 6 months, or at least 1 year or longer, for example, 5 days to 2 years, 5 days to 1 year, 5 days to 6 months, 5 days to 3 months, 2 weeks to 1 year, 2 weeks to 6 months, 1 month to 1 year, 1 month to 6 months, and other ranges.

[0255] As an alternative, the aged composite material may be stored or aged at an elevated temperature for at least one day, said elevated temperature being, for example, a temperature of at least 40°C, such as the temperature range of: 40°C to 200°C, 40°C to 180°C, 40°C to 150°C, 40°C to 120°C, 40°C to 100°C, 40°C to 90°C, 40°C to 75°C. The temperatures range from 50°C to 200°C, 50°C to 180°C, 50°C to 150°C, 50°C to 120°C, 50°C to 100°C, 50°C to 90°C, 50°C to 75°C, 60°C to 200°C, 60°C to 180°C, 60°C to 150°C, 60°C to 120°C, 60°C to 100°C, or 60°C to 90°C. In some embodiments, the composite material can be stored at elevated temperatures for at least 7 days, at least 2 weeks, at least 3 weeks, or at least 1 month up to a maximum of 6 months or a maximum of 1 year. Alternatively, storage at elevated temperatures may be carried out for no longer than 1 month, no longer than 2 weeks, or no longer than 1 week, for example, storage for 5 days to 1 month.

[0256] This document also discloses articles made from or containing the composite materials or vulcanized products disclosed herein.

[0257] The composite material can be used to produce products containing elastomers or rubber. Alternatively, the elastomer composite material can be used to produce vulcanized products for use, for example, to form various parts to be incorporated into a tire, such as the tire tread (e.g., road or off-road tire tread), including the cap and base, bottom tread, airtight layer, tire sidewall, tire carcass, tire sidewall inserts, wire-skim for the tire, and cushioning rubber for retreaded tires, pneumatic tires, and non-pneumatic or solid tires. Alternatively or additionally, the elastomer composite material (and subsequent vulcanized products) can be used in hoses, seals, gaskets, weatherstripping, windshield wipers, automotive components, bushings, pads, shells, wheel and track components, tire sidewall inserts, wire-skim for the tire, and cushioning rubber for retreaded tires, pneumatic tires, and non-pneumatic or solid tires. Alternatively or additionally, elastomeric composites (and subsequent vulcanized products) can be used in hoses, seals, gaskets, vibration damping products, tracks, track pads for tracked propulsion equipment (e.g., bulldozers), engine mounts, seismic stabilizers, mining equipment such as screens, mining equipment liners, conveyor belts, chute liners, slurry pump liners, mud pump assemblies such as impellers, valve seats, valve bodies, piston hubs, piston rods, plungers, impellers for various applications such as mixing slurry and slurry pump impellers, grinding mill liners, cyclone separators and hydrocyclones, expansion joints, marine equipment such as liners for pumps (e.g., dredging 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, drive shafts, liners for conveying pipes such as oil sands and / or tar sands, and other applications where abrasion resistance and / or enhanced dynamic properties are desired. In addition, through vulcanization, elastomer composites can be used in the following applications: for rollers, cams, shafts, pipes, bushings, or other applications where wear resistance and / or enhanced dynamic properties are desired.

[0258] Accordingly, articles include vehicle tire treads, including a cap and base, sidewalls, bottom tread, airtight layer, wire skim assembly, tire carcass, engine mounts, bushings, conveyor belts, vibration dampers, weatherstripping, windshield wipers, automotive components, seals, gaskets, hoses, pads, mats, shells, and wheel or track elements. For example, articles may be multi-component treads, as disclosed in U.S. Patent Nos. 9,713,541, 9,713,542, 9,718,313, and 10,308,073, the disclosures of which are incorporated herein by reference.

[0259] Example

[0260] The mixing and all blending processes in Examples I and II were performed using a BR-1600 Banbury® mixer (“BR1600”; manufacturer: Farrell) at a plunger pressure of 2.8 bar. The BR1600 mixer operates via two 2-blade tangential rotors (2WL) and provides a capacity of 1.6 L. The mixing in Example III was performed using a BB-16 tangential mixer (“BB-16”; Kobelco Kobe Steel Group) equipped with two tangential 4-blade rotors (4WN type) (providing a capacity of 16.2 L).

[0261] The water content in the discharged composite material was measured using a moisture balance (model: HE53, manufacturer: Mettler Toledo NA, Ohio). The composite material was cut into small pieces (dimensions: length, width, height <5 mm), and 2 to 2.5 g of material was placed on a disposable aluminum pan / plate placed inside the moisture balance. Weight loss was recorded at 125°C for 30 minutes. At the end of 30 minutes, the moisture content of the composite material was recorded as follows:

[0262]

[0263] The following tests are used to measure the rubber properties of each vulcanized product:

[0264] - Tensile stress at 100% elongation (M100) and tensile stress at 300% elongation (M300) were evaluated using ASTM D412 (Test Method A, Die C) at 23°C, 50% relative humidity, and a crosshead speed of 500 mm / min. Tensile strain was measured using an elongation meter. The ratio of M300 to M100 is called the tensile stress ratio (or modulus ratio).

[0265] - Maximum tanδ was measured using an ARES-G2 rheometer (manufacturer: TA Instruments) in torsion mode with an 8 mm diameter parallel plate geometry. The vulcanized product specimens were 8 mm in diameter and approximately 2 mm thick. The rheometer was operated at a constant temperature of 60°C and a constant frequency of 10 Hz. Strain scans were performed from 0.1% to 68% of the strain amplitude. Measurements were taken at ten points per decimal place, and the maximum measured tanδ (“maximum tanδ”), also referred to as “tanδ”, was recorded unless otherwise specified. The Payne ratio was calculated based on the ratio of the dynamic storage modulus G’ at 0.1% strain to G’ at 50% strain (i.e., G’(0.1%) / G’(50%)).

[0266] Example I

[0267] This embodiment describes the preparation of composite materials and corresponding vulcanized products, wherein a solid elastomer is mixed with wet fillers and binders.

[0268] All samples were tested with ASTM grade N234 carbon black (as VULCAN). ® 7H carbon black (“V7H”; Cabot Corporation) is prepared. Wet carbon black pellets with a moisture content of 55.2% are prepared by milling using an 8” MicroJet mill to produce loose carbon black pellets with a particle size diameter less than 10 micrometers at 99.5%. This loose carbon black is then wetted using a needle pelletizer to regenerate wetted pellets. The elastomer used is standard grade SMR5 natural rubber (Hokson Rubber, Malaysia). A technical description of this natural rubber is widely available, for example in Rubber World Magazine's Blue Book published by Lippincott and Peto, Inc. (Akron, Ohio, USA). The linker used is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate, which can be used as a Sumilink. ® 200 coupling agent (“S200”; Sumitomo Chemical) is commercially available.

[0269] Two examples were prepared in which a binder was added in the same mixing stage as wet carbon black. The following comparisons were prepared: conventionally mixed natural rubber and carbon black (Dry 1), and conventionally mixed natural rubber, carbon black, and S200 (Dry 2).

[0270] The formulations are shown in Table 1. Carbon black loading is on a dry basis.

[0271] Table 1

[0272]

[0273] 6PPD = N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine. Wax beads are... Wax beads, and BBTS (N-tert-butyl-2-benzothiazole sulfinamide) is an accelerator for BBTS, are both available from Akrochem, Akron, Ohio.

[0274] The first-stage mixing scheme is summarized in Table 2 (dry mixing) and Table 3 (mixing with wet filler). The time intervals listed in the following mixing methods refer to the time period from the start of mixing (defined as "0 s"). For Ex. 1, the binder is added at a temperature of 140°C, while for Ex. 2, the binder is added at 210 s of the total mixing time.

[0275] Table 2

[0276]

[0277] Table 3

[0278]

[0279] All composite materials were sheeted at 50°C on a 2-roll mill running at approximately 37 rpm, followed by six pass-throughs with a nip gap of approximately 5 mm. After stage 1 mixing, the moisture content of the Ex. 1 and Ex. 2 composite materials was 0.8% and 0.9% by weight, respectively.

[0280] The vulcanized product was formed by compounding the composite material with the Stage 2 formulation according to the scheme in Table 4, followed by compounding with the curing agent (Stage 3 formulation) according to the scheme in Table 5. After each compounding stage, the compound was sheeted on a 2-roll mill running at 50°C and approximately 37 rpm, followed by six passes with a trommel gap of approximately 5 mm. The final compound was sheeted to a thickness of 2.4 mm on a 2-roll mill running at 60°C. The final compound was cured for 30 min in a heated press (2500 lbs) at 150°C.

[0281] Table 4

[0282]

[0283] Table 5

[0284]

[0285] The properties of the vulcanized products are shown in Table 6.

[0286] Table 6

[0287]

[0288] The data in Table 6 show that the composite material mixed with wet filler and binder has a maximum dynamic hysteresis loss (tanδ) that is lower than that of the comparative Dry 1 and Dry 2 examples. The tensile stress ratios (M300 / M100) of Ex. 1 and Ex. 2 are higher than those of the dry-mixed examples. This confirms that improved rubber properties can be achieved through a combination of mixing with wet filler and using a binder.

[0289] Example II

[0290] This embodiment describes the preparation of composite materials and corresponding vulcanized products, wherein a solid elastomer is mixed with wet filler that has been co-granulated with a binder.

[0291] Three linkers were evaluated: cystamine dihydrochloride (“Cystamine”; 96%, Sigma-Aldrich), hexamethylene-1,6-bis(thiosulfate) (“Duralink”); Tire additives (Eastman Chemical Co.) and thiourea (Sigma-Aldrich). All samples were tested with ASTM grade N234 carbon black (as VULCAN). ® 7H carbon black is supplied by Cabot Corporation (“V7H”). The elastomer used is standard grade SMR20 natural rubber (Hokson Rubber, Malaysia). Technical descriptions of this natural rubber are widely available, for example in Rubber World Magazine's Blue Book published by Lippincott and Peto, Inc. (Akron, Ohio, USA).

[0292] The co-granules containing binder and carbon black (wet or dry) were loaded into the mixer. The co-granules containing binder and carbon black were formed by combining 6 g of a solution of binder with DI water (310 g) and 250 g of loose V7H carbon black as prepared in Example I. Granulation was performed using a 10HP heated needle pelletizer with a dwell time of 5 minutes at 60°C. For Ex. 3, Ex. 4, and Ex. 5, the resulting wet granules were used without drying. For Examples Dry 3, Dry 4, and Dry 5, the resulting wet granules were dried overnight in an oven at 125°C before mixing. For Comparative Example Dry 6, granules containing carbon black and without binder were prepared as described in this example.

[0293] The formula is shown in Table 7.

[0294] Table 7

[0295]

[0296] 6PPD = N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine. Wax beads are... The wax beads, and CBS being N-cyclohexyl-2-benzothiazole sulfinamide, are both available from Akrochem, Akron, Ohio.

[0297] Table 8 shows the mixing schemes for all mixtures with dry fillers (i.e., Dry 6 and Dry 3 to Dry 5).

[0298] Table 8

[0299]

[0300] Schemes Ex. 3, Ex. 4 and Ex. 5 for mixing with wet co-granules are shown in Table 9.

[0301] Table 9

[0302]

[0303] The moisture content of the Ex. 3, Ex. 4, and Ex. 5 composites after stage 1 mixing was 0.74%, 0.35%, and 0.55% relative to the weight of the composites. All composites underwent a second compounding stage (schemes in Table 10), in which curing agents and additives were added (for composites derived from wet co-particles; curing agents were only for dry-mixed composites).

[0304] Table 10

[0305]

[0306] The compound was sheeted on a 2-roll mill running at 50°C and approximately 37 rpm, banded for 1 minute, followed by four passes with a trommel gap of approximately 5 mm. The compound was then sheeted to a thickness of 2.4 mm on a 2-roll mill running at 60°C. The final compound was cured in a heated press at 150°C for 21 minutes (2500 lbs). The properties of the vulcanized product are shown in Table 11.

[0307] Table 11

[0308]

[0309] As can be seen from the data in Table 11, compared with the corresponding comparative dry-mixed examples, the vulcanized products of the composite material prepared from wet co-granules with a binder exhibit lower maximum tanδ, higher tensile stress ratio (M300 / M100), or both. Compared with comparative example Dry 6, the vulcanized products of Ex. 3, Ex. 4, and Ex. 5 all exhibit lower maximum tanδ and higher tensile stress ratio.

[0310] Example III

[0311] This embodiment describes the preparation of a composite material by mixing a wet filler with natural rubber and a binder, and the evaluation of the properties of the composite material and the properties of the compound prepared from the composite material.

[0312] All samples were tested with ASTM grade N234 carbon black (as VULCAN). ®7H carbon black (“V7H”; Cabot Corporation) is supplied for preparation. Wet carbon black granules with a moisture content of 56% are prepared by milling using an 8” MicroJet mill to produce loose carbon black granules with a particle size diameter less than 10µm at 99.5%. This loose carbon black is then wetted using a needle pellet mill to regenerate wetted granules. The elastomer used is standard grade RSS3 natural rubber (Von Bundit Co. Ltd., Thailand). A technical description of this natural rubber is widely available, for example in Rubber World Magazine's Blue Book published by Lippincott and Peto, Inc. (Akron, Ohio, USA). The linker used is sodium (2Z)-4-[(4-aminophenyl)amino]-4-oxo-2-butenoate, which can be used as a Sumilink. ® 200 coupling agent (“S200”; Sumitomo Chemical) is commercially available.

[0313] The mixing of wet carbon black and natural rubber was carried out in two stages, followed by two stages of compounding. The formulations used are shown in Table 12. Carbon black loading is on a dry basis.

[0314] Table 12

[0315]

[0316] Tables 13 (Stage 1) and 14 (Stage 2) outline the two-stage mixing scheme. The time intervals listed in the following mixing methods refer to step times. All mixing was performed under the following conditions: TCU temperature = 90°C, fill factor = 66%, and plunger pressure = 112 barg. The first-stage mixing was carried out on a BB-16 mixer equipped with a 4WN rotor (16.2L capacity) at a plunger pressure of 112 barg, and is outlined in Table 13. Following the first-stage mixing, the composite material was processed in a TSR-125 twin-screw discharge extruder (Kobelco Kobe Steel Group) equipped with a fixed blade.

[0317] Following the scheme in Table 13, the second stage of mixing was performed on a BB-16 mixer equipped with a 6WI rotor (14.4L capacity). Mixing was carried out with the plunger raised to its highest position. After initial plasticization, mixing was performed under PID control (proportional-integral-differential), which allowed for automatic batch temperature control via a feedback loop. The batch temperature was measured via a thermocouple inserted through the mixer drop door and transmitted to the PID controller. The controller output was used to control the speed of the mixer rotor. The second stage mixing conditions were: TCU temperature = 65°C; fill factor = 35%; mixing time = 582s.

[0318] Table 13

[0319]

[0320] Table 14

[0321]

[0322] The moisture content of the composite material after the first stage of mixing was 4.96%; the moisture content after the second stage of mixing was 0.51%. The second-stage composite material was processed in a TSR-125 twin-screw extruder (Kobelco KobeSteel Group) equipped with a roller die. The resulting sheets were cooled in ambient air.

[0323] The composite material was stored in air for 30 or 180 days. After the storage period, the vulcanized product was formed by compounding the composite material with the Stage 3 formulation according to the scheme in Table 15, followed by compounding with the curing agent (Stage 4 formulation) according to the scheme in Table 16. After each compounding stage, the composite material was sheeted on a 2-roll mill running at 50°C and approximately 37 rpm, followed by six passes with a trommel gap of approximately 5 mm. The final compound was sheeted to a thickness of 2.4 mm on a 2-roll mill running at 60°C. The final compound was cured for 30 min in a heated press (2500 lbs) at 150°C.

[0324] Table 15

[0325]

[0326] Table 16

[0327]

[0328] The properties of the vulcanized products prepared from two samples each of the composite material samples aged for 30 days (Ex. 6 and Ex. 7) and 180 days (Ex. 8 and Ex. 9) are shown in Table 17.

[0329] Table 17

[0330]

[0331] As can be seen from the data in Table 17, the properties of vulcanized products prepared from aged composites containing binders are surprisingly similar, regardless of whether the composites are stored for 30 days (Ex. 6, Ex. 7) or 180 days (Ex. 8, Ex. 9). Even more surprisingly, the maximum tanδ value of all vulcanized products did not change. These data suggest that binders can help reduce the degradation of composite properties over time (e.g., for at least up to 180 days).

[0332] The terms “a,” “an,” and “the” are to be interpreted as encompassing both the singular and plural unless otherwise stated herein or clearly contradicted by the context. The terms “comprising,” “having,” “including,” and “containing” are to be interpreted as open-ended terms (i.e., meaning “including but not limited to”) unless otherwise stated. References to ranges of values ​​herein are intended merely as a way of individually referring to each individual value falling within that range, unless otherwise stated herein, and each individual value is incorporated into the specification as if it were individually referenced herein. All methods described herein may be performed in any suitable order unless otherwise stated herein or clearly contradicted by the context. The use of any and all exemplary or illustrative language (e.g., “for example”) provided herein is intended merely to better illustrate the invention and not to limit the scope of the invention, unless otherwise required. No language in the specification should be construed as indicating that any non-claimed element is essential to the practice of the invention.

Claims

1. Methods for preparing composite materials, including: (a) Loading a first mixer with at least a solid elastomer and a wet filler comprising carbon black and liquid, wherein the liquid is present in an amount of at least 20% by weight based on the total weight of the wet filler; (b) In one or more mixing steps, the at least solid elastomer and wet filler are mixed to form a mixture, and at least a portion of the liquid is removed from the mixture by evaporation; (c) Discharge from the first mixer a mixture comprising filler dispersed in the elastomer at a load of at least 20 phr, wherein the mixture has a liquid content reduced to less than the liquid content at the beginning of step (b), and wherein the mixture has a material temperature ranging from 100°C to 180°C. (d) The mixture from (c) is mixed in a second mixer to obtain a composite material; and (e) Discharge from the second mixer a composite material having a liquid content of less than 3% by weight based on the total weight of the composite material. A linker is loaded into the first mixer, the second mixer, or both the first and second mixers, wherein the linker is selected from compounds having at least two functional groups. The first functional group is selected from -N(R) 1 (R) 2 ), -N(R 1 (R) 2 (R) 3 ) + A - -S-SO3M 1 and the structures represented by equations (I) and (II), (AND) (II) Where A - The ions are chloride, bromide, iodide, hydroxide, nitrate, or acetate, where X = NH, O, or S, and Y = H or OR. 4 NR 4 R 5 -S n R 4 And n is an integer selected from 1 to 6, and The second functional group is selected from thiocarbonyl, nitriles, nitrile ketones, nitrile imines, and -S-SO3M. 2 -S x -R 6 -SH, -C(R) 6 )=C(R 7 )-C(O)R 8 , -C(R 6 )=C(R 7 )-CO2R 8 , -C(R 6 )=C(R 7 )-CO2M 2 ,and R 1 -R 8 Each is independently selected from H and C1-C8 alkyl groups; M 1 and M 2 Each is independently selected from H and Na. + K + Li + N(Rʹ)4 + Each Rʹ is independently selected from H and C1-C 20 Alkyl group, and x is an integer selected from 1 to 8.

2. The method of claim 1, wherein the binder is loaded into the first mixer, and step (b) comprises mixing the at least solid elastomer, wet filler and binder to form a mixture.

3. The method of claim 1 or 2, wherein the binder is loaded into the second mixer, and step (d) comprises mixing the mixture from (c) and the binder in the second mixer to obtain a composite material.

4. The method of any one of claims 1-3, wherein the first and second mixers are identical.

5. The method of any one of claims 1-3, wherein the first and second mixers are different.

6. The method of any one of claims 1-5, wherein the second mixer operates under at least one of the following conditions: (i) 5 psi or lower plunger pressure; (ii) The plunger is raised to at least 75% of its maximum plunger level; (iii) The plunger operates in floating mode; (iv) The plunger is positioned such that it is essentially not in contact with the mixture; (v) The mixer is plungerless; and (vi) The fill factor of the mixture ranges from 25% to 70%.

Images