Method for producing a composite material with elastomer, filler and binders, and an object produced thereby

Abstract

A method for producing a composite material, comprising: (a) feeding a mixer with at least one solid elastomer, a wet filler containing carbon black and a liquid in an amount of at least 20% by weight, based on the total weight of the wet filler, and a binder; (b) in one or more mixing steps, mixing the at least one solid elastomer, the wet filler, and the binder to form a mixture, and removing at least some of the liquid from the mixture by evaporation; and (c) discharging the composite material, which contains the filler dispersed in the elastomer in a loading of at least 20 phr, from the mixer, wherein the composite material has a liquid content of not more than 10% by weight.-%, based on the total weight of the composite material, wherein the binder is selected from compounds with at least two functional groups, wherein: a first functional group is selected from -N(R1)(R2), -N(R1)(R2)(R3)+A-, -S-SO3M1 and structures of formula (I) and formula (II), where A is chloride, bromide, iodide, hydroxy, nitrate or acetate, X = NH, O or S, Y = H, OR4, NR4R5, -SnR4, and n is an integer from 1-6, and a second functional group is selected from thiocarbonyl, nitrile oxide, nitrones, nitrilimine, -S-SO3M2, -Sx-R6, -SH, -C(R6)=C(R7)-C(O)R8, -C(R6)=C(R7)-CO2R8, - C(R6)=C(R7)-CO2M2, and R1- R8 are each independently selected from H and C1-C8 alkyl; and M1 and M2 are each independently selected from H, Na+, K+, Li+, N(R')4+, where each R' is independently selected from H and C1-C20 alkyl and x is an integer selected from 1-8.

Description

Field of invention

[0001] This document discloses processes for the production of composite materials by combining a solid elastomer, a wet filler, and a binder. Also disclosed are composite materials produced according to the present processes and corresponding vulcanizates derived from these composite materials. background

[0002] In the rubber industry, there is always a desire to develop methods for dispersing fillers in elastomers, and it is particularly desirable to develop methods that can achieve this efficiently in terms of the quality of the filler dispersion, time, effort and / or cost.

[0003] Numerous commercially important products are formed from elastomer compositions in which a reinforcing filler is dispersed in various synthetic elastomers, natural rubber, or elastomer blends. Carbon black and silica, for example, are commonly used to reinforce natural rubber and other elastomers. Typically, a masterbatch is prepared, i.e., a premix of reinforcing filler, elastomer, and various optional additives, such as extender oil. Such masterbatches are then blended with processing and curing additives, and after curing, yield numerous products of economic importance. These products include, for example, pneumatic and non-pneumatic tires or solid rubber tires for vehicles, including the tread components (including cap and substructure), undertread, inner liner, sidewall, wire bead, carcass, and others. Other products include, for example...Engine mounts, bushings, conveyor belts, windscreen wipers, rubber components for the aerospace and marine industries, vehicle track elements, seals, linings, sealing rings, wheels, bumpers, anti-vibration systems and the like.

[0004] Although there are a number of methods for incorporating fillers into solid elastomers, there is a constant need for new methods to achieve acceptable or improved dispersion quality and functionality of elastomer composites made from elastomer composite masterbatches, which can result in acceptable or improved properties in the corresponding vulcanized rubber compounds and rubber articles. Summary

[0005] One aspect is a process for manufacturing a composite material, encompassing: (a) Feeding a mixer with at least one solid elastomer, a wet filler containing carbon black and a liquid in an amount of at least 20% by weight, based on the total weight of the wet filler, and a binder; (b) in one or more mixing steps, mixing the at least one solid elastomer, the wet filler and the binder to form a mixture, and removing at least some of the liquid from the mixture by evaporation; and (c) Discharge of the composite material containing the filler dispersed in the elastomer in a loading of at least 20 phr from the mixer, wherein the composite material has a liquid content of not more than 10 wt.%, based on the total weight of the composite material, wherein the binder is selected from compounds with at least two functional groups, wherein: a first functional group is selected from -N(R 1 )(R 2 ), -N(R 1 )(R 2 )(R 3 ) + A - , -S-SO3M 1 and structures of formula (I) and formula (II), where A - chloride, bromide, iodide, hydroxy, nitrate or acetate, X = NH, O or S, Y = H, OR 4 , NR 4 R 5 , -S n R 4 is and n is an integer from 1-6, and a second functional group is selected from thiocarbonyl, nitrile oxide, nitrones, 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 , and R 1 - R 8 Each is independently selected from H and C1-C8 alkyl; and M 1 and M 2Each were selected independently from H, Na + , K + , Li + , N(R')4 + , where each R' is independently selected from H and C1-C 20 -Alkyl and x is an integer chosen from 1-8.

[0006] Another aspect is a process for manufacturing a composite material, encompassing: (a) Feeding a first mixer with at least one solid elastomer and a wet filler containing carbon black and a liquid 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, mixing the at least one solid elastomer and the wet filler to form a mixture, and removing at least some of the liquid from the mixture by evaporation; (c) Discharge of the mixture comprising the filler dispersed in the elastomer in a loading of at least 20 phr from the first mixer, wherein the mixture has a liquid content reduced to an amount less than the liquid content at the beginning of step (b), and wherein the mixture has a material temperature in the range of 100°C to 180°C; (d) Mixing the mixture from (c) in a second mixer to obtain the composite material; and (e) Discharge of the composite material having a liquid content of less than 3 wt.%, based on the total weight of the composite material, from the second mixer, wherein a binder is supplied to the first mixer, the second mixer or both the first and the second mixer, the binder being selected from compounds having at least two functional groups, wherein: a first functional group is selected from -N(R 1 )(R 2 ), -N(R 1 )(R 2 )(R 3 ) + A - , -S-SO3M 1 and structures of formula (I) and formula (II), where A - chloride, bromide, iodide, hydroxy, nitrate or acetate, X = NH, O or S, Y = H, OR 4 , NR 4 R 5 , -S n R 4 is and n is an integer from 1-6, and a second functional group is selected from thiocarbonyl, nitrile oxide, nitrones, 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 , and R 1 - R 8 Each is independently selected from H and C1-C8 alkyl; and M 1 and M 2Each were selected independently from H, Na + , K + , Li + , N(R')4 + , where each R' is independently selected from H and C1-C 20 -Alkyl and x is an integer chosen from 1-8.

[0007] Another aspect is a process for producing a vulcanizate, which includes hardening the composite material produced according to one of the processes described here in the presence of at least one hardening agent to form the vulcanizate. Further aspects include composite materials, vulcanizates, and objects manufactured from them.

[0008] With respect to each aspect or method or embodiment disclosed herein, the method may, where applicable, further comprise 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 independently selected from H and C1-C8 alkyl and y is an integer selected from 1-10; the binder is selected from thiourea, cystamine and compounds of formula (1), formula (2) and formula (3), H2N-Ar-N(H)-C(O)-C(R 6 )=C(R 7 )-CO2M 2 (1) H2N-(CH2) n -SSO3M 2 (2) M 1 O3S-S-(CH2) n-S-SO3M 2 (3) wherein M 1 and M 2 each independently of each other from H, Na + and N(R')4 + are selected and R 6 and R 7 are selected independently of each other from H and C1-C6 alkyl; the binder is selected from compounds of formula (1) and R 6 and R 7 Each is H; the binder is sodium (2Z)-4-[(4-Aminophenyl)amino]-4-oxo-2-butenoate.

[0009] With respect to each aspect, method, or embodiment disclosed herein, the method may also, where applicable, comprise one or more of the following embodiments: the feeding comprises feeding the mixer with separate batches of the binder and the wet filler; the feeding comprises multiple additions of the solid elastomer, the wet filler, and / or the binder; the mixing is carried out in one mixing step; the mixing is carried out in two or more mixing steps; the mixing in (b) is a second mixing step, wherein a first mixing step comprises mixing at least a portion of the solid elastomer and at least a portion of the wet filler, followed by feeding the mixer with the binder; the feeding in (a) comprises feeding the mixer with a mixture comprising the binder and the wet filler;The feeding in (a) comprises feeding the mixer with a co-granulate comprising the binder and the wet filler; the process comprises, in at least one of the mixing steps, carrying out the mixing, wherein the mixer has at least one temperature control means that is set to a temperature, T; z , is set at 65°C or higher; the process includes, in at least one of the mixing steps, carrying out the mixing with one or more rotors of the mixer operating at a peak speed of at least 0.6 m / s for at least 50% of the mixing time; a resulting total specific energy for mixing is at least 1,300 kJ / kg of composite material.

[0010] With respect to each aspect, method, or embodiment disclosed herein, the method may, where applicable, further comprise one or more of the following embodiments: the wet filler further comprises at least one material selected from carbonaceous materials, silicon dioxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, or combinations thereof, as well as coated and treated materials thereof; the wet filler further comprises silicon dioxide; the wet filler contains a liquid in an amount of 20 to 80% by weight, based on the total weight of the wet filler; the wet filler is in the form of a powder, a paste, a pellet, or a cake.

[0011] With respect to each aspect or method or embodiment disclosed herein, the method may, where applicable, also include one or more of the following embodiments: 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, fluoroelastomers, perfluoroelastomers, silicone elastomers and mixtures 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 mixtures thereof.

[0012] With regard to each aspect or method or embodiment disclosed herein, the method may, where applicable, also include one or more of the following embodiments: the one or more mixing steps are a continuous process; the one or more mixing steps are a batch process.

[0013] With respect to each aspect, method, or embodiment disclosed herein, the method may, where applicable, further comprise one or more of the following embodiments: the method further comprises aging the composite material to form an aged composite material; the composite material has been aged for at least 5 days at a temperature of at least 20°C; the composite material has been aged for at least 1 day at a temperature of at least 40°C; a vulcanizate produced from the aged composite material has a maximum tan δ value that is increased by no more than 10% of the value of a vulcanizate produced from an unaged composite material;A vulcanizate produced from the aged composite material exhibits a Payne effect that is increased by no more than 10% of the value of a vulcanizate produced from an unaged composite material. Detailed description

[0014] In part, processes for producing or forming a composite material by mixing a solid elastomer with a wet filler are disclosed herein. Furthermore, composite materials, vulcanizates, and articles made therefrom are disclosed in part herein.

[0015] When mixing fillers with elastomers, one challenge is ensuring that the mixing time is long enough to guarantee sufficient incorporation and dispersion of the filler before the elastomer in the mixture is exposed to high temperatures and degrades. In typical dry mixing processes, the mixing time and temperature are controlled to avoid such degradation, and optimization of filler incorporation and dispersion is often not possible.

[0016] PCT Publication No. WO 2020 / 247663, referenced herein, describes mixing processes using a solid elastomer and a wet filler (e.g., comprising a filler and a liquid) to enable batch time and temperature control exceeding that achievable with known dry mixing processes. Further advantages can be gained, such as improved filler dispersion, enabling rubber-filler interactions, and / or improved rubber compound properties compared to conventionally blended masterbatches when compounded and vulcanized. At least one of two properties can be improved, e.g., the ratio of tensile stress at 300% elongation to stress at 100% elongation (M300 / M100) and the tangent delta (tan δ) measured at 60°C.It is assumed that a higher M300 / M 100 value is associated with improved tire wear resistance and a lower tan δ value with improved tire energy efficiency.

[0017] This document discloses processes that involve the use of a wet filler in a mixing process with a solid elastomer and also include a binder. The composite material formed by the processes disclosed herein can be considered an uncured mixture of filler(s) and elastomer(s). The composite material formed can be considered a mixture or masterbatch. As an option, the composite material formed can be an intermediate product that can be used in subsequent rubber compounding and one or more vulcanization processes.The composite material may also be subjected to additional processes prior to compounding and vulcanization, 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 grinding steps, one or more granulation steps, one or more baling steps, one or more twin-screw extrusion steps, or one or more rubber processing steps, in order to obtain a rubber compound or rubber article.

[0018] In one aspect, a method for producing a composite material is disclosed here, comprising the following: (a) Feeding a mixer with at least one solid elastomer, a wet filler containing carbon black and a liquid in an amount of at least 20% by weight, based on the total weight of the wet filler, and a binder; (b) in one or more mixing steps, mixing the at least one solid elastomer, the wet filler and the binder to form a mixture, and removing at least some of the liquid from the mixture by evaporation; and (c) Discharge of the composite material containing the filler dispersed in the elastomer in a loading of at least 20 phr from the mixer, wherein the composite material has a liquid content of not more than 10 wt.%, based on the total weight of the composite material, wherein the binder is selected from compounds with at least two functional groups, wherein: a first functional group is selected from -NR 1 R 2 , -N(R 1 )(R 2 )(R 3 ) + A - , -S-SO3M 1 and structures of formula (I) and formula (II), where A - chloride, bromide, iodide, hydroxy, nitrate or acetate, X = NH, O or S, Y = H, OR 4 , NR 4 R 5 , -S n R 4 is and n is an integer from 1-6, and a second functional group is selected from thiocarbonyl, nitrile oxide, nitrones, 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 , and R 1 - R 8 Each is independently selected from H and C1-C8 alkyl; and M 1 and M 2Each were selected independently from H, Na + , K + , Li + , N(R')4 + , where each R' is independently selected from H and C1-C 20 -Alkyl and x is an integer chosen from 1-8.

[0019] Without being bound to any specific theory, it is assumed that the mixing process with wet filler can improve the dispersion of the filler, while the binder can interact with the filler and / or the elastomer to create a stronger interaction between the filler and the elastomer. As one possibility, the binder can have at least two functional groups, with the first and second functional groups being able to interact with the elastomer and / or the filler. This interaction can occur through adsorption or chemical bonding, e.g., through ionic interactions, dipole-dipole interactions, hydrogen bonds, covalent bonds, etc. In the composite material, the binder can be in the same form in which it is supplied to the mixer or in a different form, e.g., if it interacts with the filler and / or the elastomer via chemical bonding.

[0020] The binder, which comprises at least two functional groups, may comprise two, three, four, or more functional groups. In each of these embodiments, the binder comprises a first functional group consisting of -NR 1 R 2 , -N(R 1 )(R 2 )(R 3 ) + A - , -S-SO3M 1 and structures of formula (I) and formula (II) can be selected, in which A - chloride, bromide, iodide, hydroxy, nitrate or acetate, X = NH, O or S, Y = H, OR 4 , NR 4 R 5 , -S n R 4 where n is an integer from 1 to 6. In certain aspects, the first functional group can be selected from -NR. 1 R 2 (e.g. -NHR) 1 or -NH2), -CO2M 1 and -S-SO3M 1 .

[0021] The binder may further contain a second functional group, which can be selected from thiocarbonyl, nitrile oxide, nitrones, nitrilimine, -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 certain cases, the second functional group can consist of -S-SO3M. 2 and -CR 6 =CR 7 -CO2M 2 be selected. If the functional group is -CO2M 1 and -S-SO3M 1 , -S-SO3M 2 and -CR 6 =CR 7 -CO2M 2 If this is the case, these can be selected from acids or their salts, e.g., M 1 and M 2 each independently of each other from H, Na + , K + , Li + , N(R')4 + chosen (e.g., ammonium salts in which each R' is independently selected from H and C1-C20 -Alkyl, such as C1-C 12 -Alkyl or C1-C6 alkyl or C1-C4 alkyl, e.g., monoalkyl, dialkyl, trialkyl, or tetraalkyl ammonium salts). If the binder contains two or more M 1 or two or more M 2 Each group contains M 1 or M 2 independent from H, Na + , K + , Li + , N(R')4 + be selected.

[0022] In the embodiments described here, R 1 - R 8 each independently selected from H and C1-C8 alkyl; and M 1 and M 2 each selected independently from H, Na + , K + , Li + , N(R')4 + , where each R' is independently selected from H and C1-C 20 -Alkyl and x is an integer chosen from 1-8.

[0023] One possibility is that the first functional group interacts with carbon black. Carbon black can have one or more types of functional surface groups, such as oxygen-containing groups like carboxylic acids (and their salts), hydroxyl groups (e.g., phenols), esters or lactones, ketones, aldehydes, anhydrides, and benzoquinones, but is not limited to these. Another possibility is that the second functional group is able to interact with the solid elastomer. Solid elastomers can be natural elastomers, synthetic elastomers, and mixtures thereof.The solid elastomers can be selected from, for example, 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, fluoroelastomers, perfluoroelastomers, silicone elastomers, and mixtures thereof. One option is to select a solid elastomer made from natural rubber, styrene-butadiene rubber, and polybutadiene rubber. The solid elastomer may contain olefin groups and / or be functionalized with a number of groups.

[0024] One possibility is to select the first functional group from -NR 1 R 2 (e.g. -NH2) and -S-SO3M 1and the second functional group can be selected from -S-SO3M 2 and -CR 3 =CR 4 -CO2M 2 .

[0025] The binder can comprise more than two functional groups. For such binders, any additional functional group, e.g., a third, fourth, etc., functional group, can be selected from the list of the first and second functional groups as disclosed here. Optionally, more than one type of binder can be used to produce a composite material.

[0026] The binder can further comprise at least one spacer between the first and second functional groups. For example, one or more spacers can be bonded to each other and ultimately to the first and second functional groups. As one possibility, the at least one spacer can be 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 from 1-10 and R 9 and R 10 each independently of each other from H and C 1 -C 8 -Alkyl are selected.

[0027] Exemplary binders are selected from compounds of formula (1), formula (2) and formula (3), H2N-Ar-N(H)-C(O)-C(R 6 )=C(R 7 )-CO2M 2 (1) H2N-(CH2) n -SSO3M 2 (2) M 1 O3S-S-(CH2) n -S-SO3M 2 (3) wherein M 1 and M 2 as defined herein, R 6 and R 7 are independently selected from H and C1-C6 alkyl (e.g., independently selected from H and C1-C6 alkyl or independently selected from H and C1-C4 alkyl). One possibility is M 1 and M 2 each independently selected from H, Na + and N(R')4 +,e.g. from H and Na + , and R 6 and R 7 are equal, e.g., R are equal 6 and R 7 Each H. An example of a binder of formula (1) is sodium (2Z)-4-[(4-Aminophenyl)amino]-4-oxo-2-butenoate, commercially available as Sumilink® 200 coupling agent, and an example of a binder of formula (2) is S-(3-Aminopropyl)thiosulfuric acid, commercially available as Sumilink® 100 coupling agent (Sumitomo). An example of a binder of formula (3) is commercially available as Duralink™ HTS tire additive (Eastman Chemical Co.). Other binders include cystamine and thiourea.

[0028] One aspect is a process for manufacturing a composite material, which includes the following: (a) Feeding a mixer with at least one solid elastomer, a wet filler containing carbon black and a liquid in an amount of at least 20% by weight, based on the total weight of the wet filler, and a binder; (b) in one or more mixing steps, mixing at least the solid elastomer, the wet filler and the binder to form a mixture, and removing at least some of the liquid from the mixture by evaporation; and (c) Discharge of the composite material containing the filler dispersed in the elastomer in a loading of at least 20 phr from the mixer, wherein the composite material has a liquid content of not more than 10 wt.%, based on the total weight of the composite material, wherein the binder is selected from: (i) Dihydrazide compounds as described in U.S. Patent No. 2012 / 0277359A1, the disclosure of which is incorporated herein by reference, including, among others, 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 as disclosed in EP0478274, the disclosure of which is incorporated herein by reference; and / or (ii) Hydrazide compounds as described in US Patent Publication No. 2019 / 0177513, the disclosure of which is incorporated herein by reference; and / or (iii) Tetrazine compounds as described in US Patent Publication No. 2020 / 0231782, the disclosure of which is incorporated herein by reference; and / or (iv) Pyrazololone-based compounds as described in PCT Publication No. WO 2020 / 045575, the disclosure of which is incorporated herein by reference (e.g. Compound 1 and Compound 2); and / or (v) Example 2, 2'-Bis(benzimidazolyl-2)ethyl disulfide, as disclosed in US Pat. No. 9,200,145, the disclosure of which is incorporated herein by reference; and / or (vi) N,N'-Bis(2-nitropropyl-1,3-diaminobenzene, as disclosed in US Pat. No. 5,213,025, the disclosure of which is incorporated herein by reference; and / or (vii) Compounds with a nitroxide residue, e.g., TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy residue), as disclosed in US Patents 6,084,015, 6,194,509, 8,584,725, and US Publication No. 2009 / 0292044, the disclosures of which are incorporated herein by reference; and / or (viii) I,3-Bis(citraconimidomethyl)benzene, commercially available as Perkalink® 900 anti-reversion agent (RheinChemie Additives, Germany).

[0029] The amount of binder supplied to the mixer can range from 10 phr or less, e.g., 6 phr or less, 5 phr or less, 4 phr or less, 3 phr or less, or 2 phr or less, and is, for example, a quantity of 0.1 phr to 10 phr, from 0.1 phr to 8 phr, from 0.1 phr to 6 phr, from 0.1 phr to 5 phr, from 0.1 phr to 4 phr, from 0.1 phr to 3 phr, from 0.2 phr to 10 phr, from 0.2 phr to 8 phr, from 0.2 phr to 6 phr, from 0.2 phr to 5 phr, from 0.2 phr to 4 phr, from 0.2 phr to 4 phr, from 0.2 phr to 3 phr, from 0.5 phr to 10 phr, from 0.5 phr to 8 phr, from 0.5 phr to 6 phr, from 0.5 phr to 5 phr, from 0.5 phr to 4 phr, from 0.5 phr to 3 phr, from 1 phr to 10 phr, from 1 phr to 8 phr, from 1 phr to 6 phr, from 1 phr to 5 phr, from 1 phr to 4 phr or from 1 phr to 3 phr.

[0030] The process for producing a composite material comprises the step of filling or introducing at least one solid elastomer, a wet filler, and a binder into a mixer, e.g., a) one or more solid elastomers and b) one or more fillers, wherein at least one filler or part of at least one filler has been wetted with a liquid prior to mixing with the solid elastomer (wet filler). The combination of the solid elastomer with the wet filler and the binder forms a mixture during the mixing stage(s). The process further comprises, in one or more mixing steps, carrying out the mixing, wherein at least part of the liquid is removed by evaporation, or an evaporation process occurring during the mixing.The liquid component of 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, e.g., volatile at the temperatures of mass mixing. A volatile liquid can be distinguished, for example, from oils (e.g., extender oils, process oils) that may be present at least during part of the mixing process, since such oils are intended to be present in the discharged composite material and therefore do not evaporate for a substantial part of the mixing time.

[0031] The filler supplied to the mixer comprises a wet filler. In their dry state, fillers may contain no or only small amounts of liquid (e.g., water or moisture) adsorbed onto their surfaces. For example, carbon black may contain 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 a liquid content (e.g., water or moisture) of 4 wt% to 7 wt% liquid, e.g., 4 wt% to 6 wt% liquid. Such fillers are referred to here as dry or non-wetted fillers. In the case of the wet fillers at hand, liquid or additional liquid may be added to the filler, which is present on a substantial part or substantially all of the filler's surfaces, including internal surfaces or pores accessible to the liquid.Thus, sufficient liquid is present to wet a substantial portion or substantially all of the filler's surfaces before mixing with the solid elastomer. During mixing, at least some of the liquid can also be removed by evaporation as the wet filler is dispersed in the solid elastomer, and the filler surfaces can then become available for interaction with the solid elastomer. The wet filler can have a liquid content of at least 20% by weight, based on the total weight of the wet filler, e.g., at least 25%, at least 30%, at least 40%, at least 50% by weight.-%, or from 20% to 99%, from 20% to 95%, from 20% to 90%, from 20% to 80%, from 20% to 70%, from 20% to 60%, from 30% to 99%, from 30% to 95%, from 30% to 90%, from 30% to 80%, from 30% to 70%, from 30% to 60%, from 40% to 99%, from 40% to 95%, from 40% to 90%, from 40% to 80%, from 40% to 70%, from 40% to 60%, from 45% to 99%, from 45% to 95%, from 45% to 90%, from 45% to 80%, from 45% to 70%, 45% to 60%, 50% to 99%, 50% to 95%, 50% to 90%, 50% to 80%, 50% to 70%, or 50% to 60% of the weight, based on the total weight of the wet filler. The liquid content of the filler can be expressed as a weight percent: 100 * [mass of liquid] / [mass of liquid + mass of dry filler].

[0032] Alternatively, the amount of liquid can be determined based on the oil adsorption capacity (OAN) of the filler, with the OAN being determined according to ASTM D2414. The OAN is a measure of the filler's structure and can be used to determine the amount of liquid required to wet the filler. For example, a wet filler, such as wet carbon black, wet silica (e.g., precipitated silica), or wet silicon-treated carbon black, may have a liquid content determined by the following equation: k * OAN / (100 + OAN) * 100. In one embodiment, k is in the range of 0.3 to 1.1, or from 0.5 to 1.05, or from 0.6 to 1.1, or from 0.7 to 1.1, or from 0.8 to 1.1, or from 0.9 to 1.1, or from 0.6 to 1.0, or from 0.7 to 1.0, or from 0.8 to 1.0, or from 0.8 to 1.05, or from 0.9 to 1.0, or from 0.95 to 1.0, or from 0.95 to 1.1, or from 1.0 to 1.1.One possibility is that the liquid content of the wet filler can be in the range of 20 to 80%, 30 to 70%, 30 to 60%, 40 to 70% or 40 to 60%.

[0033] One possibility is that the wet filler can have the consistency of a solid. Alternatively, a dry filler is wetted only to the extent that the resulting wet filler retains the form of a powder, particles, pellets, cake, or paste, or a similar consistency and / or appearance. The wet filler does not flow like a liquid (at zero applied tension). Another possibility is that the wet filler can retain its shape at 25°C when formed into such a shape, regardless of whether it consists of individual particles, agglomerates, pellets, cakes, or pastes.The wet filler is not a composite material produced by a liquid masterbatch process, nor is it any other premixed composite material consisting of a filler dispersed in a solid elastomer (from an elastomer in a liquid state), where the elastomer is the continuous phase. The wet filler is not a slurry of filler and does not have the consistency of a liquid or slurry.

[0034] The liquid used to wet the filler may be or contain an aqueous liquid, such as water, but is not limited to this. The liquid may contain at least one other component, such as a base(s), an acid, a salt, a solvent, a surfactant, a coupling agent (e.g., if the filler also contains silicon dioxide), and / or a processing aid, and / or any combination thereof. More specific examples of the component 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 acids 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 that is immiscible with the elastomer used (e.g., alcohols such as ethanol). Alternatively, the liquid may consist of approximately 80% to 100% water by weight or 90% to 99% water by weight, based on the total weight of the liquid.

[0035] In the processes described here, at least the solid elastomer, the wet filler, and the binder are fed (e.g., added, introduced) into the mixer. The feeding of the solid elastomer and / or the filler and / or the binder can be carried out in one or more steps or additions. The feeding can be carried out in any manner, including, but not limited to, conveying, metering, tipping, and / or feeding the solid elastomer and the wet filler into the mixer in a batch, semi-continuous, or continuous flow. The solid elastomer and the wet filler are not introduced into the mixer as a premix in which the premix was prepared by means other than the combination of solid elastomer and wet filler.The solid elastomer and the wet filler may be added together, but not as a mixture prepared by means other than the combination of solid elastomer and wet filler (e.g., not if the wet filler is predispersed into the elastomer by means other than the combination of solid elastomer and wet filler, with the elastomer being the continuous phase). A mixture or premix of solid elastomer, wet filler, and binder may be fed to the mixer and prepared by any number of known methods, e.g., in a mixer or a container.

[0036] The feeding of the solid elastomer, wet filler, and binder can be performed simultaneously or sequentially and in any order. The feeding can involve separate batches of the binder and wet filler. Alternatively, the feeding can involve a mixture containing the wet filler and the binder. For example: (a) all of the solid elastomer is added first, (b) all of the wet filler is added first, (c) all of the solid elastomer is added first with a portion of the wet filler and binder, followed by the addition of one or more remaining portions of the wet filler and binder, (d) a portion of the solid elastomer is added, followed by a portion of the wet filler and / or binder, (e) at least a portion of the wet filler is added first, followed by at least a portion of the solid elastomer and / or at least a portion of the binder.(f) a portion of the solid elastomer, a portion of the wet filler, and a portion of the binder are added to the mixer as separate batches, or (g) at least a portion of the solid elastomer and at least a portion of the wet filler are added in any order and in one or more portions, the at least a portion of the solid elastomer and at least a portion of the wet filler being mixed, the mixer being charged with at least a portion of the binder, and the solid elastomer, the wet filler, and the crosslinking agent being mixed to form the mixture. Other applicable methods for charging the mixer with the solid elastomer and the wet filler are described in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference.

[0037] In a mixture containing the wet filler and the binder, the wet filler and binder can be a particulate mixture, such as a powder. If the binder is a liquid, it can be applied to the wet filler or otherwise combined with it by any number of methods known in the prior art, such as dipping, spraying, etc. If the binder is a solid, it can be applied to the wet filler or combined with it by a solution or dispersion, such as an aqueous solution or dispersion. The powder can be placed in the mixer as is, or it can be formed into a pellet, i.e., a pellet that is a mixture containing the binder.Another possibility is to combine a solution or dispersion containing the binder with flaky carbon black (and optionally silica and / or other fillers). In addition to the combination, the solution can also wet the carbon black (and optionally silica and / or other filler types) to form the wet filler. The resulting wet filler (which consists of or contains, for example, wet carbon black) can then be fed to a pin granulator and granulated according to the procedures described herein.

[0038] The wet filler described here comprises carbon black. On a dry basis, the filler comprises, 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, based on the total weight of the filler, or substantially all of the filler is carbon black. The filler may also contain other types of filler besides carbon black, i.e., at least one additional filler. The additional filler may be particulate, fibrous, or platelet-shaped. A particulate filler, for example, consists of discrete bodies. Such fillers may often have an aspect ratio (e.g., length to diameter) of 3:1 or less, 2:1 or less, or 1.5:1 or less. Fibrous fillers may have an aspect ratio of, for example, 2:1 or more, 3:1 or more, 4:1 or more, or higher.

[0039] As one option, at least one additional filler is selected from carbon-containing materials, carbon black, silicon dioxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, recovered carbon, recovered carbon black (e.g., as defined in ASTM D8178-19, rCB), graphenes, graphene oxides, reduced graphene oxide (e.g., reduced graphene oxide worms as described in PCT Publication No. WO 2019 / 070514A1, the disclosure of which is incorporated herein by reference), or compacted reduced graphene oxide granules (as disclosed in US Prov. Appl. No. 62 / 857,296, filed on June 5, 2019, and PCT Publication No. 2020 / 247681, the disclosures of which are incorporated herein by reference). are), 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 thereof (e.g.B. chemically treated carbon black). Other suitable fillers are carbon nanostructures (CNSs, singular CNS), a variety of carbon nanotubes (CNTs) cross-linked in a polymeric structure by branching, for example, by dendritic branching, interweaving, entanglement, and / or sharing common walls. CNS fillers are described in US Pat. No. 9,447,259 and PCT Publication No. PCT / US2021 / 027814, the disclosures of which are incorporated herein by reference. Mixtures of additional fillers may also be used, e.g., mixtures 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 carbon black with attached organic group(s) or may contain them.The filler may have one or more coatings (e.g., silicon-coated materials, silicon dioxide-coated materials, carbon-coated materials). The filler may be oxidized and / or have other surface treatments. There is no restriction on the type of filler that can be used (e.g., silicon dioxide, carbon black, or another filler).

[0040] The additional filler may comprise a fibrous filler that includes natural fibers, semi-synthetic fibers, and / or synthetic fibers (e.g., nanoscale carbon filaments), such as short fibers described in PCT Publication No. WO 2021 / 153643, the disclosure of which is incorporated herein by reference. Other fibrous fillers include poly(p-phenylene terephthalamide) pulp, which is commercially available as Kevlar® pulp (DuPont).

[0041] Other suitable fillers include bio-produced or bio-based (derived from biological sources) materials, recycled materials, or other fillers considered renewable or sustainable, such as hydrothermal carbon (HTC, where the filler comprises lignin treated by hydrothermal carbonization, as described in U.S. Patents 10,035,957 and 10,428,218, the disclosures of which are incorporated herein by reference), rice hull silica, carbon from methane pyrolysis, artificially produced polysaccharide particles, starch, silica, crumb gum, and functionalized crumb gum. Examples of artificially produced polysaccharides are those described in U.S. Patents 2020 / 0181370 and 2020 / 0190270, the disclosures of which are incorporated herein by reference.The polysaccharides can be selected, for example, from: poly-alpha-1,3-glucan; polyalpha-1,3-1,6-glucan; a water-insoluble alpha-(1,3-glucan) polymer with 90% or more α-1,3-glycosidic bonds, less than 1 wt% α-1,3,6-glycosidic branching points, and a number-mean degree of polymerization in the range of 55 to 10,000; dextran; a composition comprising a poly-alpha-1,3-glucan ester compound; and water-insoluble cellulose with a weight-mean degree of polymerization (DPw) of about 10 to about 1000 and a cellulose II crystal structure.

[0042] As one possibility, the filler of the wet filler can be or contain a mixture of carbon black and at least one additional filler (e.g. silicon dioxide, silicon-treated carbon black, etc.) in any weight ratio, as long as at least 50 wt% of the filler (or at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%) is dry-based carbon black. The wet filler can contain a liquid in an amount of approximately 25% to approximately 75% by weight, e.g., approximately 30% to approximately 75%, approximately 40% to approximately 75%, approximately 45% to approximately 75%, approximately 50% to approximately 75%, approximately 30% to approximately 70%, approximately 40% to approximately 70%, approximately 45% to approximately 70%, approximately 50% to approximately 70%, approximately 30% to approximately 65%, approximately 40% to approximately 65%, approximately 45% to approximately 65%, approximately 50% to approximately 65%, approximately 30% to approximately 60% by weight, approximately 40% to approximately 60%, approximately 45% to approximately 60%, or approximately 50% to approximately 60% by weight.-%, based on the weight of the total wet filler. The at least one additional filler can be wetted such that the filler mixture has a liquid content of at least 20% by weight, based on the total weight of the wet filler, or one of the amounts described herein.

[0043] In addition to the wet filler, the mixture may, as one possibility, contain one or more non-wetted fillers (e.g., all fillers that are not wetted as described here, such as dry fillers, or fillers with no more than 10% liquid by weight). If non-wetted filler is present, the total amount of filler may be such that at least 50%, 60%, 70%, 80%, 90%, or 95% of the total weight of the filler is a wet filler, etc. B. 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, 90% to 99% or 95% to 99% of the total amount of filler may be a wet filler, with the remainder of the filler being in a non-wetted state or not considered a wet filler.

[0044] The amount of filler (e.g., wet filler alone or wet filler with another filler) incorporated into the mixture can be adjusted (on a dry weight basis) to a target amount of at least 20 phr, at least 30 phr, at least 40 phr, or a range of 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, 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. The phr value can be set to 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 quantities within or outside one or more of these ranges. The phr values ​​mentioned above can also apply to the filler dispersed in the elastomer (filler loading).Other types of fillers, mixtures, combinations, etc., may also be used, such as those described in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference.

[0045] The solid elastomer used and mixed with the wet filler can be considered a dry or 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 from 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 forth. The solid elastomer (e.g., the starting solid elastomer) may consist entirely of elastomer (with a starting liquid content, e.g., water, of 5 wt% or less), or it may be an elastomer that also contains one or more fillers and / or other components. For example, the solid elastomer can consist of 50 to 99.9 wt.% elastomer with 0.1 to 50 wt.-% filler predispersed in the elastomer, the predispersed filler being present in addition to the wet filler. Such elastomers can be produced by dry mixing processes between non-wetted filler and solid elastomers. Alternatively, a composite produced by mixing a wet filler and a solid elastomer (e.g., according to the processes described herein) can be used as the solid elastomer and further blended with a wet filler according to the processes described herein. However, the solid elastomer is not a composite, mixture, or compound produced by a liquid masterbatch process, nor is it another premixed composite of filler dispersed in an elastomer while the elastomer is in a liquid state, e.g., a latex, suspension, or solution.

[0046] Any solid elastomer can be used for the procedures presented here. Examples of 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-extended 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 rubbers (NBR), hydrogenated nitrile rubber (HNBR), fluoroelastomers, perfluoroelastomers, and silicone rubber, etc. B. Natural rubber and mixtures thereof, e.g. natural rubber, styrene-butadiene rubber, polybutadiene rubber and mixtures thereof, e.g. a mixture of a first and a second solid elastomer.Other synthetic polymers that can be used in the present processes (either alone or as mixtures) include hydrogenated SBR and thermoplastic block copolymers (e.g., those that are recyclable). Synthetic polymers include copolymers of ethylene, propylene, styrene, butadiene, and isoprene. Other synthetic elastomers are synthesized using metallocene chemistry, with the metal selected from Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Tm, Yb, Lu, Co, Ni, and Ti. Polymers from bio-based monomers can also be used, such as monomers containing modern carbon according to ASTM D6866. B. Polymers made from bio-based styrene monomers described in US Pat. 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.When two or more elastomers are used, they can be added to the mixer simultaneously as a mixture (as one batch or two or more batches), or they can be added separately in any order and quantity. For example, the solid elastomer can consist of natural rubber blended with one or more of the elastomers described here, such as butadiene rubber and / or styrene-butadiene rubber, or SBR blended with BR, etc. Alternatively, the additional solid elastomer can be added to the mixer separately, and the natural rubber can also be added separately.

[0047] The solid elastomer may be or contain natural rubber. If the solid elastomer is a mixture, it may contain at least 50% by weight, at least 70% by weight, or at least 90% by weight of natural rubber. The mixture may further comprise synthetic elastomers such as one or more styrene-butadiene rubbers, functionalized styrene-butadiene rubbers, and polybutadiene rubbers, and / or any other elastomers described herein.

[0048] Natural rubber can also be chemically modified in various 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 different monomers or other chemical groups such as chlorine. Other examples include epoxidized natural rubber and natural rubber with a nitrogen content of no more than 0.3 wt%, as described in PCT Publication No. WO 2017 / 207912.

[0049] Other exemplary elastomers include, but are not limited to, rubbers, polymers (e.g., homopolymers, copolymers and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene, where alkyl may be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propylene and the like.

[0050] Other applicable solid elastomers that can be used in the processes described herein are disclosed in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference.

[0051] Regarding the mixer, which can be used in any of the processes described herein, any suitable mixer capable of combining a filler with a solid elastomer (e.g., mixing or compounding them) may be used. The mixer(s) may be a batch mixer or a continuous mixer. A combination of mixers and processes may be used in any of the processes described herein, and the mixers may be used sequentially, in tandem, and / or integrated with other processing equipment. The mixer may be an internal or closed mixer, an open mixer, an extruder, a continuous compounder, a kneading mixer, or a combination thereof.The mixer may be able to introduce filler and binder into a solid elastomer and / or disperse the filler and binder in the elastomer and / or distribute the filler and binder in the elastomer.

[0052] The mixer can have one or more rotors (at least one rotor). The at least one rotor, or the one or more rotors, can be screw rotors, intermeshing rotors, tangential rotors, kneading rotors, rotors used for extruders, a rolling mill that provides significant total specific energy, or a creping mill. Generally, one or more rotors are used in the mixer; for example, the mixer can contain one rotor (e.g., a screw rotor), two, four, six, eight, or more rotors. Sets of rotors can be arranged in parallel and / or in series in a given mixer configuration.

[0053] As for mixing, it can occur in one or more mixing steps. Mixing begins when at least the solid elastomer and the wet filler are fed into the mixer and energy is supplied to a mixing system that drives one or more of the mixer's rotors. The one or more mixing steps can occur after the loading step is completed or 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 added to the mixer before or after the start of the mixing process. Subsequently, the mixer can be fed with one or more additional portions of the solid elastomer and / or filler and / or binder. In batch mixing, the loading step is completed before the mixing step.

[0054] One possibility is that control via mixer surface temperatures, regardless of the mechanism(s), can provide a way to achieve longer mixing or residence times, which can lead to improved dispersion of the filler and / or improved rubber-filler interactions and / or more uniform mixing and / or more efficient mixing, compared to mixing processes without temperature control of at least one mixer surface.

[0055] The temperature control device can be, but is not limited to, the flow or circulation of a heat transfer fluid through channels in one or more parts of the mixer. The heat transfer fluid can be, for example, water or heat transfer oil. The heat transfer fluid can flow, for example, through the rotors, the walls of the mixing chamber, the piston, and the outlet. In other embodiments, the heat transfer fluid can flow in a jacket (e.g., a jacket with fluid flow devices) or in coils around one or more parts of the mixer. Another possibility is that the temperature control (e.g., the heat input) is achieved by electrical elements integrated into the mixer.The temperature control system may further include devices for measuring the temperature of the heat transfer fluid or the temperature of one or more parts of the mixer. The temperature measurements can be transmitted to systems used to control 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 adjusting the temperature of the heat transfer fluid in channels adjacent to one or more parts of the mixer, such as walls, gates, rotors, etc.

[0056] The temperature of at least one temperature control unit can be set and maintained, for example, by one or more temperature control units (“TCUs”). This set temperature, or TCU temperature, is also referred to here as “T”. z“ denoted. In temperature control devices containing heat transfer fluids, T z an indication of the temperature of the liquid itself.

[0057] One possibility is to set the temperature control device to a temperature, T z, can be set in the range of 30°C to 150°C, 40°C to 150°C, 50°C to 150°C or 60°C to 150°C, e.g., 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 with commercially available equipment.

[0058] Compared to dry mixing, under similar conditions with respect to filler type, elastomer type, and mixer type, the present methods allow for a higher energy input. The controlled removal of water from the mixture enables longer mixing times and consequently improves the dispersion of the filler. As described here, the present method offers operating conditions that balance longer mixing times with the advantage of evaporating or removing water within a reasonable timeframe.

[0059] Other operating parameters to consider include the maximum pressure that can be used. Pressure affects the temperature of the filler and rubber compound. If the mixer is a batch mixer with a piston, the pressure in the mixing chamber can be controlled by adjusting the pressure exerted on the piston cylinder.

[0060] Another possibility is to optimize the rotor peak speeds. The energy introduced into the mixing system is at least partially a function of the rotational speed of the at least one rotor and the rotor type. The peak speed, which takes into account the rotor diameter and the rotor speed, can be calculated using the following formula: Peak speed,m / s=π×(rotor diameter,m)×(rotational speed,rpm) / 60.

[0061] Since peak velocities can vary during mixing, one option is to achieve a peak velocity of at least 0.5 m / s or at least 0.6 m / s for at least 50% of the mixing time, e.g., at least 60%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or substantially throughout the entire mixing time. The peak velocity can 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 for at least 50% of the mixing time or other portions of the mixing process listed above. The peak speeds can be selected to minimize the mixing time, or they can be set from 0.6 m / s to 10 m / s, from 0.6 m / s to 8 m / s, from 0.6 to 6 m / s, from 0.6 m / s to 4 m / s, from 0.6 m / s to 3 m / s, from 0.6 m / s to 2 m / s, from 0.7 m / s to 4 m / s, from 0.7 m / s to 3 m / s, from 0.7 m / s to 2 m / s, from 0.7 m / s to 10 m / s, from 0.7 m / s to 8 m / s, from 0.7 to 6 m / s, from 1 m / s to 10 m / s, from 1 m / s to 8 m / s, from 1 m / s to 6 m / s, from 1 m / s to 4 m / s, from 1 m / s to 3 m / s or from 1 m / s to 2 m / s, (e.g., for at least 50% of the mixing time or other mixing times described herein).

[0062] Any combination of commercially available mixers with one or more rotors, temperature control device and other components, as well as associated mixing processes for the production of rubber compounds, may be used in the present processes, such as those described in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference.

[0063] The term "one or more mixing steps" means that the steps described here may include an initial mixing step followed by further mixing steps before emptying. The one or more mixing steps may be a single mixing step, such as a single-stage or single-stage mixing step or process, in which mixing takes place under one or more of the following conditions: at least one of the mixer temperatures is controlled by temperature-controlled devices, with one or more rotors operating at a peak speed of at least 0.6 m / s for at least 50% of the mixing time, and / or the at least one temperature control device is set to a temperature T z, set at 65°C or higher, and / or continuous mixing; each of these is described in more detail herein. In certain cases, the composite material can be discharged in a single stage or mixing step with a liquid content of not more than 10 wt%. In other embodiments, two or more mixing steps or stages may be carried out, provided that one of the mixing steps is carried out under one or more of the conditions mentioned.

[0064] As already mentioned, during one or more mixing steps in each of the processes described here, at least some of the liquid present in the mixture and / or the introduced wet filler is removed, at least partially, by evaporation. Alternatively, during one or more mixing steps or stages, some of the liquid can be removed from the mixture by pressing, compacting, and / or wringing, or a combination thereof. Another option is to drain some of the liquid from the mixer after or during the unloading of the mixture.

[0065] During the mixing cycle, after most of the liquid has been released from the composite and the filler incorporated, the mixture experiences a temperature increase. It is desirable to avoid excessive temperature increases that would degrade the elastomer. Drainage (e.g., "dumping" during batch mixing) can be controlled based on time, temperature, or specific energy or power parameters selected to minimize such degradation.

[0066] In all processes disclosed herein, the emptying step takes place from the mixer and results in a composite material comprising the filler dispersed in the natural rubber with a total loading of at least 20 phr, e.g., 20 to 250 phr, or other loadings described herein. One possibility is that the emptying can be based on a defined mixing time. The mixing time between the start of mixing and emptying can be approximately 1 minute or more, e.g., from approximately 1 minute to 40 minutes, from approximately 1 minute to 30 minutes, from approximately 1 minute to 20 minutes, or from 1 minute to 15 minutes, or from 3 minutes to 30 minutes, from 5 minutes to 30 minutes, or from 5 minutes to 20 minutes, or from 5 minutes to 15 minutes, or from 1 minute to 12 minutes, or from 1 minute to 10 minutes, or other times.Alternatively, for batch-operated internal mixers, the plunger's descent time can be used as a parameter to monitor batch mixing times, e.g., the time the mixer operates with the plunger in its lowest position, such as in the fully lowered position or with a plunger deflection (as described in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference). The plunger's descent time can be less than 30 minutes, less than 15 minutes, less than 10 minutes, or in the range of 3 to 30 minutes, 5 to 15 minutes, or 5 to 10 minutes. One possibility is that emptying can be based on the pouring or emptying temperature.For example, the mixer can have a discharge temperature of 120°C to 190°C, 130°C to 180°C, 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.

[0067] The processes further include emptying the formed composite material from the mixer. The discharged composite material may have a liquid content of no more than 10 wt.%, based on the total weight of the composite material, as shown in the following equation: Liquid content of the composite material %=100%[mass of liquid] / [mass of liquid+mass of dry composite material]

[0068] In each of the processes described herein, the discharged composite material may have a liquid content of no more than 10 wt.%, based on the total weight of the composite material, such as no more than 9%, no more than 8%, no more than 7%, no more than 6%, no more than 5%, no more than 2%, or no more than 1 wt.%, based on the total weight of the composite material. This amount may be in the range of 0.1% to 10%, 0.5% to 9%, 0.5% to 7%, 0.5% to 5%, or 0.5% to 3%, based on the total weight of the composite material discharged from the mixer at the end of the process. In each of the processes described herein, the liquid content (e.g., "moisture content") may be the measured weight percentage of the liquid present in the composite material, based on the total weight of the composite material.

[0069] In all the methods described here, the liquid content in the composite material can be measured as the weight percentage of the liquid present in the composite, relative to the total weight of the composite. A variety of instruments are known for measuring the liquid content (e.g., water) in rubber materials, such as a coulometric Karl Fischer titration system or a moisture balance, e.g., from Mettler (Toledo International, Inc., Columbus, OH).

[0070] In all the processes described here, the discharged composite material may have a liquid content of 10 wt.% or less, but there may be liquid (e.g., water) present in the mixer that is not contained in the discharged composite material. This excess liquid is not part of the composite material and is not included in the calculation of the composite material's liquid content.

[0071] In all processes described here, the total liquid content (or total water content or total moisture content) of the material fed into the mixer is higher than the liquid content of the composite material discharged at the end of the process. For example, the liquid content of the discharged composite material can be 10% to 99.9% (wt% vs. wt%), 10% to 95%, or 10% to 50% lower than the liquid content of the material fed into the mixer.

[0072] Optionally, the method further comprises the addition of the binder and, optionally, anti-degradants during the feeding or mixing process, i.e., during one or more mixing steps. In each embodiment described herein, the method may, as a further option, after the commencement of mixing at least the solid elastomer and the wet filler and before the unloading step, further comprise the addition of the binder and, optionally, at least one anti-degradant agent to the mixer, so that the binder and the at least one anti-degradant agent are mixed with the solid elastomer and the wet filler.One possibility is that the mixture consists essentially of the solid elastomer and the wet filler; the mixture consists essentially of the solid elastomer, the wet filler, and the degradation inhibitor; the composite consists essentially of the filler dispersed in the elastomer and the degradation inhibitor; the composite consists of the filler dispersed in the elastomer; the composite consists of the filler dispersed in the elastomer and the degradation inhibitor. Another possibility is that the binder and the degradation inhibitor(s) can be added before the formation of the composite, which has a water content of 10 wt.% or less, or 5 wt.% or less.

[0073] The binder and, optionally, the decomposition inhibitor(s) can be added at any time before the emptying step, for example, before or after the mixer reaches a displayed mixer temperature of 120°C or higher. This displayed mixer temperature can be measured by a temperature measuring device in the mixing chamber. The displayed mixer temperature can be the same as the maximum temperature of the mixture or composite reached during the mixing phase (which can be determined by removing the composite from the mixer and inserting a thermocouple or other temperature measuring device into the composite), or it can differ from it 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).In this mixing process, one option is to add the binder and, if applicable, the decomposition inhibitor to the mixer when the mixer reaches a temperature of 120°C or more. In other embodiments, the specified temperature can 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, from 130°C to 170°C, from 135°C to 170°C, from 140°C to 170°C, from 145°C to 170°C, from 150°C to 170°C, and the like.

[0074] Examples of degradation inhibitors that may be introduced include N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and others described in other sections herein. The degradation inhibitor may be added in an amount ranging from 1% to 5%, 0.5% to 2%, or 0% to 3% by weight, based on the weight of the composite material formed. Adding degradation inhibitors during feeding or mixing may help prevent elastomer degradation during mixing; however, due to the presence of water in the mixture, the rate of elastomer degradation is lower than in dry mixing processes, and the addition of the degradation inhibitor may be delayed.

[0075] After the composite material has been formed and discharged, the process may include the further optional step of mixing the composite with an additional elastomer to form a composite material comprising a mixture of elastomers. The “additional elastomer” or second elastomer may be an additional natural rubber or an elastomer that is not a natural rubber, such as any elastomer described herein, e.g. B. synthetic elastomers (e.g. styrene-butadiene rubbers (SBR, such as SSBR, ESBR, etc.), polybutadiene (BR) and polyisoprene rubbers (IR), ethylene propylene rubber (e.g., EPDM), isobutylene-based elastomers (e.g., butyl rubber), polychloroprene rubber (CR), nitrile rubbers (NBR), hydrogenated nitrile rubbers (HNBR), polysulfide rubbers, polyacrylate elastomers, fluoroelastomers, perfluoroelastomers, and silicone elastomers).Mixtures of two or more elastomer types (mixtures of first and second elastomer), including mixtures of synthetic and natural rubber or with two or more types of synthetic or natural rubber, can also be used.

[0076] The mixer can be charged with two or more batches of different elastomers to form a composite mixture. For example, the mixer can be charged with never-dried natural rubber and at least one other elastomer, where the at least one other elastomer is also a coagulum or a solid elastomer (e.g., with less than 5% water). Alternatively, the mixer can be charged with an elastomer mixture. As another possibility, the process can involve mixing the discharged composite with additional elastomer to form the mixture. The discharged composite (e.g., after single-stage or two- or multi-stage mixing) can have a moisture content of no more than 5% by weight, 3% by weight, or 2% by weight of the composite when mixed with one or more additional elastomers (e.g.,A composite material comprising carbon black and natural rubber can be mixed with synthetic elastomers, such as BR or SBR. Furthermore, both elastomers and fillers (wet or dry, such as wet or dry carbon black and / or silicon dioxide and / or silicon-treated carbon black) can be combined with the composite material.

[0077] Alternatively, a composite material comprising a filler (e.g., carbon black and / or silica) and an elastomer (e.g., natural rubber and / or SBR and / or BR), prepared according to the processes described herein, can be combined with a masterbatch containing natural rubber and / or synthetic polymers, prepared according to any prior art process, such as known dry-mix or solvent-based masterbatch processes. For example, silicon dioxide / elastomer masterbatches can be prepared as described in U.S. Patents 9,758,627 and 10,125,229, or neodymium-catalyzed polybutadiene masterbatches as described in U.S. Patent 9,758,646, the disclosures of which are incorporated herein by reference. The masterbatch may contain a fibrous filler, such as poly(p-phenylene terephthalamide) pulp, as in US Pat. No.Masterbatches can include fillers such as graphene, graphene oxides, reduced graphene oxides, or densified reduced graphene oxide granules, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanostructures, masterbatches of the latter being disclosed in US Patent No. 9,447,259 and PCT Note No. PCT / US2021 / 027814, the disclosures of which are incorporated herein by reference. Other suitable masterbatches can include composite materials produced by mixing wet filler and solid elastomer, as described in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference. The masterbatch may contain, for example, a filler such as carbon black and / or silica, and an elastomer such as natural rubber and / or SBR and / or butadiene rubber.Commercially available masterbatches can also be used, e.g., commercially available masterbatches such as Emulsil™ silicon dioxide / SBR masterbatch or Emulblack™ carbon black / SBR masterbatch (both available from the Dynasol Group).

[0078] Exemplary masterbatches comprising elastomer blends (regardless of whether the blend is formed in a first or single-stage blending or in a multi-stage blending) include: blends of natural rubber with synthetic, bio-based 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.

[0079] In addition to the solid elastomer, the wet filler, and the binder, the mixer can be fed with one or more batches of at least one other elastomer to form a composite mixture. Alternatively, the process can involve mixing the discharged composite with additional elastomer to form the mixture. The at least one additional elastomer can be the same as the solid elastomer or different from it.

[0080] Alternatively, the discharged composite material may contain at least one additive selected from decomposition inhibitors and adhesion promoters (e.g., if the wet filler also contains silicon dioxide or if the mixer is fed with dry silicon dioxide), which can be added at any time during the feeding or mixing process.

[0081] The carbon black can be untreated carbon black, treated carbon black, or a mixture thereof. The filler can be or comprise wet carbon black in the form of pellets, flaky powder, granules, and / or agglomerates. Wet carbon black can be formed into pellets, granules, or agglomerates, for example, in a pelletizing plant, a fluidized bed, or other equipment for producing the wet filler.

[0082] The wet soot can be one or more of the following substances: - never dried soot; and / or - never dried soot pellets; and / or - dried carbon black pellets that have been re-moistened, for example with water in a pelletizing plant, and / or - dried carbon black pellets that were ground and then re-moistened with water in a pelletizing plant; and / or - dried carbon black pellets in combination with water; and / or - flaky powder, granules or agglomerates in combination with water.

[0083] In typical carbon black production, the carbon black is initially produced as a dry, finely divided (flaky) material. This flaky carbon black can be compacted using a conventional pelletizing process, for example, by combining the carbon black with a liquid, such as water, and feeding the mixture into a pin pelletizing machine. The liquid can be a solution or dispersion containing the binding agent. Pin pelletizing machines are well-known in the prior art and include the one described in US Patent No. 3,528,785. The resulting wet pellets are then heated under controlled temperature and time parameters to remove the liquid from the pellets before they are further processed and shipped. Alternatively, carbon black pellets can be produced in a process that omits the drying step.In such a process, the pelletized soot contains at least 20 wt.% process water, based on the total weight of the wet soot, e.g. at least 30 wt.% or at least 40 wt.%.

[0084] Alternatively, dried carbon black pellets (e.g., commercially available carbon black pellets) can be re-moistened in a pelletizing plant. The pellets can be granulated, ground, classified, and / or milled, e.g., in a jet mill. The resulting carbon black has a flaky form and can be re-pelleted in a pelletizing plant or otherwise compressed or agglomerated in the presence of water to moisten the carbon black. One possibility is to re-pellete the carbon black in the pelletizing plant in the presence of a solution or dispersion containing the binder. Alternatively, the flaky carbon black can be pressed into other shapes, e.g., bricks, using equipment known in the art. Another possibility is to moisten the carbon black, such as the carbon black pellets or the flaky carbon black, e.g., using a fluidized bed, a spray device, a mixer, a rotating drum, and the like.If the liquid is water, dried or rehydrated soot can never reach a water content of 20 wt.% to 80 wt.%, 30 wt.% to 70 wt.% or other ranges, e.g. 55 wt.% to 60 wt.%, based on the total weight of the wet soot.

[0085] The soot may be a furnace soot, a gas soot, a thermal soot, an acetylene soot or a lamp soot, a plasma soot, a recovered soot (e.g., as defined in ASTM D8178-19), or a carbon product containing silicon-containing species and / or metal-containing species and the like.

[0086] The carbon black used in any of the processes described here can be any class of reinforcing carbon blacks and semi-reinforcing carbon blacks or other carbon blacks with a statistical thickness surface area (STSA) of 20 m². 2 / g up to 250 m 2 / g or higher. STSA (statistical thickness surface area) is determined according to ASTM test method D-5816 (measured by nitrogen adsorption). Examples of ASTM intensifying classes are carbon blacks N110, N121, N134, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, and N375. Examples of ASTM semi-intensifying classes are carbon blacks N539, N550, N650, N660, N683, N762, N765, N774, N787, N990, and / or N990 thermal carbon blacks.

[0087] The soot can have any statistical thickness surface area (STSA), e.g. in the range of 20 m. 2 / g up to 250 m 2 / g or higher. STSA (statistical thickness surface area) is determined according to ASTM test method D-5816 (measured by nitrogen adsorption). The carbon black can have a compression oil absorption number (COAN) of approximately 30 mL / 100g to approximately 150 mL / 100g. The compression oil absorption number (COAN) is determined according to ASTM D3493. As one possibility, the carbon black can have an STSA in the range of 20 m 2 / g up to 180 m 2 / g or from 60 m 2 / g up to 150 m 2 / g with a COAN in the range of 40 mL / 100g to 115 mL / 100g or from 70 mL / 100g to 115 mL / 100g.

[0088] As previously mentioned, the carbon black can be a rubber carbon black, specifically a reinforcing carbon black class or a semi-reinforcing carbon black class. Carbon blacks available under the trademarks Regal®, Black Pearls®, Spheron®, Sterling®, Propel®, Endure®, and Vulcan® from Cabot Corporation; under the trademarks Raven®, Statex®, Furnex®, and Neotex®, as well as the CD and HV lines from Birla Carbon (formerly available from Columbian Chemicals); and under the trademarks Corax®, Durax®, Ecorax®, and Purex®, as well as the CK line from Orion Engineered Carbons (formerly Evonik and Degussa Industries), as well as other fillers suitable for use in rubber or tire applications, can also be used for various applications. Suitable chemically functionalized carbon blacks include those described in WO 96 / 18688 and US 2013 / 0165560, the disclosures of which are hereby incorporated by reference. Mixtures of any of these soots can also be used.

[0089] Each of the processes described here relates in part to processes for the production of a composite material that include at least two mixing steps or stages. These two (or more) mixing steps can be considered multi-stage mixing or multi-stage mixing with a first mixing step or stage and at least one second mixing step or stage. One or more of the multi-stage mixing processes can be carried out batchwise, continuously, semi-continuously, or in combinations thereof.

[0090] In multi-stage processes, the methods for producing the composite material include the step of feeding or introducing into a first mixer at least a) one or more solid elastomers, b) one or more fillers, wherein at least one filler or part of at least one filler is a wet filler as described herein (e.g., a wet filler comprising a filler and a liquid present in an amount of at least 20% by weight, based on the total weight of the wet filler), and optionally c) the binder. By combining the solid elastomer with the wet filler and optionally the binder, a mixture or composite material is formed during this mixing step or these mixing steps, which may be considered the first mixing step or first mixing stage.The process further comprises mixing the mixture in this first mixing step to such an extent that at least some 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 this first stage is carried out using one or more of the previously described processes that form a composite material, and it is not necessary for the mixture discharged from the mixer after the first mixing step (e.g., a discharged mixture) to have a liquid content of no more than 10% by weight. In other words, in the multi-stage process(s), the mixture obtained from the first mixer (or the first mixing step) after completion of the first mixing operation may have a liquid content of more than 10% by weight.-%, but has a liquid content that is reduced compared to the liquid content of the combined solid elastomer and wet filler at the beginning of the first mixing step (in wt.%).

[0091] Before the first mixer or another mixer in the second mixing step is used, there may be an optional settling period during which the composite material formed from the first mixing rests or cools, or both, in the first mixer, in another container, or at another location (e.g., mixing, stopping, and then mixing again). This settling period may be designed, for example, to ensure that the mixture reaches a material temperature (also known as probe temperature) of less than 180°C before the next mixing step begins (e.g., the discharged mixture may have a material temperature in the range of approximately 100°C to approximately 180°C, approximately 70°C to 179°C, approximately 100°C to approximately 170°C, or approximately 120°C to approximately 160°C). Alternatively, the settling period before the start of the next or second mixing step may range from approximately 1 minute to 60 minutes or more.The material temperature can be determined by a number of methods known in the prior art, e.g. by inserting a thermocouple or other temperature measuring device into the mixture or composite material.

[0092] The process then includes mixing or further mixing the mixture in at least one second mixing step or stage using the same mixer (i.e., the first mixer) and / or using a second mixer(s) that differs from the first mixer. In a multi-stage mixing process, the binder can be added either to the first mixer, the second mixer, or both.

[0093] After the initial mixing, the subsequent mixing step(s) performed in multi-stage mixing may utilize one or more of the mixing methods, parameters, or steps used in the initial mixing step, as described herein. Thus, the same or a different mixer design and / or the same or different operating parameters as used for the initial mixer may be employed in the subsequent mixing step or stage. The mixers and their options and / or the operating parameters previously described for the initial mixing step may, if appropriate, be used in the subsequent or second mixing step (e.g., the mixing steps described herein, which maintain a peak velocity 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 zincluding those operating at 65°C or higher, among others described herein or in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference.

[0094] In multi-stage processes, a second mixing step (second mixing stage) can also include feeding the mixer with other components in addition to the mixture discharged from the first mixing step. For example, if the binder is not fed to the first mixer, it can be fed to the second mixer, e.g., as a separate batch or as a mixture (particle mixture or co-pellet) with filler (wet or dry filler, the same or a different filler as in the first mixer). Additionally or alternatively, the process can, for example, include the addition of additional filler, such as dry filler, wet filler, or a mixture thereof, before or during the second mixing step. The additional filler can be the same or a different filler than the filler already present in the mixture, e.g., one of the additional fillers described herein.For example, the mixture discharged from the first mixer can be considered a masterbatch, in which either all or part of it is combined with additional filler. For instance, wet or dry carbon black, silicon dioxide, silicon-treated carbon black (and mixtures thereof) can be added to the mixture discharged from the first mixing step, such as a mixture of carbon black and natural rubber.

[0095] For the multi-stage mixing process, at least one option uses at least one second mixer in the subsequent mixing step(s). If this option is used, the second mixer can have the same or a different design as the first mixer and / or have the same or one or more different operating parameters as the first mixer. Specific, non-restrictive examples of the first mixer and the second mixer option are given below. The first mixer can be, for example, a tangential mixer or an intermeshing mixer, and the second mixer can be a tangential mixer, an intermeshing mixer, an extruder, a kneader, or a rolling mill. The first mixer can be, for example, an internal mixer, and the second mixer a kneader, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a continuous compounder, or a rolling mill. The first mixer can be, for example,The first mixer may be a tangential mixer, and the second mixer a different tangential mixer. For example, the first mixer may be operated with a plunger, and the second mixer without a plunger. The second mixer may be operated, for example, with a mixture fill factor, based on dry weight, of 25% to 70%, 25% to 60%, 25% to 50%, 30% to 50%, or with other fill factor values ​​described herein.

[0096] As one possibility, the method includes mixing or further mixing the mixture in at least one second mixing step or stage using the same mixer (i.e., the first mixer) and / or using a second mixer(s) that is / are different from the first mixer. The mixing with the second mixer can be carried out such that the second mixer or the second mixing is operated at a ram pressure of 5 psi or less and / or with a ram raised to at least 75% of the ram's highest level (e.g., at least 85%, at least 90%, at least 95%, or at least 99% or 100% of the ram's highest level) and / or with a ram operated in a state of suspension and / or with a ram positioned so that it does not substantially touch the mixture and / or with a ramless mixer and / or with a mixture fill factor in the range of 25% to 70%.The process then includes discharging the formed composite material from the last mixer used, so 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 a second mixer are described in PCT Publication No. WO 2020 / 247663, the disclosure of which is incorporated herein by reference.

[0097] Additives can also be incorporated into the mixing and / or compounding steps (e.g., in a single-stage mixing process or in the second or third stage of a multi-stage mixing process) and may include degradation inhibitors and one or more rubber chemicals to facilitate the dispersion of the filler in the elastomer. Rubber chemicals, as defined herein, include one or more of the following: processing aids (to facilitate the mixing and processing of rubber, e.g., various oils and plasticizers, waxes), activators (to activate the vulcanization process, e.g., zinc oxide and fatty acids), accelerators (to accelerate the vulcanization process, e.g., sulfonamides and thiazoles), vulcanizing agents (or curing agents to crosslink rubbers, e.g., sulfur, peroxides), and other rubber additives, such as retarders, co-agents, peptizers, adhesion promoters, etc.B. Use of cobalt salts to promote the adhesion of steel cables to rubber-based elastomers (e.g., as described in US Pat. No. 5,221,559 and US Pat. Publication No. 2020 / 0361242, the disclosures of which are incorporated herein by reference), resins (e.g., tackifiers, traction resins), flame retardants, dyes, blowing agents, and heat-reducing additives (HBU). As one option, the rubber chemicals may include processing aids and activators. Another option is to select one or more other rubber chemical(s) from zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, and processing oil. Examples of resins include those selected from one or more C5 resins, C5-C9 resins, C9 resins, rosin resins, terpene resins, aromatically modified terpene resins, dicyclopentadiene resins, alkylphenol resins, and resins described in US Pat. Nos.10,738,178, 10,745,545 and US Pat. Pub. No. 2015 / 0283854, the disclosures of which are incorporated herein by reference.

[0098] In each process described herein for the production of a composite material, the process after the formation of the composite material may include one or more of the following steps: - one or more halting steps; - One or more drying steps can be applied to further dry the composite material in order to obtain a dried composite material; - one or more extrusion steps; - one or more calender steps; - one or more grinding steps to obtain a ground composite material; - one or more granulation steps; - one or more cutting steps; - one or more baling steps to obtain a baled product or mixture; - the bale mixture or the product can be broken up to form a granulated mixture; and / or - one or more mixing or compounding steps; and / or - one or more rolling steps.

[0099] As another example, the following sequence of steps can be performed, and each step can be repeated as many times as desired after the composite material has been formed (with the same or different settings): - one or more holding steps to develop further elasticity - one or more cooling steps - further drying of the composite material to obtain another dried composite material; - Mixing or compounding the composite material to obtain a compounded mixture; - Grinding the compounded mixture to obtain a ground mixture (e.g., roller milling); - Granulate the ground mixture; - if necessary, baling the mixture after granulation to obtain a baled mixture; - possibly break up and mix the bale mixture.

[0100] Additionally or alternatively, the composite material can be mixed with one or more degradation inhibitors, zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, processing oil, and / or curing agents and vulcanized to form a vulcanizate. Such vulcanized composites may exhibit one or more improved properties, such as improved rubber properties, including, but not limited to, improved hysteresis, wear resistance, and / or rolling resistance (e.g., in tires), or improved mechanical strength and / or tensile strength, or an improved tan delta and / or tensile stress ratio, and the like.

[0101] In a compounding step, for example, the components, with the exception of sulfur or another crosslinking agent and the accelerator, are combined with the pure composite material in a mixing device (the non-curing agents and / or degradation inhibitors are often premixed and referred to as "smalls"). The most common mixing device is the internal mixer, e.g., the Banbury or Brabender mixer, but other mixers, such as continuous mixers (e.g., extruders), can also be used. Then, in a final or second compounding step, the crosslinking agent, e.g., sulfur, and (if required) an accelerator (collectively referred to as the curing agent) are added.As a further option, compounding can involve combining the composite material with one or more of the following substances: decomposition inhibitors, zinc oxide, fatty acids, zinc salts of fatty acids, wax, accelerators, resins, processing oil, and curing agents in a single compounding stage or step. For example, the curing agents can be added along with small amounts in the same compounding stage. The compounding step is often carried out in the same type of equipment as the mixing step, but it can also be performed in a different type of mixer or extruder, or in a rolling mill. Those skilled in the art will recognize that vulcanization begins after the addition of the curing agents as soon as the correct activation conditions for the crosslinking agent are reached. Therefore, when using sulfur, the temperature during mixing is preferably kept well below the curing temperature.

[0102] This document also describes methods for producing a vulcanizate. The method may include at least the steps of curing a composite material in the presence of at least one curing agent. Curing may be effected by applying heat, pressure, or both, as is known in the prior art.

[0103] With regard to this vulcanizate, the vulcanizate may exhibit one or more elastomeric properties. For example, the vulcanizate may have a tensile stress ratio M300 / M100 of at least 5.9, e.g., at least 6.0, at least 6.1, at least 6.2, as evaluated according to ASTM D412, where M100 and M300 refer to the tensile stress at 100% and 300% elongation, respectively.

[0104] Alternatively or additionally, the volcanic material can have a maximum tan δ (60°C) of no more than 0.22, e.g. no more than 0.21, no more than 0.2, no more than 0.19, no more than 0.18, e.g. no more than 0.16, no more than 0.15, no more than 0.14, no more than 0.13, no more than 0.12, or no more than 0.11.

[0105] The vulcanizates produced from the composite materials present (e.g. those produced by one of the processes described herein for mixing wet filler, solid elastomer and binder under the described mixing conditions of T zor at peak speed, regardless of whether single- or multi-stage processes are used, can exhibit improved properties. For example, vulcanizates produced from the present composite materials may have better properties than a vulcanizate produced from a composite material manufactured by dry mixing solid elastomer, non-wetted filler, and binder (“dry mix composite”), especially those dry mix composites having the same composition (“dry mix equivalent”). Thus, the comparison is drawn between dry mixes and the present mixing processes using comparable fillers, elastomers, filler contents (e.g., ± 5 wt.%, ± 2 wt.%), and mixture formulations (including binders), as well as optional curing additives.Under these conditions, the vulcanizate exhibits a tan δ value that is lower than the tan δ value of a vulcanizate produced from a dry-mix composite of the same composition. Additionally or alternatively, the vulcanizate exhibits a tensile stress ratio M300 / M100 that is greater than the tensile stress ratio of a vulcanizate produced from a dry-mix composite of the same composition, where M100 and M300 refer to the tensile stress at 100% and 300% strain, respectively.

[0106] It is known that elastomers (e.g., diene-based elastomers) degrade in the presence of air / oxygen. Degradation can occur in the form of cleavage and / or cross-linking of polymer chains, which can impair the rubber properties. Elastomeric composites can be cured in the presence of vulcanizing agents, such as sulfur, to induce cross-linking, resulting in a vulcanizate that is hardened (with respect to the composite) and exhibits greater stability with respect to degradation; degradation can still occur, but to a lesser extent than in uncured composites. However, it may be necessary to store (and / or transport) uncured elastomeric composites for extended periods (e.g., 3, 6, 9 months, or up to 1 year, or even up to 2 years).Furthermore, the elevated temperatures often found in warehouses or during transport (trucks, shipping containers) can accelerate the degradation rate. To slow this rate, composite materials can be stored in refrigerators or under air conditioning. However, such storage solutions require significant energy consumption and refrigeration equipment.

[0107] It has been found that composite materials containing the binder can exhibit reduced degradation at temperatures of at least 20°C for periods of, for example, 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 1 year (12 months), or even up to 2 years. Such stored or aged composite materials are referred to as "aged composites." Alternatively, aged composites can be those that have been stored or aged at elevated temperatures for at least 1 day. The degradation of aged composites can be monitored by observing the rubber properties of the composite or vulcanizate.For example, vulcanizates produced from composites manufactured with the binder according to the procedures described herein have certain properties that are retained over time. Aging the composites described herein for periods of at least 1 day, 5 days, etc., up to 1 year, can lead to improved hysteresis properties of vulcanizates produced from the aged composites, as indicated by maximum tan δ, Payne effect, and / or Payne ratio values ​​that are increased by no more than 10% of the value of a vulcanizate produced from a composite that was not aged, e.g., for no more than 2 days or no more than 1 day. Thus, for example, the rheological properties of the composite (and of compounds produced from such composites) can be improved.An example of such a property is the Payne effect of the vulcanizate, which can be expressed by the Payne ratio or the Payne difference. The Payne ratio is defined as G'(0.1%) / G'(50%), where G'(0.1%) is a dynamic storage modulus measured at a strain amplitude of 0.1%, and G'(50%) is a dynamic storage modulus measured at a strain amplitude of 50%. The Payne difference is the difference between G'(0.1%) and G'(50%).

[0108] At room temperature (e.g., 20°C), aged composite materials can be stored or aged for a minimum of 5 days or other periods specified here. The aging period can be determined from the day of manufacture (day 0). For example, the aged composite materials can be those that have been stored or aged at temperatures of at least 20°C, e.g., from 20°C to 200°C, or under ambient conditions, such as temperatures from 20°C to 40°C or from 20°C to 30°C, either in a climate-controlled environment or in an area without climate control (e.g., warehouse, truck). The aging period can be a minimum of 7 days, a minimum of 2 weeks, a minimum of 1 month, a minimum of 3 months, a minimum of 6 months, or a minimum of 1 year or longer, e.g.,from 5 days to 2 years, from 5 days to 1 year, from 5 days to 6 months, from 5 days to 3 months, from 2 weeks to 1 year, from 2 weeks to 6 months, from 1 month to 1 year, from 1 month to 6 months and other areas.

[0109] As another option, aged composite materials can be stored or aged for at least one day at elevated temperatures, e.g. B., a temperature of at least 40°C, such as temperatures in the range of 40°C to 200°C, from 40°C to 180°C, from 40°C to 150°C, from 40°C to 120°C, from 40°C to 100°C, from 40°C to 90°C, from 40°C to 75°C, from 50°C to 200°C, from 50°C to 180°C, from 50°C to 150°C, from 50°C to 120°C, from 50°C to 100°C, from 50°C to 90°C, from 50°C to 75°C, from 60°C to 200°C, from 60°C to 180°C, from 60°C to 150°C, from 60°C to 120°C, from 60°C to 100°C, or from 60°C to 90°C. In certain 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 6 months or up to 1 year. Alternatively, storage at elevated temperatures can be limited to no longer than 1 month, no longer than 2 weeks, or no longer than 1 week, e.g.Storage from 5 days to 1 month.

[0110] This section also describes objects that are made from or contain the composite materials or vulcanizates described here.

[0111] The composite material can be used to manufacture a product containing elastomer or rubber. One possibility is that the elastomer composite material can be used or manufactured for use in various parts of a tire, for example, to form a vulcanizate that is incorporated into different parts of a tire, such as tire treads (like on-road or off-road tire treads), including the top and bottom layers, undercut strips, inner liner, tire sidewalls, tire carcasses, tire sidewall inserts, wire carcasses for tires, and cushioning rubber for retreaded tires, in pneumatic tires as well as in non-pneumatic or solid tires.Alternatively or additionally, elastomer composites (and subsequently vulcanizates) can be used for hoses, seals, sealing rings, weather protection strips, windshield wipers, vehicle parts, linings, padding, housings, wheel and track components, tire sidewall liners, wire carcasses for tires, and rubber buffers for retreaded tires, in pneumatic tires, and also in non-pneumatic or solid tires. Alternatively or additionally, elastomer composites (and subsequently vulcanizates) can be used for hoses, seals, sealing rings, vibration damping components, track chains, and track cushions for tracked equipment such as bulldozers, etc., engine bearings, earthquake stabilizers, mining equipment such as screens, mining equipment linings, conveyor belts, chute linings, slurry pump linings, slurry pump parts such as impellers, valve seats, valve bodies, piston hubs, piston rods, pistons, impellers for various applications such as mixed slurries and slurry pump impellers, grinding mill linings, cyclones and hydrocyclones, compensators, marine equipment such as pump linings (e.g. dredge pumps and outboard motor pumps), hoses (e.g. dredge hoses and outboard motor hoses) and other marine equipment, shaft seals for the marine, oil industry, aerospace and other applications, propeller shafts, pipeline linings for transporting e.g. oil sands and / or tar sands and other applications where abrasion resistance and / or improved dynamic properties are desired.Furthermore, the elastomer composite material can be used via the vulcanized elastomer composite material in rollers, cams, shafts, pipes, bushings for vehicles or other applications where abrasion resistance and / or improved dynamic properties are desired.

[0112] Accordingly, the articles include vehicle tire treads, including superstructure and substructure, sidewalls, underrun surfaces, inner liners, wire casing components, tire casings, engine mounts, bushings, conveyor belts, vibration damping devices, weather protection strips, windshield wipers, vehicle components, seals, sealing rings, hoses, linings, pads, housings, and wheel or track elements. The article may, for example, be a multi-component tread such as those described in U.S. Patents 9,713,541, 9,713,542, 9,718,313, and 10,308,073, the disclosures of which are incorporated herein by reference. Examples

[0113] The mixing for Examples I and II and all compounding processes were performed using a Banbury® BR-1600 mixer (“BR1600”; manufacturer: Farrell) with a plunger pressure of 2.8 bar. The BR1600 mixer was operated with two 2-blade tangential rotors (2WL) and had a capacity of 1.6 L. The mixing for Example III was performed using a BB-16 tangential mixer (“BB-16”; Kobelco Kobe Steel Group), which was equipped with two tangential 4-blade rotors (type 4WN) and had a capacity of 16.2 L.

[0114] The moisture content of 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 (size: length, width, height < 5 mm), and 2 to 2.5 g of the material were placed on a disposable aluminum disc / plate, which was then inserted into the moisture balance. The weight loss was recorded for 30 minutes at 125°C. At the end of the 30 minutes, the moisture content of the composite material was recorded as follows: Moisture content of the composite material = (initial weight − final weight / initial weight) ⋅ 100

[0115] The following tests were performed to measure the rubber properties of each of the vulcanizates: The tensile stress at 100% elongation (M100) and the tensile stress at 300% elongation (M300) were determined according to ASTM D412 (Test Method A, Die C) at 23°C, 50% relative humidity, and a crosshead speed of 500 mm / min. Strain gauges were used to measure the tensile strain. The ratio of M300 / M100 is referred to as the tensile stress ratio (or modulus ratio). The maximum tan δ was measured using an ARES-G2 rheometer (manufacturer: TA Instruments) with a parallel plate geometry of 8 mm diameter in torsion mode. The vulcanizate sample had a diameter of 8 mm and a thickness of approximately 2 mm. The rheometer was operated at a constant temperature of 60°C and a constant frequency of 10 Hz. Strain sweeps of 0.1–68% strain amplitude were performed. Measurements were taken at ten points per decade, and the maximum measured tan δ (“max tan δ”), also referred to as “tan δ” unless otherwise specified, was recorded. The Payne ratio was calculated from the ratio of the dynamic storage modulus G' at 0.1% strain to G' at 50% strain, i.e., G'(0.1%) / G'(50%). Example I

[0116] This example describes the production of composite materials and corresponding vulcanizates, in which solid elastomer was mixed with wet filler and a crosslinking agent.

[0117] All samples were produced using ASTM grade N234 carbon black supplied as VULCAN® 7H carbon black (“V7H”; Cabot Corporation). The wet carbon black pellets had a moisture content of 55.2% and were produced by milling with an 8-inch model of a MicroJet mill to create flaky carbon black particles, 99.5% of which had a particle diameter of less than 10 microns. This flaky carbon black was then wetted with the pin pelletizer to regenerate the wetted pellets. The elastomer used was standard-grade SMR5 natural rubber (Hokson Rubber, Malaysia). Technical descriptions of this natural rubber are widely available, for example, in the Blue Book of Rubber World Magazine, published by Lippincott and Peto, Inc. (Akron, Ohio, USA). Sodium (2Z)-4-[(4-Aminophenyl)amino]-4-oxo-2-butenoate, which is commercially available as Sumilink® 200 coupling agent (“S200”; Sumitomo Chemical), was used as a binder.

[0118] Two samples were produced in which the binder was added at the same mixing stage as the wet carbon black. The following comparison products were prepared: conventionally mixed natural rubber and carbon black (Dry 1), and conventionally mixed natural rubber, carbon black, and S200 (Dry 2).

[0119] The formulations are given in Table 1. The target specification for the soot loading was based on dry conditions. Table 1 Formulations Dry 1 Dry 2 Example 1 Example 2 Stage 1 Formulation SMR5 100 100 100 100 V7H 50 50 V7H wet 50 50 S200 0 2 2 2 6PPD 2 2 2 2 Stage 2 Formulation TMQ 1,5 1,5 1,5 1,5 zinc oxide 3 3 3 3 Stearic acid 2 2 2 2 wax beads 1,5 1,5 1,5 1,5 6PPD 0,5 0,5 0,5 0,5 Stage 3 Formulation BBTS 1,4 1,4 1,4 1,4 sulfur 1,2 1,2 1,2 1,2

[0120] 6PPD = N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine. The wax beads were Akrowax™ 5031 wax beads and BBTS (N-tert-Butyl-2-benzothiazole-sulfenamide) was Accelerator BBTS, all available from Akrochem, Akron, Ohio.

[0121] The protocols for the first mixing stage are given in Table 2 (dry mixing) and Table 3 (mixing with wet filler). The time intervals listed in the mixing methods below refer to the time elapsed from the start of mixing, defined as "0 s". In Example 1, the binder was added at a temperature of 140°C, and in Example 2, the binder was added after a total mixing time of 210 s. Table 2 Dry 1 and Dry 2 : TCU-Temperature = 50°C; 80 rpm; FF = 70% Time (s) or temperature (°C) Description 0s Add number 30s Add 2 / 3 V7H 150s Sweep / Add remaining V7H 180s Sweep 140°C Add 6PPD (and for dry, add 2 S200) 145°C Sweep / Scrape 160°C Unloading Table 3 TCU temperature = 90°C; 105 rpm; FF = 70% Time (s) or temperature (°C) Example 1 Description Example 2 Description 0 Add number Add number 30 Add 3 / 4 CB (soot). Add 3 / 4 CB (soot). 150s or 125°C Sweep / Add remaining CB Sweep / Add remaining CB 180s Sweep Sweep 210s Add S200 140°C Add 6PPD and S200 Add 6PPD 145°C Sweep / Scrape Sweep / Scrape 160°C Unloading Unloading

[0122] All composite materials were rolled into sheets on a 2-roll mill at 50°C and approximately 37 rpm, followed by six passes and a roll gap of approximately 5 mm. The moisture contents for both Example 1 and Example 2 after the first mixing stage, based on the weight of the composite material, were 0.8% and 0.9%, respectively.

[0123] Vulcanizates were produced by compounding the composites with the Stage 2 formulation according to the protocol in Table 4 and subsequently compounding with crosslinking agents (Stage 3 formulation) according to the protocol in Table 5. After each compounding stage, the composites were rolled into sheets on a two-roll mill at 50°C and approximately 37 rpm, followed by six passes and a roll gap of approximately 5 mm. The final composites were rolled to a thickness of 2.4 mm on a two-roll mill at 60°C. The finished composites were cured in a heated press (2500 lbs) at 150°C for 30 minutes. Table 4 TCU temperature = 50''C; 80 rpm; FF = 68% Time (s) Description 0 Add stage 1 composite material 30 Add components to the Level 2 formulation 90 Sweep 150 Unloading, adjusting rotation speed < 125°C Table 5 TCU temperature = 60°C; 80 rpm; FF = 65% Time (s) Description 0 Add stage 2 composite material and crosslinking agent. 30 Sweep 90 Unloading

[0124] The properties of the vulcanizate are given in Table 6. Table 6 Dry 1 Dry 2 Example 1 Example 2 M100 (MPa) 2,89 2,91 2,51 2,51 M300 (MPa) 15,53 16,47 15,67 15,46 M300 / M100 5,38 5,65 6,24 6,15 Max tan δ (60°C) 0,174 0,144 0,140 0,131

[0125] The data in Table 6 show that the dynamic hysteresis loss Max tan δ of composites mixed with wet filler and binder was lower than that of the comparison examples Dry 1 and Dry 2. The tensile stress ratio, M300 / M100, of Examples 1 and 2 was higher than that of the dry mixtures. This demonstrates that improved rubber properties can be achieved by combining mixing with wet filler and the use of a binder. Example II

[0126] This example describes the production of composite materials and corresponding vulcanizates in which solid elastomer was mixed with wet filler that had been co-pelleted with a binder.

[0127] Three binders were investigated: cystamine dihydrochloride (“Cystamine”; 96%, Sigma-Aldrich), hexamethylene 1,6-bis(thiosulfate) (“Duralink”; Duralink™ HTS tire additive, Eastman Chemical Co.), and thiourea (Sigma-Aldrich). All samples were prepared with ASTM grade N234 carbon black supplied as VULCAN® 7H carbon black (“V7H”; Cabot Corporation). The elastomer used was standard-grade SMR20 natural rubber (Hokson Rubber, Malaysia). Technical descriptions of this natural rubber are widely available, for example, in the Blue Book of Rubber World Magazine, published by Lippincott and Peto, Inc. (Akron, Ohio, USA).

[0128] Co-pellets containing the binder and carbon black (wet or dry) were added to the mixer. The binder-carbon black co-pellets were formed by combining a solution of 6 g of the binder with DI water (310 g) and 250 g of flaky V7H carbon black, prepared as in Example 1. Pelletizing was carried out using a 10 HP heated pin pelletizer for a residence time of 5 minutes at 60°C. For Examples 3, 4, and 5, the resulting wet pellets were used without drying. For Examples Dry 3, Dry 4, and Dry 5, the resulting wet pellets were dried overnight in an oven at 125°C before mixing. For the comparative example Dry 6, pellets containing carbon black and no binder were prepared as described in that example.

[0129] The wording is given in Table 7. Table 7 formulation Dry 6 Dry 3 Example 3 Dry 4 Example 4 Dry 5 Example 5 Stage 1 Formulation SMR20 100 100 100 100 100 100 100 N234 V7H 50 Cystamine + V7H Co pellet, dry 51,2 Cystamine + V7H Co pellet, wet 51,2 Duralink + V7H Co-granules, dry 51,2 Duralink + V7H Co granules, wet 51,2 Thiourea + V7H Co-Pellet, dry 51,2 Thiourea + V7H Co pellet, wet 51,2 6PPD 1 1 1 1 1 1 1 Stage 2 formulation (or “smalls” for dry pellets) TMQ 0 0 0 0 0 0 0 zinc oxide 3 3 3 3 3 3 3 Stearic acid 2 2 2 2 2 2 2 wax beads 0 0 0 0 0 0 0 6PPD 0 0 0 0 0 0 0 CBS 1,2 1,2 1,2 1,2 1,2 1,2 1,2 sulfur 1,2 1,2 1,2 1,2 1,2 1,2 1,2 6PPD = N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine. The wax beads were Akrowax™ 5031 wax beads, and CBS is N-cyclohexyl-2-benzothiazole sulfenamide, all available from Akrochem, Akron, Ohio.

[0130] Mixing protocols are shown in Table 8 for all mixtures with dry filler (i.e. Dry 6 and Dry 3 to Dry 5). Table 8 TCU temperature = 50°C; 80 rpm; FF = 70% Time (s) Description 0 Add SMR20 30 Add filler 60 Sweep 150 Add smalls 180 Sweep 240 Unloading

[0131] Protocols for mixing with wet co-pellets, e.g. 3, e.g. 4, and e.g. 5, are given in Table 9. Table 9 TCU temperature = 90°C; 105 rpm; FF = 70% Time or temperature Description 0 s Add SMR20 30 s Add 3 / 4 co-pellets 150s or 125°C Sweep / Add remaining co-pellets 180s Sweep 140°C Add 6PPD 145°C Sweep / Scrape 160°C Unloading

[0132] The moisture contents for Examples 3, 4, and 5 after the first mixing stage were 0.74%, 0.35%, and 0.55% respectively, based on the weight of the composite material. All composite materials underwent a second mixing stage (see Table 10 for the protocol), in which the crosslinking agents and Smalls (for the composites made from wet co-granules; crosslinking agents only for dry-mixed composites) were added. Table 10 TCU temperature = 60°C; 60 rpm; FF = 65%. Time (s) Description 0 Add Stage 1 composite material and Stage 2 formulation 30 Sweep 90 Unloading

[0133] The mixtures were rolled into sheets on a two-roll mill at 50°C and approximately 37 rpm, formed into strips for one minute, and then rolled four times with a roll gap of approximately 5 mm. The composites were then formed into sheets 2.4 mm thick on a two-roll mill at 60°C. The finished composites were cured in a heated press for 21 minutes at a temperature of 150°C (2500 lbs). The vulcanizate properties are listed in Table 11. Table 11 sample Dry 6 Dry 3 Example 3 Dry 4 Example 4 Dry 5 Example 5 M100 (MPa) 2,69 3,07 2,86 3,03 2,91 3,35 2,90 M300 (MPa) 14,64 16,35 17,23 16,11 17,67 17,88 17,68 M300 / M100 5,44 5,33 6,02 5,32 6,08 5,34 6,09 tan δ max (60°C) 0,183 0,138 0,137 0,140 0,130 0,101 0,121

[0134] The data in Table 11 show that vulcanizates of composite materials produced from the wet co-pellets with binders exhibit either a lower max tan δ, a higher tensile stress ratio (M300 / M100), or both, compared to the corresponding dry-mixed reference examples. The vulcanizates of Examples 3, 4, and 5 all showed both a lower max tan δ and a higher tensile stress ratio than the dry-mix reference example 6. Example III

[0135] This example describes the production of a composite material by mixing wet filler with natural rubber and a binder, and an evaluation of the properties of the composite material as well as the properties of the mixture produced from the composite material.

[0136] All samples were produced using ASTM grade N234 carbon black supplied as VULCAN® 7H carbon black (“V7H”; Cabot Corporation). The wet carbon black pellets had a moisture content of 56% and were produced by milling with an 8-inch model of a MicroJet mill to create flaky carbon black particles, 99.5% of which had a particle diameter of less than 10 microns. This flaky carbon black was then wetted with the pin pelletizer to regenerate the wetted pellets. The elastomer used was standard grade RSS3 natural rubber (from Bundit Co. Ltd., Thailand). Technical descriptions of this natural rubber are widely available, for example, in the Blue Book of Rubber World Magazine, published by Lippincott and Peto, Inc. (Akron, Ohio, USA). Sodium (2Z)-4-[(4-Aminophenyl)amino]-4-oxo-2-butenoate, which is commercially available as Sumilink® 200 coupling agent (“S200”; Sumitomo Chemical), was used as a binder.

[0137] The mixing of wet carbon black with natural rubber was carried out as a two-stage mixing process followed by two-stage compounding. The formulations are given in Table 12. The target carbon black content was determined based on the dry composition. Table 12 Formulations (phr) Stage 1 Formulation RSS3 100 V7H wet 50 S200 2 6PPD 2 Stage 3 Formulation TMQ 1,5 zinc oxide 3 Stearic acid 2 wax beads 1,5 6PPD 0,5 Stage 4 Formulation BBTS 1,4 sulfur 1,2

[0138] The two-stage mixing protocol is detailed in Table 13 (Stage 1) and Table 14 (Stage 2). The time intervals listed in the mixing methods below refer to the stage time. Mixing was performed under the following conditions: TCU temperature = 90°C, fill factor = 66%, ram pressure = 112 barg. The first mixing stage was performed using the BB-16 mixer with 4WN rotors (capacity 16.2 l) and a ram pressure of 112 barg, as detailed in Table 13 of the protocol. Following the first mixing stage, the composite material was processed in a TSR-125 twin-screw extruder equipped with stationary knives (Kobelco Kobe Steel Group).

[0139] The second mixing stage was performed using the BB-16 mixer with 6WI rotors (capacity 14.4 l) according to the protocol in Table 13. Mixing was carried out with the piston raised to its highest position. After initial kneading, mixing was performed under PID (proportional-integral-differential) control, which allows for automatic control of the batch temperature via a feedback loop. A thermocouple inserted through the mixer's drop door measures the batch temperature, which is transmitted to a PID controller. The controller's output is used to control the speed of the mixer rotors. The second-stage mixing conditions were: TCU temperature = 65°C; fill factor = 35%; mixing time = 582 s. Table 13 Time or temperature Rotor speed (rpm) Description 20 s 50 Feeding rubber to the mixer 110°C 60 Knead rubber up to 110°C 20 s 60 1. Add filler (75%) 120 s or 130°C 85 Mix until the earlier temperature of 120 seconds and 130°C is reached. 20 s 60 Add S200, followed by the second filler addition. 20 s 60 Mix for 20 seconds at 60 rpm to allow the hydraulic system to build up pressure. 155°C 85 Mix until the temperature of the 6PPD addition is reached (155°C) 20 s 60 Add 6PPD. 160°C 85 Mix until the discharge temperature (160°C) is reached. 30 s 50 Unloading after 30 seconds Table 14 Rotor speed (rpm) Time or temperature. Mixing protocol description 35 20s Add composite material to the mixer 35 90s Knead with the pestle raised for 90 seconds. (variable) 35-54s Kneading under PID temperature control with the ram raised. The batch temperature is automatically controlled via a PID controller with a setpoint of 135°C. 30 Unload mixer and close trapdoor after 30 seconds.

[0140] The moisture content of the composite material after the first mixing stage was 4.96%; the moisture content after the second mixing stage was 0.51%. The composite material from the second stage was processed in a TSR-125 twin-screw extruder equipped with a plate die (Kobelco Kobe Steel Group). The resulting plate was cooled in ambient air.

[0141] The composites were stored in air for 30 or 180 days. After storage, vulcanizates were formed by compounding the composites with the Stage 3 formulation according to the protocol in Table 15, followed by compounding with crosslinking agents (Stage 4 formulation) according to the protocol in Table 16. After each compounding stage, the composites were rolled into sheets on a two-roll mill at 50°C and approximately 37 rpm, followed by six passes and a roll gap of approximately 5 mm. The finished mixtures were deformed to a thickness of 2.4 mm on a two-roll mill at 60°C. The finished mixtures were cured in a heated press (2500 lbs) at 150°C for 30 minutes. Table 15 TCU temperature = 50°C; 80 rpm; FF = 68% Time (s) Description 0 Add composite material 30 Add components to the Level 2 formulation 90 Sweep 150 Unloading at 150 s Table 16 TCU temperature = 60°C; 80 rpm; FF = 65% Time (s) Description 0 Add 1 / 2 of the Stage 2 composite material / Add Stage 3 formulation (crosslinking agent) / remaining composite material 30 Sweep 90 Unloading

[0142] The properties of the vulcanizates produced 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 given in Table 17. Table 17 Example 6 Example 7 Example 8 Example 9 Storage time (days) 30 30 180 180 Max tan δ (60°C) 0,14 0,14 0,14 0,14 G'(0.1%) (MPa), mixture 4,7 5,1 4,4 4,5 G'(50%) (MPa), mixture 1,82 1,85 1,69 1,64 Payne ratio, mixture 2,59 2,78 2,62 2,74

[0143] As can be seen from the data in Table 17, the properties of the vulcanizate produced from aged composites containing the binder are surprisingly similar, regardless of whether the composite was stored for 30 days (Ex. 6, Ex. 7) or 180 days (Ex. 8, Ex. 9). Even more surprisingly, the maximum tan δ values ​​are unchanged for all vulcanizates. These data show that the binder can help to reduce the degradation of the composite's performance over time, e.g., for at least up to 180 days.

[0144] The use of the terms "a" and "the" is to be interpreted as encompassing both the singular and the plural unless otherwise stated or clearly contradicted by the context. The terms "encompassing," "with," "including," and "containing" are to be understood as open terms (i.e., in the sense of "including but not limited to") unless otherwise stated. The mention of ranges of values ​​is intended merely as shorthand for the individual mention of each value falling within the range unless otherwise stated herein, and each individual value will be included in the description as if it were listed here individually. All procedures described herein may be carried out in any suitable order unless otherwise stated herein or clearly contradicted by the context. The use of examples or illustrative expressions (e.g.,The phrase "how" is used solely for the purpose of better illustrating the invention and does not constitute a limitation of the scope of the invention unless otherwise claimed. No wording in the description should be interpreted as implying that an unclaimed element is essential for the embodiment of the invention. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] WO 2020247663 [0016, 0036, 0044, 0050, 0062, 0066, 0077, 0093, 0096] US 2012 / 0277359 A1

[0028] EP 0478274

[0028] WO 2020045575

[0028] WO 2019 / 070514 A1

[0039] US 62 / 857296

[0039] US 2020 / 247681

[0039] US 9447259

[0039] US 2021 / 027814 PCT

[0039] WO 2021153643

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[0041] WO 2017207912

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[0112]

Claims

[1] Method for producing a composite material, comprising: (a) Feeding a mixer with at least one solid elastomer, a wet filler containing carbon black and a liquid in an amount of at least 20% by weight, based on the total weight of the wet filler, and a binder; (b) in one or more mixing steps, mixing the at least one solid elastomer, the wet filler and the binder to form a mixture, and removing at least some of the liquid from the mixture by evaporation; and (c) Discharge of the composite material containing the filler dispersed in the elastomer in a loading of at least 20 phr from the mixer, wherein the composite material has a liquid content of not more than 10 wt.%, based on the total weight of the composite material, wherein the binder is selected from compounds with at least two functional groups, wherein: a first functional group is selected from -N(R 1 )(R 2 ), -N(R 1 )(R 2 )(R 3 ) + A - , -S-SO3M 1 and structures of formula (I) and formula (II), where A - chloride, bromide, iodide, hydroxy, nitrate or acetate, X = NH, O or S, Y = H, OR 4 , NR 4 R 5 , -S n R 4 is and n is an integer from 1-6, and a second functional group is selected from thiocarbonyl, nitrile oxide, nitrones, 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 , and R 1 - R 8Each is independently selected from H and C1-C8 alkyl; and M 1 and M 2 Each were selected independently from H, Na + , K + , Li + , N(R')4 + , where each R' is independently selected from H and C1-C 20 -Alkyl and x is an integer chosen from 1-8. [2] The method of claim 1, wherein the binder further comprises at least one spacer between the first and the second functional group, 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-, wherein R 9 and R 10 Each can be chosen independently from H and C1-C8 alkyl, and y is an integer chosen from 1-10. [3] Method according to claim 1, wherein the binder is selected from thiourea, cystamine and compounds of formula (1), formula (2) and formula (3), H2N-Ar-N(H)-C(O)-C(R 6 )=C(R 7 )-CO2M 2 (1) H2N-(CH2) n -SSO3M 2 (2) M 1 O3S-S-(CH2) n -S-SO3M 2 (3) [4] Method according to any one of claims 1-3, wherein M 1 and M 2 and each independently of each other from H, Na + and N(R')4 + are selected and R 6 and R 7 are independently selected from H and C1-C6 alkyl. [5] Method according to claim 4, wherein the binder is selected from compounds of formula (1) and R 6 and R 7 Each is H. [6] Method according to any one of claims 1 to 5, wherein the binder is sodium(2Z)-4-[(4-Aminophenyl)amino]-4-oxo-2-butenoate. [7] Method according to any one of claims 1 to 6, wherein the feeding comprises feeding the mixer with separate batches of the binder and the wet filler. [8] Method according to any one of claims 1 to 7, wherein the feeding comprises multiple additions of the solid elastomer, the wet filler and / or the binder. [9] Method according to any one of claims 1 to 8, wherein the mixing takes place in a single mixing step. [10] Method according to any one of claims 1 to 8, wherein the mixing is carried out in two or more mixing steps. [11] Method according to claim 10, wherein the mixing in (b) is a second mixing step, wherein a first mixing step comprises mixing at least a part of the solid elastomer and at least a part of the wet filler and subsequently feeding the mixer with the binder. [12] Method according to any one of claims 1 to 11, wherein the feeding in (a) comprises feeding the mixer with a mixture comprising the binder and the wet filler. [13] Method according to any one of claims 1 to 11, wherein the feeding in (a) comprises feeding the mixer with a co-pellet containing the binder and the wet filler. [14] A method according to any one of claims 1 to 13, wherein the method comprises carrying out the mixing in at least one of the mixing steps, wherein the mixer has at least one temperature control device which is set to a temperature, T z , is set to 65°C or higher. [15] Method according to any one of claims 1 to 14, wherein in at least one of the mixing steps the method comprises carrying out the mixing with one or more rotors of the mixer which operate at a peak speed of at least 0.6 m / s for at least 50% of the mixing time. [16] Method according to any one of claims 1 to 15, wherein the resulting total specific energy for mixing is at least 1,300 kJ / kg composite material. [17] Method according to any one of claims 1 to 16, wherein the wet filler further comprises at least one material selected from carbon-containing materials, silicon dioxide, nanocellulose, lignin, clays, nanoclays, metal oxides, metal carbonates, pyrolysis carbon, graphenes, graphene oxides, reduced graphene oxide, carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes or combinations thereof, as well as coated and treated materials thereof. [18] Method according to any one of claims 1 to 16, wherein the wet filler also contains silicon dioxide. [19] Method according to any one of claims 1 to 18, wherein the wet filler contains a liquid in an amount of 20 wt.% to 80 wt.%, based on the total weight of the wet filler. [20] Method according to any one of claims 1 to 19, wherein the wet filler is in the form of a powder, a paste, a pellet or a cake. [21] Method according to any one of claims 1 to 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, fluoroelastomers, perfluoroelastomers, silicone elastomers and mixtures thereof. [22] Method according to any one of claims 1 to 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 mixtures thereof. [23] Method according to any one of claims 1 to 22, wherein one or more mixing steps are a continuous process. [24] Method according to any one of claims 1 to 22, wherein one or more of the mixing steps are a batch process. [25] Method for producing a composite material, comprising: (a) Feeding a first mixer with at least one solid elastomer and a wet filler containing carbon black and a liquid 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, mixing the at least one solid elastomer and the wet filler to form a mixture, and removing at least some of the liquid from the mixture by evaporation; (c) Discharge of the mixture comprising the filler dispersed in the elastomer in a loading of at least 20 phr from the first mixer, wherein the mixture has a liquid content reduced to an amount less than the liquid content at the beginning of step (b), and wherein the mixture has a material temperature in the range of 100°C to 180°C; (d) Mixing the mixture from (c) in a second mixer to obtain the composite material; and (e) Discharge of the composite material having a liquid content of less than 3 wt.%, based on the total weight of the composite material, from the second mixer, wherein a binder is supplied to the first mixer, the second mixer or both the first and the second mixer, the binder being selected from compounds having at least two functional groups, wherein: a first functional group is selected from -N(R 1 )(R 2 ), -N(R 1 )(R 2 )(R 3 ) + A-, -S-SO3M 1 and structures of formula (I) and formula (II), where A - chloride, bromide, iodide, hydroxy, nitrate or acetate, X = NH, O or S, Y = H, OR 4 , NR 4 R 5 , -S n R 4 is and n is an integer from 1-6, and a second functional group is selected from thiocarbonyl, nitrile oxide, nitrones, 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 , and R 1 - R 8 Each is independently selected from H and C1-C8 alkyl; and M 1 and M 2Each were selected independently from H, Na + , K + , Li + , N(R')4 + , where each R' is independently selected from H and C1-C 20 -Alkyl and x is an integer chosen from 1-8. [26] Method according to claim 25, wherein the binder is fed to the first mixer and step (b) comprises mixing the at least one solid elastomer, the wet filler and the binder to form the mixture. [27] Method according to claim 25 or 26, wherein the binder is added to the second mixer and step (d) comprises mixing the mixture of (c) and the binder in the second mixer to obtain the composite material. [28] Method according to any one of claims 25 to 27, wherein the first and the second mixer are the same. [29] Method according to any one of claims 25 to 27, wherein the first and the second mixer are different. [30] Method according to any one of claims 25 to 29, wherein the second mixer is operated under at least one of the following conditions: (i) a plunger pressure of 5 psi or less; (ii) a plunger raised to at least 75% of its maximum height; (iii) a plunger that operates in floating mode; (iv) a plunger positioned so that it does not substantially touch the mixture; (v) the mixer is plungerless; and (vi) a filling factor of the mixture in the range of 25% to 70%. [31] Method for the production of a vulcanizate, comprising: Curing the composite material produced according to one of claims 1 to 30 in the presence of at least one crosslinking agent to form the vulcanizate. [32] Method according to any one of claims 1 to 31, further comprising aging the composite material to form an aged composite material. [33] Method according to claim 32, wherein the composite material has been aged for at least 5 days at a temperature of at least 20°C. [34] Method according to claim 32, wherein the composite material has been aged for at least 1 day at a temperature of at least 40°C. [35] Method according to claim 32, wherein a vulcanizate produced from the aged composite material has a maximum tan δ value that is not increased by more than 10% compared to the value of a vulcanizate produced from a non-aged composite material. [36] Method according to claim 32, wherein a vulcanizate produced from the aged composite material has a Payne effect that is not more than 10% higher than the value of a vulcanizate produced from a non-aged composite material. [37] Subject matter comprising the vulcanizate produced according to the method of any one of claims 31 to 36.