rubber composition

Abstract

A rubber composition is disclosed. This rubber composition may be prepared by using at least a lignin-based filler and rubber, and optionally a plasticizer. Furthermore, an article containing this rubber composition is disclosed.

Description

[Technical Field]

[0001] This disclosure relates to rubber compositions. Furthermore, this disclosure relates to articles containing the rubber compositions disclosed herein. [Background technology]

[0002] The rubber industry relies primarily on fossil fuel-based and highly CO2-intensive raw materials. As a result, end products such as tires, profiles, sealants, and hoses have a very high CO2 load per unit weight, which contributes significantly to the overall carbon footprint of end-user products, such as automobiles. The main contributing components (drivers) are typically the compound components in terms of their major share (amount in the compound), namely rubber, functional fillers, and plasticizers. The inventors have come to recognize the ongoing need to find sustainable solutions for various applications to reduce emissions. [Overview of the Initiative] [Means for solving the problem]

[0003] A rubber composition is disclosed. This rubber composition is prepared by using at least a lignin-based filler and rubber, and optionally a plasticizer. The above lignin-based packing material is prepared from lignin subjected to hydrothermal carbonization treatment. The total amount of lignin-based filler in the rubber composition is 2 to 500 phr. The total biogenic carbon content of the rubber composition is determined to be 50-100% according to standard ASTM D6866-22. However, if no plasticizer is used to produce the rubber composition, at least one type of bio-based rubber is used, and if both rubber and a plasticizer are used to produce the rubber composition, at least one type of bio-based rubber and / or at least one type of bio-based plasticizer is used.

[0004] Furthermore, articles comprising the rubber composition disclosed herein are disclosed. [Modes for carrying out the invention]

[0005] A rubber composition is disclosed. This rubber composition is prepared by using at least a lignin-based filler and rubber, and optionally a plasticizer. The above lignin-based packing material is prepared from lignin subjected to hydrothermal carbonization treatment. The total amount of lignin-based filler in the rubber composition is 2 to 500 phr. The total biocarbon content of the rubber composition is 50-100%, as measured according to standard ASTM D6866-22. However, if no plasticizer is used to produce the rubber composition, at least one type of bio-based rubber is used, and if both rubber and a plasticizer are used to produce the rubber composition, at least one type of bio-based rubber and / or at least one type of bio-based plasticizer is used.

[0006] In one embodiment, the above proviso is: i) If no plasticizer is used to produce the rubber composition, the rubber includes bio-based rubber. ii) When a plasticizer is used to produce the rubber composition, • The rubber includes bio-based rubber, and the plasticizer includes bio-based plasticizers, or • The rubber includes bio-based rubber, and the plasticizer includes fossil-based plasticizer, or • The rubber includes fossil-based rubber, and the plasticizers include bioplasticizers. That's the situation.

[0007] In one embodiment, the above proviso is: i) If no plasticizer is used to produce the rubber composition, the rubber is a bio-based rubber. ii) When a plasticizer is used to produce the rubber composition, • The rubber is bio-based rubber, and the plasticizer is a bio-based plasticizer, or • The rubber is bio-based rubber, and the plasticizer is a fossil-based plasticizer, or • Rubber is fossil-based rubber, while plasticizers are bio-based plasticizers. That's the situation.

[0008] Furthermore, articles comprising the rubber compositions disclosed herein are disclosed. These articles may be profiles, hoses, sealants, O-rings, weatherstrips, gaskets, pipe materials, membranes, insulators, cables, wiper blades, bushings (bearing tubes), tapes, foils, linings, flooring materials, plugs, nipples, conveyor belts, seals, or tires.

[0009] Rubber is a type of material that may be produced from natural sources (e.g., natural rubber) or synthesized on an industrial scale (fossil rubber). Rubber possesses elasticity, resilience, and toughness, making it suitable as a basic component in tires used, for example, in automobiles, aircraft, and bicycles. The main chemical components of rubber may also be elastomers.

[0010] If no plasticizer is used to produce the rubber composition, at least one type of bio-based rubber is used. Therefore, fossil-based rubber may also be used to produce the rubber composition in such circumstances, but at least one type of bio-based rubber should be used. Accordingly, a mixture of bio-based rubber and fossil-based rubber may be used.

[0011] When both rubber and plasticizers are used to produce the rubber composition, at least one bio-based rubber and / or at least one bio-based plasticizer is used. Therefore, fossil-based rubber and / or fossil-based plasticizers may also be used to produce the rubber composition in such circumstances, but at least one bio-based rubber and / or at least one bio-based plasticizer should be used. Accordingly, a mixture of bio-based rubber and fossil-based rubber may be used together with a mixture of bio-based plasticizer and fossil-based plasticizer.

[0012] In one embodiment, the rubber composition is prepared by using at least a lignin-based filler and a biological rubber. In one embodiment, the rubber composition is prepared by using at least a lignin-based filler, a biological rubber, and a plasticizer. In one embodiment, the rubber composition is prepared by using at least a lignin-based filler, a fossil rubber, and a biological plasticizer. In one embodiment, the rubber composition is prepared by using at least a lignin-based filler, a biological rubber, and a biological plasticizer.

[0013] In one embodiment, no fossil rubber is used to prepare the rubber composition. In one embodiment, no fossil plasticizer is used to prepare the rubber composition. In one embodiment, neither fossil rubber nor fossil plasticizer is used to prepare the rubber composition.

[0014] The use of a renewable lignin-based filler in the rubber composition has the additional utility of providing excellent environmental performance because its CO2 footprint is rather negative. Thus, the lignin-based filler may act as a pseudo CO2 absorbent when replacing traditional functional fillers in the rubber composition. This effect may be further enhanced by the lightweight property of the lignin-based filler, which results in a lower final composition density. This has an additional positive contribution because rubber articles are often volume-based. Thus, a lower composition density means that less raw material is required per piece. Thus, the carbon footprint value of the rubber composition is at least 10%, or at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 100% lower compared to a fossil rubber composition prepared in the same manner as the rubber composition defined in the present disclosure except for using only fossil-based components.

[0015] When the rubber composition is determined according to Standard ASTM D 2240-15(2021), it may show a hardness value of 20 to 100, or 30 to 90, or 40 to 85, or 45 to 75, or 50 to 65. The rubber composition is determined according to Standard ASTM D1646-19a, and has a Mooney viscosity M of 20 to 110 MU, or 25 to 100 MU, or 30 to 90 MU, or 35 to 95 MU, or 40 to 85 MU, or 45 to 75 MU, or 50 to 70 MU, or 55 to 65 MU L (1 + 4) It may show 100 °C. The inventors have surprisingly noticed that properties such as hardness and Mooney viscosity can be maintained simultaneously at the same level as those of fossil-based rubber compositions, and highly bio-based origin rubber compositions can be produced.

[0016] The total bio-origin carbon content of the rubber composition may be 50 to 100%, 50 to 99%, or 60 to 98%, or 70 to 97%, or 80 to 96%, or 90 to 95% when determined according to Standard ASTM D6866-22. Bio-origin carbon is carbon stored in biological materials such as plants or soil. Carbon accumulates in plants through the process of photosynthesis, and thus bio-based products may contribute to reducing the level of carbon dioxide in the atmosphere.

[0017] The total organic carbon content of the rubber composition may be 30 to 100%, 40 to 100%, 50 to 99%, 60 to 98% when determined according to DIN EN 15936:2012-11. The total organic carbon content of the rubber composition may be 90 to 100%, or 93 to 99%, or 96 to 98% when determined according to DIN EN 15936:2012-11. The term "total organic carbon (TOC)" may be interpreted as the amount of carbon found in organic compounds or in the rubber composition in this case. Therefore, the rubber composition disclosed in this disclosure may have a high total organic carbon content.

[0018] The plasticizer used to produce the rubber composition may be a bioplasticizer or a fossil plasticizer. The plasticizer used in the rubber composition may be derived from fossil resources and / or bio-resources. A combination or mixture of bioplasticizers and fossil plasticizers may also be used to produce the rubber composition. The bioplasticizer may be selected from bio-oils, bio-waxes, or bio-liquid polymers. The use of a bioplasticizer may increase the total bio-based carbon content of the rubber composition and may affect the properties of the rubber composition.

[0019] The weight ratio of the total amount of plasticizer to the total amount of rubber may be 0 to 2, or 0.01 to 1.75, or 0.02 to 1.5.

[0020] The total amount of bio-based rubber in the rubber composition may be 0 to 100 phr, 5 to 95 phr, or 10 to 90 phr. The total amount of bio-based rubber in the rubber composition may be 0 to 100 phr, 5 to 95 phr, 10 to 90 phr, 20 to 80 phr, 30 to 70 phr, 40 to 60 phr, or 50 to 55 phr. The remainder of the rubber may be fossil-based rubber.

[0021] In one embodiment, the weight ratio of the total amount of plasticizer to the total amount of lignin-based filler is 0 to 40, or 0.05 to 20, or 0.1 to 10, or 0.2 to 5, or 0.5 to 2.

[0022] In one embodiment, the total amount of lignin-based filler in the rubber composition is 2 to 500 phr, or 5 to 200 phr, or 10 to 150 phr, or 20 to 100 phr, or 25 to 75 phr.

[0023] The term "phr" refers to "parts per 100 parts of rubber." Parts per 100 parts of rubber is a measure commonly used by rubber chemists to describe how much of a particular component is needed in a composition in relation to the total amount of rubber in the composition.

[0024] In addition to the lignin-based filler, further fillers may be used to produce the rubber composition. The further fillers may be fossil-based fillers.

[0025] The rubber used to produce the rubber composition may be bio-based rubber or fossil-based rubber. The rubber used in the rubber composition may be derived from fossil resources and / or bio-based resources. A combination or mixture of bio-based rubber and fossil-based rubber may also be used to produce the rubber composition.

[0026] The term "bio-based rubber" is used herein to refer to rubber derived from bio-resources. Therefore, the term "bio-based rubber" may include rubber prepared by synthesis using bio-based raw materials, as well as natural rubber found in nature. Bio-based rubber is an important method for the sustainable development of the rubber industry.

[0027] (Bio-based) rubber may be selected from ethylene propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPR), butadiene rubber (BR), styrene-butadiene rubber (SBR), epichlorohydrin rubber (ECO), chloroprene rubber (CR), natural rubber (NR), epoxidized natural rubber (ENR), butyl rubber (IIR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), hydrogenated nitrile rubber (HNBR), bromobutyl rubber (BIIR), chlorobutyl rubber (CIIR), or any combination or mixture thereof.

[0028] The bio-based rubber may be selected from ethylene propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPR), butadiene rubber (BR), styrene-butadiene rubber (SBR), epichlorohydrin rubber (ECO), chloroprene rubber (CR), natural rubber (NR), epoxidized natural rubber (ENR), butyl rubber (IIR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), hydrogenated nitrile rubber (HNBR), bromobutyl rubber (BIIR), chlorobutyl rubber (CIIR), or any combination or mixture thereof. In one embodiment, the bio-based rubber is natural rubber or bio-based EDPM.

[0029] The fossil rubber may be selected from ethylene propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPR), butadiene rubber (BR), styrene-butadiene rubber (SBR), epichlorohydrin rubber (ECO), chloroprene rubber (CR), epoxidized natural rubber (ENR), butyl rubber (IIR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), hydrogenated nitrile rubber (HNBR), bromobutyl rubber (BIIR), chlorobutyl rubber (CIIR), or any combination or mixture thereof. In one embodiment, the fossil rubber is fossil EPDM.

[0030] Any combination or mixture of the above rubbers may also be used. In one embodiment, the rubber is a mixture of bio-based and fossil-based rubbers. These rubbers may be found in nature, prepared by synthesis from bio-resources, or have fossil origins.

[0031] The rubber composition may be prepared by using at least rubber, a lignin-based filler, and optionally a plasticizer. Further components or materials, such as additives, lubricants, stabilizers, antioxidants, curing agents, and foaming agents, may also be used to prepare the rubber composition. In one embodiment, the combination of rubber and a lignin-based filler also includes the combination of one or more plasticizers, additives, lubricants, stabilizers, antioxidants, curing agents, and / or foaming agents to form the rubber composition.

[0032] One or more silane compounds may also be used to produce the rubber composition. Examples of silane compounds include 3,3'-bis-(triethoxysilylpropyl)-tetrasulfide (TESPT), 3,3'-bis-(triethoxysilylpropyl)-disulfide (TESPD), 3-thiocyanatopropyltriethoxysilane, γ-mercaptopropyl-trimethoxysilane, vinyltriethoxysilane, and chloropropyltriethoxysilane. Of these, 3,3'-bis-(triethoxysilylpropyl)-tetrasulfide (TESPT) and 3,3'-bis-(triethoxysilylpropyl)-disulfide (TESPD) may be preferred for use in the rubber composition. The total amount of silane compound in the rubber composition may be 0.25 to 20 phr, or 0.5 to 16 phr, or 0.75 to 12 phr, or 1.0 to 10 phr, or 1.5 to 8 phr, or 2.0 to 6 phr, or 2.5 to 5 phr.

[0033] The rubber composition may be prepared by mixing or combining the above components according to conventional procedures.

[0034] Articles containing the rubber composition can be obtained by mixing the rubber composition with other possible components, compounding them, and then curing them according to conventional procedures.

[0035] The article may contain, in addition to the above rubber composition, additional fillers such as carbon black, precipitated silica, Neuburg siliceous earth, and white fillers (talc, white chalk, kaolin). The additional fillers may be used in amounts of 5 to 200 phr, or 10 to 150 phr, or 15 to 125 phr, or 20 to 100 phr, or 25 to 75 phr.

[0036] The temperature used when combining different components may vary depending on the type of rubber used. Appropriate temperatures for each type of rubber are readily available to those skilled in the art. Rubber suppliers also specify suitable processing temperatures for different types of rubber. Generally, temperatures such as 20–350°C, 40–330°C, 70–300°C, 120–280°C, or 150–250°C may be used.

[0037] The rubber composition may be further cured at high temperatures in a subsequent process after mixing (bio-based) rubber, a lignin-based filler, and optionally a (bio) plasticizer.

[0038] The density of the rubber composition was determined according to ASTM D792-20, ranging from 0.7 to 2.0 g / cm³. 3 , or 0.8~1.6 g / cm³ 3 , or 0.9~1.3 g / cm³ 3 , or 1.0~1.2 g / cm³ 3 The use of lignin-based fillers for preparing the rubber composition has the additional benefit of being a lightweight material, thus affecting the final weight and density of the manufactured rubber composition. This may have additional benefit in final products requiring less weight.

[0039] In one embodiment, the ash content of the rubber composition is determined according to DIN 51719:1997-07 to be less than 25% by weight, less than 20% by weight, less than 15% by weight, less than 10% by weight, or less than 5% by weight. Having a lower ash content has the additional benefit of affecting the density and weight of the rubber composition in a way that reduces them. Furthermore, a high ash content may adversely affect the bio-content of the rubber composition.

[0040] The amount of renewable material in the rubber composition may be 5-100%, 10-95%, 15-90%, or 20-85%.

[0041] The lignin-based filler used to produce the rubber composition is a lignin-based filler prepared from lignin subjected to hydrothermal carbonization treatment (HTC). Hydrothermal carbonization treatment of lignin refers to the thermochemical conversion process of lignin-containing materials in an aqueous suspension. Hydrothermal carbonization treatment of lignin produces lignin derivatives with high carbon content and functional groups.

[0042] Lignin is a biopolymer and an important structural material in the supporting tissues of most living plants. It is a renewable material that can be used in several applications.

[0043] Lignin may be derived from any suitable source. For example, lignin may be derived from wood, such as hardwood, softwood, hardwood timber, or a combination thereof, or from any other biomass, such as sugarcane. The wood may be derived from, for example, pine, poplar, beech, aspen, spruce, eucalyptus, ash, or birch. The wood may be any combination or mixture of these.

[0044] In one embodiment, the lignin-based filler is prepared from lignin derived from an enzymatic hydrolysis process and / or a Kraft process and subjected to hydrothermal carbonization. In one embodiment, the lignin-based filler is prepared from lignin derived from an enzymatic hydrolysis process and subjected to hydrothermal carbonization. In one embodiment, the lignin-based filler is prepared from lignin derived from a Kraft process and subjected to hydrothermal carbonization.

[0045] In one embodiment, the enzymatic hydrolysis process includes the enzymatic hydrolysis of a plant-based feedstock, such as a wood-based feedstock. In one embodiment, the enzymatic hydrolysis process includes the enzymatic hydrolysis of cellulose. In one embodiment, the lignin-based filler is prepared from lignin derived from wood pulping, such as kraft lignin.

[0046] Lignin-based fillers may be prepared as disclosed below. The lignin used may be derived, for example, from a process in which lignin is formed in the enzymatic hydrolysis of lignocellulose raw materials, or the lignin may be derived from a krafting process. Other lignin sources may also be used.

[0047] In one embodiment, the starting material for preparing a lignin-based filler is lignin obtained from an enzymatic hydrolysis process. Enzymatic hydrolysis is a process in which enzymes (multiple types may be used) assist in the cleavage of bonds in a molecule by the addition of the element water. In one embodiment, the enzymatic hydrolysis includes the enzymatic hydrolysis of cellulose. In one embodiment, the lignin-based filler is prepared from lignin derived from the enzymatic hydrolysis process and subjected to hydrothermal carbonization.

[0048] The inventors have surprisingly found that when lignin derived from, for example, an enzymatic hydrolysis process is used to manufacture lignin-based fillers, the ash content of the lignin-based filler can be reduced. A lower ash content has the additional benefit of, for example, higher purity of the lignin-based filler.

[0049] Lignin may be derived from second-generation biomass. Second-generation (2G) biomass may be interpreted as referring to non-food and non-food biomass. Conversely, the term second-generation biomass should be interpreted as first-generation biomass, which is food biomass.

[0050] The derived lignin may be dissolved in an alkaline solution such as NaOH. Dissolution may be achieved by heating the mixture of lignin and the alkaline solution to about 80°C, adjusting the pH to a value greater than 7, such as 9-11, and mixing the mixture of lignin and the alkaline solution for a predetermined time. The mixing time may be continued for about 2-3 hours. The exact pH value is determined based on the product grade target.

[0051] The dissolved lignin may then be subjected to hydrothermal carbonization (HTC).

[0052] The hydrothermal carbonization treatment may be carried out in a batch-operated reactor (HTC reactor), or in several parallel reactors if necessary. The dissolved lignin may be added to the HTC reactor after preheating. The temperature in the HTC reactor may be 150-250°C and the pressure may be 20-30 bar. The residence time in the HTC reactor may be about 3-6 hours. In the HTC reactor, the lignin is carbonized, thereby precipitating a stabilized lignin derivative with a high specific surface area. The formed slurry containing the carbonized lignin may then be removed and cooled.

[0053] This results in the formation of a slurry containing a lignin-based packing agent.

[0054] The slurry containing the lignin-based packing material may be supplied to a separation unit, in which the precipitated lignin may be separated from the slurry. The separated lignin-based packing material may be dried and recovered. Before drying, the lignin-based packing material may be washed as needed. The recovered lignin-based packing material may be further processed before being used as a lignin-based packing material, for example, by crushing, further drying, or grinding. The lignin-based packing material thus formed is a renewable bio-based packing material.

[0055] During the process described above, the lignin polymers are linked together. Therefore, a lignin-based packing material may be considered to contain, or consist of, lignin polymers that are linked together. The linked or connected lignin polymers may no longer be soluble. However, smaller lignin polymer chains remain soluble and can therefore be subjected to standard analytical techniques such as size exclusion chromatography or nuclear magnetic resonance spectroscopy (NMR spectroscopy), which require the analyte to be dissolved in a solvent. Thus, different properties of the soluble fraction of the lignin-based packing material may be determined.

[0056] The lignin-based filler may contain a total amount of ash of 0.1 to 3% by weight, or 0.1 to 2.5% by weight, or 0.2 to 2.0% by weight, or 0.3 to 1.5% by weight, or 0.4 to 1.0% by weight. The ash content can be determined according to standard DIN 51719:1997-07. Surprisingly, the inventors have found that when lignin derived from, for example, an enzymatic hydrolysis process is used to produce the lignin-based filler, the ash content of the lignin-based filler can be reduced. A lower ash content has the additional benefit of, for example, higher purity of the lignin-based filler.

[0057] The lignin-based filler may contain a total amount of carbon of 62-70% by weight, 63-69% by weight, or 64-68% by weight. The amount of carbon in the lignin-based filler may be determined according to standard DIN 51732 (1997).

[0058] The solubility of lignin-based packing materials in 0.1 M NaOH may be 1-40% by weight, 3-35% by weight, or 5-30% by weight. Solubility may be measured as follows: First, the sample is dried at 60°C for 4 hours. A mass of 0.5 grams of the sample is weighed and suspended in 50 ml of 0.1 M NaOH at 22°C at a concentration of 1%. Mixing is continued for 1 hour, after which the sample is placed on glass microfiber paper (1.6 μm), and the filter paper containing the sample is dried at 60°C for 2 hours. The portion of the dissolved sample can be determined by gravimetric analysis.

[0059] The lignin-based packing material may have a weight-average molecular weight (Mw) of 1000-4000 Da, 1300-3700 Da, 1700-3200 Da, 2500-3000 Da, 2600-2900 Da, or 2650-2850 Da, depending on the soluble fraction of the lignin-based packing material. The weight-average molecular weight may be determined by size exclusion chromatography (SEC) using 0.1 M NaOH as the eluent and a sample volume of approximately 1 mg / ml dissolved in 0.1 M NaOH. The molecular weight is measured against a polystyrene sulfonate standard. A UV detector with a wavelength of 280 nm is used.

[0060] The polydispersity index (PDI) of the lignin-based packing material may be 1.5–5.0, or 1.8–4.5, or 1.9–4.3, or 2.1–4.0, or 2.4–3.5, or 2.6–3.2, depending on the soluble fraction of the lignin-based packing material. The polydispersity index may also be determined by size exclusion chromatography (SEC). PDI is a measure of the distribution of molecular mass in a given polymer sample. PDI is calculated by dividing the weight-average molecular weight (Mw) by the number-average molecular weight (Mn). PDI indicates the distribution of individual molecular masses in a batch of polymer.

[0061] This lignin-based filler is suitable for 3 to 150 m 2 / g, or 5-100m 2 / g, or 7 - 60 m 2 It may have an STSA number of / g. The STSA number may be determined according to the standard ASTM D6556.

[0062] The lignin - based filler may have a density of up to 1.5 g / cm 3 In one embodiment, the lignin - based filler has a density of 1.0 - 1.5 g / cm 3 , or 1.15 - 1.35 g / cm 3 , or 1.1 - 1.4 g / cm 3 The density of the lignin - based filler may be determined according to the standard ISO21687.

[0063] The rubber composition disclosed in the present disclosure has an additional utility of having a high bio - based content and thus may be used to replace many fossil - based rubber compositions for various applications. Thus, the rubber composition may have a high renewable share of its components while having properties such as hardness values similar to those of fossil - type rubber compositions. The rubber composition has an additional utility of being a sustainable rubber composition, and its use may have the potential to reduce emissions compared to fossil - based rubber compositions.

Examples

[0064] Hereinafter, embodiments of the present disclosure will be referred to in detail.

[0065] The following description discloses some embodiments in sufficient detail for those skilled in the art to utilize the above - mentioned methods based on the present disclosure. Since many steps will be apparent to those skilled in the art based on the present disclosure, not all steps of the embodiments will be discussed in detail.

[0066] Example 1 - Manufacture of a Rubber Composition In this example, rubber compositions were prepared. The purpose was to evaluate the performance of renewable lignin-based fillers (LBFs) in different rubber compositions with (bio-based) rubbers and, optionally, (bio-based) plasticizers, and to compare them with rubber compositions prepared using fossil components. Comparative examples were prepared by using carbon black or silica instead of lignin-based fillers in the rubber compositions. Fossil-based rubbers and / or fossil-based plasticizers were used in place of bio-based rubbers and / or bioplasticizers in some of the (comparative) examples.

[0067] The lignin-based filler was prepared in accordance with the description provided above by using lignin material obtained from the enzymatic hydrolysis process of beech wood-based raw materials subjected to hydrothermal carbonization treatment.

[0068] The rubber composition was prepared by the following method: In the first step, rubber (EPDM), lignin-based filler or carbon black, process oil (plasticizer), polyethylene glycol, stearic acid, and zinc oxide were mixed for 6.25 minutes using a laboratory kneader (ERMAFA interlocking closed-type kneader TMI0.6). In the second mixing step, accelerators (MBT, ZDTP, and TBzTD) and sulfur were added to the basic mixture and mixed for a total of 4 minutes. This mixture was then sheeted and cured at a temperature of 170°C for t90+2 minutes using a MonTech Werkstoffpruefmaschinen GmbH hydraulic press model LP3000 600kN.

[0069] Table 1 below shows the components used to prepare the rubber composition and the properties measured for the manufactured rubber composition.

[0070] [Table 1(1)] [Table 1(2)]

[0071] ML = Minimum Torque MH = Maximum Torque t s2 = induction time t 90 = Optimal curing time RT=room temperature

[0072] Test method used: * MDR: ASTM D 5289-19a Mooney viscosity (MU): ASTM D 1646-19a Density: ASTM D792-20 Hardness:ASTM D 2240-15(2021) Ash content: DIN 51719:1997-07 Total biogenic carbon content: ASTM D6866-22

[0073] From Table 1 above, it can be seen that the rubber compositions of Examples 1, 2, and 3 exhibit properties as good as those of fossil-based compositions, while also showing a high bio-based carbon content.

[0074] Example 2 - Production of rubber composition In this example, rubber compositions were prepared. The purpose was to evaluate the performance of using renewable lignin-based fillers (LBFs) in different rubber compositions. Comparative examples were prepared by using carbon black or silica instead of lignin-based fillers in the rubber compositions.

[0075] The lignin-based filler was prepared in accordance with the description provided above by using lignin material obtained from the enzymatic hydrolysis process of beech wood-based raw materials subjected to hydrothermal carbonization treatment.

[0076] The rubber composition was prepared by the following method: In the first step, natural rubber (NR), lignin-based filler or carbon black or silica, antioxidant, stearic acid, and zinc oxide were mixed for 5.75 minutes using a laboratory kneader (ERMAFA interlocking closed-type kneader TMI0.6). In the second mixing step, an accelerator (CBS) and sulfur were added to the basic mixture and mixed for a total of 4.5 minutes. This mixture was then sheeted and cured at a temperature of 150°C for t90+2 minutes using a MonTech Werkstoffpruefmaschinen GmbH hydraulic press model LP3000 600kN.

[0077] The components used to prepare the rubber composition and the properties measured for the manufactured rubber composition are shown in Table 2 below.

[0078] [Table 2]

[0079] ML = Minimum Torque MH = Maximum Torque t s2 = induction time t 90 = Optimal curing time RT=room temperature

[0080] Test method used: * MDR: ASTM D 5289-19a Mooney viscosity (MU): ASTM D 1646-19a Density: ASTM D792-20 Hardness:ASTM D 2240-15(2021) Ash content: DIN 51719:1997-07 Total biogenic carbon content: ASTM D6866-22

[0081] The above results indicate that rubber compositions with good performance and a high bio-based share can be prepared. Rubber compositions formed using lignin-based fillers are further lightweight (low density).

[0082] Those skilled in the art will see that, with advances in the technology, the basic idea may be implemented in a variety of ways. Therefore, the embodiments are not limited to the examples given above, and instead, the embodiments may vary within the scope of the claims.

[0083] The embodiments described herein may be used in any combination with one another. Some of the embodiments may be combined together to form further embodiments. The rubber compositions and articles disclosed herein may include at least one of the embodiments described herein. It will be understood that the above benefits and advantages may relate to one embodiment or to several embodiments. The embodiments are not limited to solving any or all of the problems described or having any or all of the benefits and advantages described. It will be further understood that a reference to an item “a” refers to one or more of these items. The term “comprising” is used herein to mean including a feature or action that follows (precedes “comprising”) without prejudice to the existence of one or more additional features or actions.

Claims

1. A rubber composition, wherein the rubber composition is prepared by using at least a lignin-based filler and rubber, and optionally a plasticizer. The lignin-based packing material is prepared from lignin subjected to hydrothermal carbonization treatment. The total amount of lignin-based filler in the rubber composition is 2 to 500 phr. The total biocarbon content of the rubber composition is determined to be 50-100% according to the standard ASTM D6866-22. However, if no plasticizer is used to produce the rubber composition, at least one type of bio-based rubber is used, and if both rubber and a plasticizer are used to produce the rubber composition, at least one type of bio-based rubber and / or at least one type of bio-based plasticizer is used. Rubber composition.

2. The aforementioned proviso means that, i) If no plasticizer is used to produce the rubber composition, the rubber includes bio-based rubber. ii) When a plasticizer is used to produce the rubber composition, The rubber includes bio-based rubber, and the plasticizer includes bio-based plasticizer, or The rubber includes bio-based rubber, and the plasticizer includes fossil-based plasticizer, or The rubber includes fossil-based rubber, and the plasticizer includes a bio-based plasticizer. The rubber composition according to claim 1.

3. The rubber composition according to claim 1 or claim 2, wherein the rubber composition is prepared by using at least a lignin-based filler, a bio-based rubber, and a bio-based plasticizer.

4. The rubber composition according to any one of claims 1 to 3, wherein the weight ratio of the total amount of plasticizer to the total amount of rubber is 0 to 2, or 0.01 to 1.75, or 0.02 to 1.

5.

5. The rubber composition according to any one of claims 1 to 4, wherein the bioplasticizer is selected from bio-based oils, bio-based waxes, or bio-based liquid polymers.

6. The rubber composition according to any one of claims 1 to 5, wherein the total amount of lignin-based filler in the rubber composition is 5 to 200 phr, or 10 to 150 phr, or 20 to 100 phr, or 25 to 75 phr.

7. The rubber composition according to any one of claims 1 to 6, wherein the weight ratio of the total amount of plasticizer to the total amount of lignin-based filler is 0 to 40, or 0.05 to 20, or 0.1 to 10, or 0.2 to 5, or 0.5 to 2.

8. The rubber composition according to any one of claims 1 to 7, wherein the rubber composition exhibits a hardness value of 20 to 100, or 30 to 90, or 40 to 85, or 45 to 75, or 50 to 65, as determined in accordance with the standard ASTM D 2240-15 (2021).

9. The rubber composition is determined according to standard ASTM D 1646-19a, with a Mooney viscosity M of 20-110 MU, or 25-100 MU, or 30-90 MU, or 35-95 MU, or 40-85 MU, or 45-75 MU, or 50-70 MU, or 55-65 MU. Ｌ A rubber composition according to any one of claims 1 to 8, which has a temperature of (1 + 4) 100°C.

10. The rubber composition according to any one of claims 1 to 9, wherein the total biocarbon content of the rubber composition is determined in accordance with standard ASTM D6866-22 to be 50-99%, or 60-98%, or 70-97%, or 80-96%, or 90-95%.

11. The rubber composition according to any one of claims 1 to 10, wherein the total organic carbon content of the rubber composition is determined in accordance with DIN EN 15936:2012-11 to be 30-100%, 40-100%, 50-99%, or 60-98%.

12. The rubber composition according to any one of claims 1 to 11, wherein the ash content of the rubber composition is determined in accordance with DIN 51719:1997-07 to be less than 25% by weight, or less than 20% by weight, or less than 15% by weight, or less than 10% by weight, or less than 5% by weight.

13. The rubber composition according to any one of claims 1 to 12, wherein the rubber is selected from ethylene propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPR), butadiene rubber (BR), styrene-butadiene rubber (SBR), epichlorohydrin rubber (ECO), chloroprene rubber (CR), natural rubber (NR), epoxidized natural rubber (ENR), butyl rubber (IIR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), hydrogenated nitrile rubber (HNBR), bromobutyl rubber (BIIR), chlorobutyl rubber (CIIR), or any combination or mixture thereof.

14. The rubber composition according to any one of claims 1 to 13, wherein the lignin is derived from second-generation biomass.

15. An article comprising the rubber composition according to any one of claims 1 to 14.

16. The article according to claim 15, which is a shaped material, hose, sealing material, O-ring, weatherstrip, gasket, pipe material, membrane, insulator, cable, wiper blade, bushing, tape, foil, backing material, flooring material, plug, nipple, conveyor belt, seal, or tire.

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