Rubber composition containing wet-process mixed lignin masterbatch as well as preparation method and application of rubber composition

Abstract

The invention relates to the technical field of rubber manufacturing, and discloses a rubber composition containing wet-process mixed lignin masterbatch as well as a preparation method and application of the rubber composition. According to the lignin masterbatch obtained by wet mixing, the dispersion effect of lignin in rubber is improved, great positive contribution is made to the mechanical property of a rubber composition, and the substitutability of lignin to filler such as carbon black is improved; by adding the metal coordination compound, the nano filler and the coupling agent in different proportions into the rubber composition, programmable regulation and control of mechanical properties and rolling resistance of the rubber composition can be realized, so that the usable rubber composition is provided for different requirements of tires, conveying belts, rubber hoses, sealing rings and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of rubber manufacturing, in particular to a rubber composition containing wet-mixed lignin masterbatch, a preparation method and application thereof. BACKGROUND

[0002] Carbon black, as a traditional rubber filler, relies on non-renewable petroleum resources, and its production process exacerbates greenhouse gas emissions, thereby exacerbating global climate change. With the improvement of environmental awareness, the development of renewable, bio-based green alternative materials has become an urgent need for the sustainable development of the rubber industry. Therefore, reducing the dependence on carbon black and promoting the research and development of bio-based fillers have important environmental and economic significance. Lignin, as a renewable bio-based material, is derived from by-products of the paper industry or bio-refining processes, and has the potential to replace petroleum-based fillers. Currently, lignin in black liquor from papermaking is mostly directly incinerated, which not only wastes resources but also increases carbon emissions. Efficient utilization of lignin can improve resource recycling rate and meet the principle of circular economy.

[0003] Studies have shown that lignin can effectively partially replace traditional carbon black as a rubber filler and exhibit good reinforcing effect in rubber composites. Its three-dimensional aromatic structure and surface active functional groups can form physical cross-linking and hydrogen bonding interactions with rubber molecular chains, thereby improving the mechanical properties of the composite. Compared with carbon black, lignin has low cost, small density, and excellent ultraviolet aging resistance. In addition, the introduction of lignin can reduce the rolling resistance of the composite, which is of great significance for the development of green tires. However, due to its rich oxygen-containing functional groups (such as phenolic hydroxyl groups and carboxyl groups) and rigid benzene ring structure, lignin has strong intermolecular forces and tends to agglomerate, resulting in poor dispersion and weak interfacial compatibility in the rubber matrix, which reduces the mechanical properties of the composite and makes its reinforcing effect inferior to that of traditional carbon black fillers.

[0004] Li Bin et al. (Modified Lignin Green Chemistry Wet Mixing for Improving the Performance of Rubber and Rubber Additives) disclosed that the bio-rubber obtained by green chemistry wet mixing of methylated modified lignin and natural rubber NR could effectively improve the adhesion, wear resistance and aging resistance of tire compounds. Chinese invention patent 201811376886.4 also disclosed a wet process for preparing a bio-based multifunctional constant viscosity glue. The lignin rubber phase solvent (de-polarized modified lignin) is mixed into natural rubber by wet blending, which can make the lignin rubber phase solvent well dispersed in the natural rubber and produce good interfacial bonding. The bio-based multifunctional constant viscosity glue produced can replace part of the natural rubber, and the overall performance of the final rubber product is improved.

[0005] In the paper "Lignin and metal coordination bond synergistically enhanced and toughened polyethylene elastomer composite", lignin is the second largest component in plants, and the functional groups such as aromatic ring and phenolic hydroxyl in the molecule endow it with functions such as ultraviolet shielding and anti-aging. By using the rich polar functional groups of lignin as the natural ligand of zinc ions, introducing 3-amino-1,2,4-triazole as a reactive compatibilizer, and using a melt blending method, a metal coordination bond is in-situ constructed at the interface between lignin and maleic anhydride grafted ethylene-octene copolymer elastomer (PM), and a thermoplastic elastomer composite with lignin as the plastic phase and PM as the rubber phase is prepared, which significantly improves the mechanical properties of the composite. This brings inspiration to our research on rubber. SUMMARY

[0006] The present application provides a rubber composition containing a wet-mixed lignin masterbatch, a preparation method and application thereof.

[0007] In order to achieve the above-mentioned purpose, the following technical solutions are adopted in the present application: A rubber composition containing a wet-mixed lignin masterbatch, the rubber composition is prepared by mixing the following components by weight of raw rubber: Rubber 100 parts; Lignin masterbatch 1-50 parts; Nano filler A 0-80 parts; Active agent 1-15 parts; Vulcanizing agent 1-5 parts; Accelerator 0.1-4 parts; Metal coordination compound 0-20 parts; Coupling agent 0-10 parts; The lignin masterbatch is prepared by wet mixing raw materials including rubber latex and water-soluble lignin.

[0008] Preferably, the rubber composition is prepared by mixing the following components by weight of raw rubber: Rubber 100 parts; Lignin masterbatch 10-30 parts; Nano filler A 20-50 parts; Active agent 5-10 parts; Vulcanizing agent 2-4 parts; Accelerator 0.5-2 parts; Metal coordination compound 3-10 parts; Coupling agent 2-6 parts.

[0009] Preferably, the lignin masterbatch is prepared by mixing the following components by weight of rubber latex: 100 parts of rubber latex; Water-soluble lignin, 1-50 parts; Water 0-500 parts; Nanofiller B: 0-80 parts; 50-500 parts flocculant; The rubber latex is on a dry weight basis; The raw material for the water-soluble lignin is selected from water-soluble lignin or non-water-soluble lignin; wherein, the non-water-soluble lignin is modified into water-soluble lignin by organic acid, and the amount of organic acid added is 1 to 3 times that of the non-water-soluble lignin.

[0010] Preferably, the lignin masterbatch is prepared by mixing raw materials comprising the following components based on 100 parts by weight of rubber latex: 100 parts rubber latex; 10-30 parts of water-soluble lignin; 100-300 parts water; Nanofiller B: 20-50 parts; 100-300 parts flocculant.

[0011] Preferably, the method for preparing the lignin masterbatch includes the following steps: (1) Place non-water-soluble lignin and organic acid solution in a container, adjust the pH to alkaline, stir the reaction in an oil bath at high temperature, cool to room temperature after the reaction is completed to precipitate, wash the precipitate repeatedly, filter and dry in an oven to obtain water-soluble lignin. (2) Dissolve water-soluble lignin in water to obtain an aqueous lignin solution; (3) Add lignin aqueous solution and nanofiller to rubber latex and stir to disperse to obtain lignin latex; (4) Add flocculant to lignin latex, flocculate, wash with water and dry to obtain lignin masterbatch; When the raw material for the water-soluble lignin is selected from water-soluble lignin, step (1) can be omitted.

[0012] Preferably, in step (1), the pH range for adjusting the pH to alkaline is 9 to 11.

[0013] Preferably, in step (1), the high-temperature stirring temperature of the oil bath is 80~140℃, the stirring time is 6~20h, and the stirring speed is 50~600rpm.

[0014] Preferably, in step (3), the stirring speed of the lignin aqueous solution, the nanofiller and the rubber latex is 50~600 rpm and the stirring time is 0.5~2h.

[0015] Preferably, in step (4), the drying temperature of the lignin masterbatch is 40℃~100℃, preferably 60℃~80℃.

[0016] Preferably, the rubber latex is selected from one or more of natural latex, modified natural latex, styrene-butadiene latex, nitrile latex, and chloroprene latex.

[0017] Preferably, the lignin is selected from one or more of sulfate lignin, sulfonated lignin, organic solvent lignin, enzymatically hydrolyzed lignin, and alkaline lignin.

[0018] Preferably, the organic acid is selected from one or more of lactic acid, itaconic acid, gluconic acid, and amino acids; gluconic acid is preferred.

[0019] Preferably, the nanofiller B is selected from one or more of carbon black, silica, carbon nanotubes, graphene, nanocellulose, montmorillonite, and calcium carbonate; preferably carbon black and / or silica.

[0020] Preferably, the flocculant is selected from acidic flocculants and / or salt flocculants; preferably, it is one or more of formic acid, acetic acid, hydrochloric acid, sulfuric acid, calcium chloride, and aluminum chloride.

[0021] Preferably, the nanofiller A is selected from one or more of carbon black, silica, carbon nanotubes, graphene, nanocellulose, montmorillonite, and calcium carbonate.

[0022] Preferably, the activator is zinc oxide and stearic acid, with zinc oxide in the amount of 1 to 10 parts and stearic acid in the amount of 1 to 5 parts.

[0023] Preferably, the vulcanizing agent is sulfur.

[0024] Preferably, the accelerator is selected from one or more of the following: accelerator DM, accelerator MBT, accelerator CZ, accelerator NS, accelerator TMTM, accelerator TMTD, and accelerator DPG.

[0025] Preferably, the metal coordination compound is selected from one or more of zinc methacrylate, magnesium methacrylate, zinc salts, polynuclear zinc complexes, and bio-based zinc salts; zinc methacrylate is preferred. Preferably, the coupling agent is selected from one or more of silicon 69, KH-550, KH560, and KH570.

[0026] Furthermore, the present invention also provides a method for preparing the rubber composition, comprising the following steps: (1) First stage of mixing: Adjust the internal mixer to a temperature of 85~95℃ and a speed of 50~70r / min, add lignin masterbatch, nano filler and additives (except sulfur and accelerator) in sequence, mix for 5.5~6.5min or discharge the glue when the temperature reaches 145~155℃; (2) Two-stage mixing: Adjust the internal mixer to a temperature of 55~65℃ and a speed of 45~55r / min. Add the first-stage compound, sulfur and accelerator in sequence. After mixing for 4 minutes, discharge the compound. The discharge temperature is ≤110℃. (3) Three-stage mixing: Adjust the open mill to a temperature of 55~65℃ and a roller gap of 1~2mm. Add the two-stage mixed rubber to the open mill for plasticizing and wrapping the rollers. After wrapping the rollers, make three triangular wraps and roll once. Adjust the roller gap to 2~3mm and then sheet to obtain the mixed rubber. (4) The compound is vulcanized to obtain a rubber composition.

[0027] Furthermore, the present invention also provides the application of the rubber composition in the preparation of tires, conveyor belts, rubber hoses, and sealing rings.

[0028] This invention employs the above-mentioned scheme, using a lignin masterbatch obtained through wet mixing to improve the dispersion of lignin in rubber, significantly contributing to the mechanical properties of the rubber composition and enhancing the substitutability of lignin for fillers such as carbon black. By adding different proportions of metal coordination compounds, nanofillers, and coupling agents to the rubber composition, programmable control of the mechanical properties and rolling resistance can be achieved, thus providing usable rubber compositions for various needs such as tires, conveyor belts, rubber hoses, and sealing rings. Furthermore, lignin is the largest renewable aromatic resource, widely available and inexpensive, conforming to green chemistry principles. Using lignin to replace some fillers and improve rubber properties is both environmentally friendly and economical. Moreover, the wet mixing process of this invention has low requirements for the source, type, and purity of lignin, making it universally applicable. Attached Figure Description

[0029] Figure 1 The strain scan diagrams of the rubber compounds in Examples 1, 2 and Comparative Example 1 are shown (RPA: 60°C, 0.1~100%, 1Hz). Detailed Implementation

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present invention.

[0031] (Examples and Comparative Examples) The rubber composition formulations for the examples and comparative examples are shown in Table 1.

[0032] Table 1 Rubber Composition Formulation

[0033] The formulations of the lignin masterbatch used in Examples 1-6 are shown in Table 2.

[0034] The lignin masterbatch LG used in Comparative Example 4 was obtained by dry mixing water-soluble lignin (obtained by gluconic acid modification of lignin LG) with natural rubber latex. The dosage was the same as that of the lignin masterbatch LG formulation in Example 1.

[0035] Table 2 Formulations of lignin masterbatch used in Examples 1-6

[0036] (Lignopolymer masterbatch mixing method) Example

[0037] Preparation of lignin masterbatch: (1) Place lignin LG and gluconic acid solution in a beaker with a stirring rotor, adjust the pH to 9.0, stir the reaction at 120°C in an oil bath for 12 hours, and cool to room temperature after the reaction to precipitate; wash the reaction product repeatedly 3 times, filter and dry to obtain water-soluble lignin; (2) Dissolve water-soluble lignin in water to obtain an aqueous lignin solution; (3) Add the lignin aqueous solution to the natural rubber latex and mechanically stir for 1 hour at a stirring speed of 300 rpm to obtain lignin latex; (4) Add hydrochloric acid to the lignin latex in batches. After complete flocculation, cut the flocs into small pieces, wash them repeatedly with water 3 times, and then dry the flocs in an oven at 65°C until constant weight to obtain lignin masterbatch. Example

[0038] Preparation of lignin masterbatch: (1) Dissolve lignin MG in water to obtain an aqueous lignin solution; (2) Add the lignin aqueous solution to the natural rubber latex and mechanically stir for 0.5 h at a stirring speed of 300 rpm to obtain lignin latex; (3) Add hydrochloric acid to the rubber latex in batches. After complete flocculation, cut the flocs into small pieces, wash them repeatedly with water 3 times, and then dry the flocs in an oven at 65°C until constant weight to obtain lignin masterbatch. Example

[0039] The preparation of lignin masterbatch is the same as in Example 2. Example

[0040] Preparation of lignin masterbatch: (1) Place lignin LG and gluconic acid solution in a beaker with a stirring rotor, adjust the pH to 9.0, stir the reaction at 120°C in an oil bath for 12 hours, and cool to room temperature after the reaction to precipitate; wash the reaction product repeatedly 3 times, filter and dry to obtain water-soluble lignin; (2) Dissolve water-soluble lignin in water to obtain an aqueous lignin solution; (3) Add lignin aqueous solution and fumed silica to natural rubber latex, and mechanically stir for 2 hours at a stirring speed of 400 rpm to obtain lignin latex; (4) Add hydrochloric acid to the lignin latex in batches. After complete flocculation, cut the flocs into small pieces, wash them repeatedly with water 3 times, and then dry the flocs in an oven at 65°C until constant weight to obtain lignin masterbatch. Example

[0041] Preparation of lignin masterbatch: (1) Place lignin LG and gluconic acid solution in a beaker with a stirring rotor, adjust the pH to 9.0, stir the reaction at 120°C in an oil bath for 12 hours, and cool to room temperature after the reaction to precipitate; wash the reaction product repeatedly 3 times, filter and dry to obtain water-soluble lignin; (2) Dissolve water-soluble lignin in water to obtain an aqueous lignin solution; (3) Add lignin aqueous solution and modified carbon nanotubes to natural rubber latex, and mechanically stir for 2 hours at a stirring speed of 300 rpm to obtain lignin latex; (4) Add hydrochloric acid to the lignin latex in batches. After complete flocculation, cut the flocs into small pieces, wash them repeatedly with water 3 times, and then dry the flocs in an oven at 65°C until constant weight to obtain lignin masterbatch. Example

[0042] Preparation of lignin masterbatch: (1) Place lignin LG and gluconic acid solution in a beaker with a stirring rotor, adjust the pH to 9.0, stir the reaction at 120°C in an oil bath for 12 hours, and cool to room temperature after the reaction to precipitate; wash the reaction product repeatedly 3 times, filter and dry to obtain water-soluble lignin; (2) Dissolve water-soluble lignin in water to obtain an aqueous lignin solution; (3) Add lignin aqueous solution, modified carbon nanotubes and fumed silica to natural rubber latex, and mechanically stir for 1 hour at a stirring speed of 300 rpm to obtain lignin latex; (4) Add hydrochloric acid to the lignin latex in batches. After complete flocculation, cut the flocs into small pieces, wash them repeatedly with water 3 times, and then dry the flocs in an oven at 65°C until constant weight to obtain lignin masterbatch.

[0043] (Rubber composition mixing method) The mixing method for this example is as follows: (1) First stage of mixing: Adjust the internal mixer to a temperature of 90℃ and a speed of 60r / min, and add lignin masterbatch, nano filler and additives (except sulfur and accelerator) in sequence. When the mixing temperature reaches 150℃, discharge the glue. (2) Two-stage mixing: Adjust the internal mixer to a temperature of 60℃ and a speed of 50r / min. Add the first-stage compound, sulfur and accelerator in sequence. After mixing for 4 minutes, discharge the compound. The discharge temperature is ≤110℃. (3) Three-stage mixing: Adjust the open mill to a temperature of 60℃ and a roller gap of 1mm. Add the two-stage mixed rubber to the open mill for plasticizing and wrapping the rollers. After wrapping the rollers, make three triangular wraps and roll once. Adjust the roller gap to 2mm and produce sheets to obtain the mixed rubber. (4) The compound rubber is hot-pressed and vulcanized at 151°C on a flat vulcanizing machine, and the vulcanization temperature is T. 90 +2min to obtain the rubber composition.

[0044] The comparative mixing method is as follows: (1) First stage of mixing: Adjust the internal mixer to a temperature of 90℃ and a speed of 60r / min, and add lignin, nano fillers and additives (except sulfur and accelerators) in sequence. When the mixing temperature reaches 150℃, discharge the glue. (2) Two-stage mixing: Adjust the internal mixer to a temperature of 60℃ and a speed of 50r / min. Add the first-stage compound, sulfur and accelerator in sequence. After mixing for 4 minutes, discharge the compound. The discharge temperature is ≤110℃. (3) Three-stage mixing: Adjust the open mill to a temperature of 60℃ and a roller gap of 1mm. Add the two-stage mixed rubber to the open mill for plasticizing and wrapping the rollers. After wrapping the rollers, make three triangular wraps and roll once. Adjust the roller gap to 2mm and produce sheets to obtain the mixed rubber. (4) The compound rubber is hot-pressed and vulcanized at 151°C on a flat vulcanizing machine, and the vulcanization temperature is T. 90 +2min to obtain the rubber composition.

[0045] (Test metrics) The sample preparation method for the performance testing of rubber compositions refers to the national standard GB / T 2941-2006.

[0046] The test methods for tensile strength (MPa), elongation at break, and stress at 300% constant elongation are in accordance with GB / T 528-2009.

[0047] The tear strength test method refers to GB / T 529-2008.

[0048] The Tanδ (60℃) test method refers to GB / T 29611-2013, RPA: 60℃, 0.1~100%, 1Hz.

[0049] All data were compared with the performance of Comparative Example 1 sample as 100. The test data are shown in Table 3.

[0050] Table 3

[0051] The difference between Comparative Example 1 and Example 1 is that Example 1 added lignin masterbatch LG, while Comparative Example 1 added untreated lignin LG. It can be seen that the overall performance of Example 1 is significantly better than that of Comparative Example 1, effectively improving the mechanical properties of the rubber composition. The analysis of Comparative Example 2 and Example 2 is consistent with that of Comparative Example 1 and Example 1. It can be seen that the lignin masterbatch obtained by pre-wet mixing improves the dispersion of lignin in the rubber, making a significant positive contribution to the mechanical properties of the rubber composition. This may be because the modified material gluconic acid possesses both carboxyl groups and multiple hydroxyl groups, providing reaction sites and exhibiting strong hydrophilicity. It can be grafted onto the lignin skeleton through esterification to introduce hydrophilic segments, improving the water solubility of lignin. The difference between Comparative Example 4 and Example 1 is the mixing method of the lignin masterbatch LG. It can be seen that wet mixing is more conducive to the dispersion of lignin in the rubber, effectively contributing to the improvement of the mechanical properties of the rubber composition by the lignin masterbatch.

[0052] Examples 2 and 3 demonstrate that the introduction of metal coordination compounds (e.g., zinc methacrylate) can improve the 300% tensile stress and tear strength of the rubber composition and reduce rolling resistance. The overall performance of the rubber composition can be effectively improved through filler pre-dispersion treatment and metal ion coordination crosslinking technology. Examples 1 and 5 show that the introduction of nanofiller A (e.g., modified carbon nanotubes) has the same effect as the metal coordination compound (e.g., zinc methacrylate). Examples 4, 5, 6, and Comparative Example 3 demonstrate that the mechanical properties and rolling resistance of the rubber composition can be programmably controlled by adjusting the amounts of lignin masterbatch, nanofiller A (e.g., silica), and coupling agent (e.g., Si-69), thereby providing usable rubber compositions for different needs such as tires, conveyor belts, rubber hoses, and seals.

[0053] The foregoing description of embodiments of the present invention, through which those skilled in the art are able to implement or use the present invention, will be readily apparent to those skilled in the art. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novelty disclosed herein.

Claims

1. A rubber composition containing wet-processed lignin masterbatch, characterized in that, The rubber composition is prepared by mixing raw materials comprising the following components based on 100 parts by weight of raw rubber: 100 parts of rubber; 1-50 parts of lignin masterbatch; Nanofiller A: 0-80 parts; Surfactant 1-15 parts; 1-5 parts of vulcanizing agent; Accelerator 0.1-4 parts; 0-20 parts of metal coordination compounds; 0-10 parts of coupling agent; The lignin masterbatch is prepared by wet mixing of raw materials including rubber latex and water-soluble lignin.

2. The rubber composition containing wet-processed lignin masterbatch according to claim 1, characterized in that, The rubber composition is prepared by mixing raw materials comprising the following components based on 100 parts by weight of raw rubber: 100 parts of rubber; 10-30 parts of lignin masterbatch; Nanofiller A: 20-50 parts; 5-10 parts of surfactant; 2-4 parts of vulcanizing agent; Accelerator 0.5-2 parts; 3-10 parts of metal coordination compound; 2-6 parts of coupling agent.

3. A rubber composition containing wet-processed lignin masterbatch according to claim 1 or 2, characterized in that, The lignin masterbatch is prepared by mixing raw materials comprising the following components based on 100 parts by weight of rubber latex: 100 parts rubber latex; Water-soluble lignin, 1-50 parts; Water 0-500 parts; Nanofiller B: 0-80 parts; 50-500 parts flocculant; The rubber latex is on a dry weight basis; The raw material for the water-soluble lignin is selected from water-soluble lignin or non-water-soluble lignin; wherein, the non-water-soluble lignin is modified into water-soluble lignin by organic acid, and the amount of organic acid added is 1 to 3 times that of the non-water-soluble lignin.

4. The rubber composition containing wet-processed lignin masterbatch according to claim 3, characterized in that, The lignin masterbatch is prepared by mixing raw materials comprising the following components based on 100 parts by weight of rubber latex: 100 parts rubber latex; 10-30 parts of water-soluble lignin; 100-300 parts water; Nanofiller B: 20-50 parts; 100-300 parts flocculant.

5. A rubber composition containing wet-processed lignin masterbatch according to claim 3 or 4, characterized in that, The preparation method of the lignin masterbatch includes the following steps: (1) Place non-water-soluble lignin and organic acid solution in a container, adjust the pH to alkaline, stir the reaction in an oil bath at high temperature, cool to room temperature after the reaction is completed to precipitate, wash the precipitate repeatedly, filter and dry in an oven to obtain water-soluble lignin. (2) Dissolve water-soluble lignin in water to obtain an aqueous lignin solution; (3) Add lignin aqueous solution and nanofiller to rubber latex and stir to disperse to obtain lignin latex; (4) Add flocculant to lignin latex, flocculate, wash with water and dry to obtain lignin masterbatch; When the raw material for the water-soluble lignin is selected from water-soluble lignin, step (1) can be omitted.

6. The rubber composition containing wet-processed lignin masterbatch according to claim 5, characterized in that, In step (1), the pH range for adjusting the pH to alkaline is 9-11; And / or, in step (1), the high temperature of the oil bath is 80~140℃, the stirring time is 6~20h, and the stirring speed is 50~600rpm; And / or, in step (3), the stirring speed of the lignin aqueous solution, the nanofiller and the rubber latex is 50~600 rpm and the stirring time is 0.5~2h; And / or, in step (4), the drying temperature of the lignin masterbatch is 40℃~100℃, preferably 60℃~80℃.

7. A rubber composition containing wet-processed lignin masterbatch according to claim 3 or 4, characterized in that, The rubber latex is selected from one or more of natural latex, modified natural latex, styrene-butadiene latex, nitrile latex, and chloroprene latex; And / or, the lignin is selected from one or more of sulfate lignin, sulfonated lignin, organic solvent lignin, enzymatically hydrolyzed lignin, and alkaline lignin; And / or, the organic acid is selected from one or more of lactic acid, itaconic acid, gluconic acid, and amino acids; gluconic acid is preferred; And / or, the nanofiller B is selected from one or more of carbon black, silica, carbon nanotubes, graphene, nanocellulose, montmorillonite, and calcium carbonate; preferably carbon black and / or silica; And / or, the flocculant is selected from acid flocculants and / or salt flocculants; preferably one or more of formic acid, acetic acid, hydrochloric acid, sulfuric acid, calcium chloride, and aluminum chloride.

8. A rubber composition containing wet-processed lignin masterbatch according to claim 1 or 2, characterized in that, The nanofiller A is selected from one or more of carbon black, silica, carbon nanotubes, graphene, nanocellulose, montmorillonite, and calcium carbonate. And / or, the activator is zinc oxide and stearic acid, wherein the amount of zinc oxide is 1 to 10 parts and the amount of stearic acid is 1 to 5 parts; And / or, the vulcanizing agent is sulfur; And / or, the accelerator is selected from one or more of the following: accelerator DM, accelerator MBT, accelerator CZ, accelerator NS, accelerator TMTM, accelerator TMTD, and accelerator DPG; And / or, the metal coordination compound is selected from one or more of zinc methacrylate, magnesium methacrylate, zinc salts, polynuclear zinc complexes, and bio-based zinc salts; preferably zinc methacrylate; And / or, the coupling agent is selected from one or more of silicon 69, KH-550, KH560, and KH570.

9. A method for preparing the rubber composition according to any one of claims 1-8, characterized in that, Includes the following steps: (1) First stage of mixing: Adjust the internal mixer to a temperature of 85~95℃ and a speed of 50~70r / min, add lignin masterbatch, nano filler and additives (except sulfur and accelerator) in sequence, mix for 5.5~6.5min or discharge the glue when the temperature reaches 145~155℃; (2) Two-stage mixing: Adjust the internal mixer to a temperature of 55~65℃ and a speed of 45~55r / min. Add the first-stage compound, sulfur and accelerator in sequence. After mixing for 4 minutes, discharge the compound. The discharge temperature is ≤110℃. (3) Three-stage mixing: Adjust the open mill to a temperature of 55~65℃ and a roller gap of 1~2mm. Add the two-stage mixed rubber to the open mill for plasticizing and wrapping the rollers. After wrapping the rollers, make three triangular wraps and roll once. Adjust the roller gap to 2~3mm and then sheet to obtain the mixed rubber. (4) The compound is vulcanized to obtain a rubber composition.

10. The use of the rubber composition according to any one of claims 1-8 in the preparation of tires, conveyor belts, rubber hoses, and sealing rings.

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