Preparation method and application of nano chitin lignin composite material

Abstract

The invention discloses a preparation method and application of a nano chitin lignin composite material, and relates to the technical field of rubber composites.The nano chitin lignin composite material comprises a rubber matrix, a reinforcing filler and a rubber nano chitin lignin compound, and the reinforcing filler is precipitated silica, carbon black and nano chitin lignin; the nano chitin lignin is a natural substance. Precipitated silicon dioxide, carbon black and nano chitin lignin are used as reinforcing filler, so that high compatibility of the nano chitin lignin and a sizing material matrix is realized, networking of the filler is reduced, energy consumed by irreversible deformation is reduced, and the service life of the sizing material is prolonged. The problems that rubber products are large in production pollution, obvious in heat generation, large in energy consumption and short in service life are solved.

Description

Technical Field

[0001] The invention relates to the technical field of rubber composite materials, in particular to a preparation method of a nano-chitin-lignin composite material and application thereof. Background Art

[0002] In recent years, with the country's great emphasis on a conservation-oriented and environmentally friendly society, nanoparticles prepared from renewable resources have become an inevitable choice as natural fillers. Chitosan has many advantages, including easy access, non-toxicity, renewability, low density, low cost, good specific mechanical properties, biodegradability, good biocompatibility, reproducibility, easy chemical and mechanical modification, coupled with the recent rise of nanotechnology, chitosan nanoparticles have attracted great attention from scholars and enterprises at home and abroad. Due to its high modulus (about 134 GPa) and high tensile strength (about 10 GPa), chitosan is expected to become a reinforcing filler for nanocomposites, and chitosan nanoparticles have been used as a new type of nanofiller as a reinforcing agent in natural and synthetic polymer matrices.

[0003] The surface of chitin contains abundant oxygen-containing groups, which provides the possibility for its physical and chemical modification. By treating chitin by mechanical and chemical methods, chitin nanomaterials containing different surface chemical groups can be prepared, and then compounded with elastomers, which not only improves the mechanical properties of the polymer, but also gives the polymer new functionality and broadens its potential application value.

[0004] In addition, as a kind of renewable resource, lignin is second only to cellulose in nature and is the world's largest renewable aromatic compound. Lignin can be used as a raw material to participate in the reaction to form polymer materials, such as phenolic resin, epoxy resin, polyester, polyurethane, etc. It can also be used as an active filler to modify polymer materials to make them flame retardant, antioxidant, and UV-resistant. Filling rubber with lignin as a filler can not only strengthen rubber, replace carbon black, and get rid of dependence on oil, but also have lower production costs. At the same time, it can give rubber excellent flame retardancy, UV resistance, and antioxidant properties. Faced with increasingly depleted oil resources, rubber is an irreplaceable strategic product. Using lignin as a substitute for carbon black will be a research direction with great strategic significance. However, due to the complexity and heterogeneity of the chemical and physical structures of lignin, it is difficult to truly form a nano-scale dispersion in the rubber matrix to achieve similar performance to carbon black-enhanced rubber, and sometimes even deteriorate the performance of the material. Therefore, it needs to be blended or modified with highly reinforcing materials to highlight the advantages of lignin without significantly reducing the reinforcement of lignin in rubber.

[0005] In view of this, how to make lignin into a filler with the same reinforcing properties as traditional fillers and apply it to rubber will be a very promising direction.

[0006] Therefore, this application proposes a preparation method and application of a nano-chitosan-lignin composite material, and uses it as a filler to partially replace the filler to reinforce rubber, so as to obtain a rubber composite material with excellent comprehensive performance, so as to reach the level of industrial fillers, which is very necessary to solve the problems in the background.

[0007] Patent document CN115093587A discloses a Xanthoceras sorbifolia nano-lignin-based composite film and a preparation method thereof. The above patent uses Xanthoceras sorbifolia lignin nanoparticles as a reinforcing agent to enhance the mechanical strength of the chitosan-polyvinyl alcohol film. The resulting composite film has the advantages of high mechanical strength and strong moisture retention, etc., and realizes high added value utilization of agricultural waste Xanthoceras sorbifolia branch and leaf resources. However, the above patent cannot achieve the heat resistance and friction resistance of rubber.

[0008] Patent document CN112831059B discloses a modified lignin and its preparation method and application in rubber composite materials. The above patent realizes the reaction of lignin with alkynyl compounds in an organic solvent to obtain a reaction solution containing modified lignin. The present invention has the following advantages: (1) The alkynylating agent contains an acyl chloride functional group in its structure, which is easy to undergo esterification reaction with the alcohol hydroxyl group and phenolic hydroxyl group in the lignin molecule to generate modified lignin grafted with unsaturated alkynyl functional groups. (2) Alkynylation modification reduces the hydroxyl content in the lignin molecule and reduces the molecular polarity, which helps to inhibit the self-aggregation tendency of lignin caused by hydrogen bonds, is conducive to grinding to obtain lignin powder with a lower particle size, improves the compatibility and affinity of lignin with non-polar natural rubber, and promotes the dispersion of lignin in the natural rubber matrix. However, the above patent cannot achieve the antioxidant and UV aging resistance of rubber products.

[0009] Patent document CN113583254B discloses a cross-linkable lignin, a preparation method thereof and an application thereof in rubber composite materials. The above patent realizes that the acid anhydride contained in the prepared cross-linkable modifier reacts with the hydroxyl groups in the lignin molecules, reduces the polar hydroxyl content, generates lignin grafted with long-chain unsaturated olefins, reduces the polarity of lignin, improves the compatibility between lignin and natural rubber, and is beneficial to the dispersion of lignin in the rubber matrix. However, the above patent cannot achieve the degradability and antibacterial properties of the raw materials.

[0010] Patent document CN115521481B discloses a new type of cut-resistant resin, its preparation method and its application in the preparation of rubber composite materials. The above patent realizes that after the modified lignin and dicyclopentadiene are polymerized, a denser cross-linked network can be formed, thereby preventing the reduction of resin performance. The ring structure of the modified lignin is similar to the structure in rubber, which further enhances the compatibility. Lignin, as the matrix of this cut-resistant resin, has its own anti-aging, reinforcement and heat reduction properties, which also makes this new type of cut-resistant resin more widely used and cheaper, but the above patent cannot achieve high modulus and high tensile strength.

[0011] In summary, the above patents cannot achieve the anti-oxidation and anti-ultraviolet aging properties of the preparation of nano-chitin lignin composite materials and rubber products, the degradability, antibacterial properties, high modulus and high tensile strength of the materials, resulting in the emission of harmful gases and wastewater during the rubber production process, causing environmental pollution, consuming a large amount of energy and raw materials, wasting resources and increasing environmental pressure, and some rubber products have poor wear resistance and durability; To this end, the present application proposes a method for preparing a nano-chitosan-lignin composite material, rubber products having antioxidant properties, anti-ultraviolet aging properties, material degradability, antibacterial properties, high modulus and high tensile strength, and its application in rubber composite materials. Summary of the invention

[0012] The purpose of the present invention is to provide a method for preparing a nano-chitin-lignin composite material and its application, so as to solve the technical problems proposed in the above-mentioned background technology that the nano-chitin-lignin composite material and rubber products cannot be prepared with antioxidant, anti-ultraviolet aging properties, material degradability, antibacterial properties, high modulus and high tensile strength, resulting in the emission of harmful gases and wastewater during the rubber production process, causing environmental pollution, consuming a large amount of energy and raw materials, wasting resources and increasing environmental pressure, and some rubber products have poor wear resistance and durability.

[0013] To achieve the above object, the present invention provides the following technical solutions: an application of a nano-chitin lignin composite material in a rubber composite material, wherein the nano-chitin lignin composite material is a rubber composition of nano-chitin lignin, and the rubber composition comprises a rubber matrix, a reinforcing filler and a rubber nano-chitin lignin composite; The reinforcing filler is precipitated silica, carbon black and nano-chitosan lignin, and the nano-chitosan lignin is a natural substance; The rubber composition comprises the following raw materials based on 100 parts by weight of the raw rubber component: Styrene butadiene rubber 100.0 parts Carbon black 10.0~90.0 parts 1.0~80.0 parts of white carbon black Operating oil 1.0~20.0 parts Silane coupling agent 1.0-8.0 parts; As well as vulcanizing agents, accelerators and activators.

[0014] Preferably, the rubber composition may further include the following raw materials based on 100 parts by weight of the raw rubber component: Styrene butadiene rubber 0~100.0 parts Butadiene rubber 0~100.0 parts Carbon black 10.0~80.0 parts 1.0~60.0 parts of white carbon black Silane coupling agent 2.0~6.0 parts Anti-aging agent 1.0~4.0 parts 1.0~5.0 parts of active agent Accelerator 1~4.0 parts 1.0 to 5.0 parts of vulcanizing agent.

[0015] Preferably, the activator is zinc oxide and stearic acid, with zinc oxide accounting for 1.0 to 4.0 parts and stearic acid accounting for 1.0 to 3.0 parts; the vulcanizing agent is sulfur accounting for 1.0 to 5.0 parts; the accelerators are accelerator DM, accelerator CZ and accelerator DPG, with accelerator DM accounting for 0.2 to 2.0 parts, accelerator DPG accounting for 0.1 to 2.0 parts and accelerator CZ accounting for 0.2 to 2.0 parts.

[0016] Preferably, the rubber nano-chitin lignin composite comprises nano-chitin, lignin and a solvent; Nano-chitosan is extracted from marine organisms. The crustaceans are deproteinized, chitosan particles are extracted by adding alkali solution, and the chitosan particles are mechanically crushed to obtain nano-scale chitosan particles.

[0017] Preferably, the lignin is extracted from plant waste, decomposed by an alkaline solution of sodium hydroxide and calcium chloride, soaked in hot water to remove soluble substances, the initially separated raw materials are dissolved by adding an organic solvent of dimethylsulfamide DMF, impurities are filtered, washed with deionized water, freeze-dried, and the lignin is dispersed by a high-pressure homogenizer to obtain nano-scale lignin particles.

[0018] Preferably, the white carbon black is prepared by a precipitation method, and the BET specific surface area is 100 to 200 m 2 / g.

[0019] Preferably, the carbon black particle size is 20 to 40 nm.

[0020] Preferably, the rubber matrix includes natural rubber, styrene-butadiene rubber, butadiene rubber, a silane coupling agent is used for surface modification, the operating oil is rubber operating oil, the antioxidant is an organic sulfide antioxidant, and the stabilizer is oil-extended sulfur.

[0021] Preferably, the mixing method of the rubber composition comprises the following steps: (1) One-stage mixing: Use an internal mixer to mix, add rubber, press down and hold for 55 to 65 seconds; Lift the pressed mass, add white carbon black, carbon black, nano-chitin lignin, silane coupling agent, activator and antioxidant; Press down and hold for 55 to 65 seconds; Raise the pressing mass and add carbon black and rubber operating oil; Press down and hold for 80 to 100 seconds; Lift and press the clump, clean it; (2) Second stage mixing: Use an open mill for mixing, discharge the rubber to the open mill, adjust the roller pitch of the two-roll open mill to 0.8-1.2mm, so that the rubber compound after mixing is wrapped around the roller; Add accelerator and vulcanizer in sequence, three times for each left and right cutter; When the roller is 0.15-0.25mm, make a triangle wrap five times; Adjust the roller distance to 1.5-2.0mm, unload the film and stop.

[0022] Preferably, the synthesis method of the rubber nano-chitin lignin composite comprises the following steps: (3) Chitosan deacetylation: First, add NaBH4 (0.3 g) to a 33 wt% NaOH (250 mL) solution and stir evenly. Then add purified chitosan (10 g) to the above-mentioned evenly stirred aqueous solution. Finally, add the above-mentioned mixture to a flask under magnetic stirring and stir at 90 ° C for about 4 hours. Then filter through a suction filtration device to remove the alkali to terminate the reaction, filter, and repeatedly wash with water and ethanol 1:1 (v:v) until the pH value of the slurry reaches 7. Finally, rinse with pure ethanol again, place the dried solid in a blast drying oven and continue to dry for about 12 hours to obtain deacetylated chitosan; (4) 2,2,6,6-tetramethylpiperidin-1-oxyl radical (TEMPO) oxidation: Deacetylated chitin (1 g), TEMPO reagent (0.016 g), and sodium chlorite (1.13 g) were added to a flask containing 0.05 mol / L sodium phosphate buffer, and then a 14 wt% sodium hypochlorite solution (0.532 g) containing sodium phosphate buffer (10 mL) was added dropwise to the flask, and the flask was sealed and stirred at 60 °C for about 4 hours. After the reaction was completed, the slurry was washed with deionized water and repeatedly washed and centrifuged (8000 rpm, 15 minutes) until the pH of the slurry was 7. Finally, the pH value of the slurry was adjusted to 11 and dispersed by water bath ultrasound for about 2 hours. After ultrasonic dispersion and centrifugation (7000 rpm, 15 minutes), a light blue suspension was obtained; (5) Purify chitin, TEMPO reagent, lignin, water, and NaBr and add them to a dry three-necked flask respectively. Stir magnetically at room temperature for about 10 minutes. Then add sodium hypochlorite solution to the flask. Measure the pH of the mixture with a pH meter while stirring at room temperature. Keep the pH value at about 10 (±0.01) by adding 0.5 mol / L NaOH solution. After 20 hours, add a certain amount of ethanol to terminate the oxidation, and adjust the pH of the system to 7 with 0.5 mol / L HCl. Centrifuge the obtained suspension (8000 rpm, 15 minutes) and wash with deionized water. Perform the centrifugal washing process at least five times. Then treat the suspension with a water bath sonicator for at least 5 hours to prepare an aqueous dispersion. (6) The prepared aqueous dispersion was added to natural rubber latex, and silane coupling agent KH550 was added. The mixture was stirred for 1 hour under alkaline conditions (pH = 10), and acid was added to precipitate the rubber and chitosan lignin complex. The mixture was dried in a forced air drying oven for 5 hours to obtain a rubber nano-chitosan lignin complex.

[0023] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention achieves high modulus and high tensile strength by using reinforcing fillers, has high reinforcement, solves the problem of poor fluidity of rubber and blockage of exhaust holes in the tire bead, resulting in defects in the bead and causing a series of safety hazards; 2. The present invention achieves excellent raw material compatibility, raw material degradability and antibacterial properties by using chitin lignin, solves the problem of adding reinforced composite materials and rubber matrix incompatibility or even reducing output during product production, and improves the manufacturability of product materials; 3. The present invention prepares a rubber nano-chitosan lignin composite to realize light networking of fillers, solves the problem of large energy loss due to irreversible deformation and significant heat generation of the rubber, improves the output rate of the required materials, and significantly reduces the heat generation of the rubber; 4. The present invention achieves the goal of enhancing the hardness, strength and wear resistance of rubber by preparing a rubber composition, thereby improving the wear resistance and service life of the tire and solving the problems of serious pollution and high energy consumption in the tire manufacturing process. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The specific flow chart of the mixing method of the rubber composition of the present invention; Figure 2 The specific flow chart of the synthesis method of the rubber nano-chitin lignin composite of the present invention; DETAILED DESCRIPTION

[0025] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example 1

[0026] See also Figure 1 , a rubber composition comprises raw materials of the following components: 80 parts of styrene-butadiene rubber, 20 parts of butadiene rubber, 40 parts of carbon black, 25 parts of white carbon black, 5 parts of rubber nano-chitin lignin complex, 15 parts of rubber operating oil, 2.5 parts of stearic acid, 1 part of antioxidant, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 parts of accelerator CBS (CZ), 2 parts of oil-extended sulfur, a total of 203.13 parts of raw materials; Further, the mixing method of the rubber composition comprises the following specific steps: One-stage mixing: use internal mixer for mixing; add rubber, press down the mass and keep it for 55-65 seconds; lift the mass, add white carbon black, carbon black, nano-chitin lignin, silane coupling agent, activator and antioxidant, press down the mass and keep it for 55-65 seconds; lift the mass and add carbon black and rubber operating oil, press down the mass and keep it for 80-100 seconds; lift the mass and clean it; Second stage mixing: use open mill for mixing; discharge rubber to open mill, adjust the roller distance of double roll open mill to 0.8-1.2mm, so that the rubber compound after mixing is wrapped around the roller; add accelerator and vulcanizer in sequence, cut the left and right knives three times each; make triangle wrapping pass five times when the roller is 0.15-0.25mm; adjust the roller distance to 1.5-2.0mm, unload the sheet and park. Example 2

[0027] See also Figure 1, a rubber composition comprises raw materials of the following components: 80 parts of styrene-butadiene rubber, 20 parts of butadiene rubber, 35 parts of carbon black, 25 parts of white carbon black, 10 parts of rubber nano-chitin lignin complex, 15 parts of rubber operating oil, 2.5 parts of stearic acid, 1 part of antioxidant, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 parts of accelerator CBS (CZ), 2 parts of oil-extended sulfur, a total of 203.13 parts of raw materials; Further, the mixing method of the rubber composition comprises the following specific steps: One-stage mixing: use an internal mixer for mixing; add 80 parts of styrene-butadiene rubber and 20 parts of butadiene rubber, press down the mass and keep it for 55 to 65 seconds; lift the mass, add 25 parts of white carbon black, 10 parts of rubber nano-chitin lignin composite, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 2.5 parts of stearic acid and 1 part of antioxidant, press down the mass and keep it for 55 to 65 seconds; lift the mass, add 35 parts of carbon black and 15 parts of rubber operating oil, press down the mass and keep it for 80 to 100 seconds; lift the mass and clean it; Second stage mixing: use open mill for mixing; discharge rubber to open mill, adjust the roller distance of double roll open mill to 0.8-1.2mm, so that the rubber compound after internal mixing can be rolled; add 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 part of accelerator CBS (CZ) and 2 parts of oil-filled sulfur in sequence, and cut three times on each side; make triangle wrapping pass five times when the roller is 0.15-0.25mm; adjust the roller distance to 1.5-2.0mm, unload the sheet and park. Example 3

[0028] See also Figure 1 , a rubber composition comprises raw materials of the following components: 80 parts of styrene-butadiene rubber, 20 parts of butadiene rubber, 30 parts of carbon black, 25 parts of white carbon black, 15 parts of rubber nano-chitin lignin complex, 15 parts of rubber operating oil, 2.5 parts of stearic acid, 1 part of antioxidant, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 parts of accelerator CBS (CZ), 2 parts of oil-extended sulfur, a total of 203.13 parts of raw materials; Further, the mixing method of the rubber composition comprises the following specific steps: One-stage mixing: use an internal mixer for mixing; add 80 parts of styrene-butadiene rubber and 20 parts of butadiene rubber, press down the mass and keep it for 55 to 65 seconds; lift the mass, add 25 parts of white carbon black, 15 parts of rubber nano-chitin lignin composite, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 2.5 parts of stearic acid and 1 part of antioxidant, press down the mass and keep it for 55 to 65 seconds; lift the mass, add 30 parts of carbon black and 15 parts of rubber operating oil, press down the mass and keep it for 80 to 100 seconds; lift the mass and clean it; Second stage mixing: use open mill for mixing; discharge rubber to open mill, adjust the roller distance of double roll open mill to 0.8-1.2mm, so that the rubber compound after internal mixing can be rolled; add 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 part of accelerator CBS (CZ) and 2 parts of oil-filled sulfur in sequence, and cut three times on each side; make triangle wrapping pass five times when the roller is 0.15-0.25mm; adjust the roller distance to 1.5-2.0mm, unload the sheet and park. Example 4

[0029] See also Figure 1 , a rubber composition comprises raw materials of the following components: 80 parts of styrene-butadiene rubber, 20 parts of butadiene rubber, 25 parts of carbon black, 25 parts of white carbon black, 20 parts of rubber nano-chitin lignin complex, 15 parts of rubber operating oil, 2.5 parts of stearic acid, 1 part of antioxidant, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 parts of accelerator CBS (CZ), 2 parts of oil-extended sulfur, a total of 203.13 parts of raw materials; Further, the mixing method of the rubber composition comprises the following specific steps: One-stage mixing: mixing with an internal mixer; adding 80 parts of styrene-butadiene rubber and 20 parts of butadiene rubber, pressing down the mass and keeping it for 55 to 65 seconds; lifting the mass, adding 25 parts of white carbon black, 20 parts of rubber nano-chitin lignin compound, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 2.5 parts of stearic acid and 1 part of antioxidant, pressing down the mass and keeping it for 55 to 65 seconds; lifting the mass, adding 25 parts of carbon black and 15 parts of rubber operating oil, pressing down the mass and keeping it for 80 to 100 seconds; lifting the mass and cleaning; Second stage mixing: use open mill for mixing; discharge rubber to open mill, adjust the roller distance of double roll open mill to 0.8-1.2mm, so that the rubber compound after internal mixing can be rolled; add 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 part of accelerator CBS (CZ) and 2 parts of oil-filled sulfur in sequence, and cut three times on each side; make triangle wrapping pass five times when the roller is 0.15-0.25mm; adjust the roller distance to 1.5-2.0mm, unload the sheet and park. Example 5

[0030] See also Figure 1 , a preparation method and application of a nano-chitin lignin composite material, two groups of comparative examples are set for Examples 1 to 4, and Comparative Example 1 and Comparative Example 2 respectively include the following components of raw materials: Comparative Example 1: 80 parts of styrene-butadiene rubber, 20 parts of butadiene rubber, 45 parts of carbon black, 25 parts of white carbon black, 0 parts of rubber nano-chitin lignin composite, 15 parts of rubber operating oil, 2.5 parts of stearic acid, 1 part of antioxidant, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 part of accelerator CBS (CZ), 2 parts of oil-extended sulfur, a total of 203.13 parts of raw materials; Comparative Example 2: 80 parts of styrene-butadiene rubber, 20 parts of butadiene rubber, 50 parts of carbon black, 10 parts of white carbon black, 0 parts of rubber nano-chitin lignin complex, 15 parts of rubber operating oil, 2.5 parts of stearic acid, 1 part of antioxidant, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin, 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 part of accelerator CBS (CZ), 2 parts of oil-extended sulfur, a total of 191.13 parts of raw materials; Further, the mixing method of the rubber composition comprises the following specific steps: Comparative Example 1, one-stage mixing: mixing is performed using an internal mixer; 80 parts of styrene-butadiene rubber and 20 parts of butadiene rubber are added, and the pressing mass is pressed down and maintained for 55 to 65 seconds; the pressing mass is raised, and 25 parts of white carbon black, 4 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin wax, 2.5 parts of stearic acid and 1 part of antioxidant are added, and the pressing mass is pressed down and maintained for 55 to 65 seconds; 40 parts of carbon black and 15 parts of rubber operating oil are raised, and the pressing mass is pressed down and maintained for 80 to 100 seconds; the pressing mass is raised and cleaned; Second stage mixing: use open mill for mixing; discharge rubber to open mill, adjust the roller distance of double roll open mill to 0.8-1.2mm, so that the rubber compound after internal mixing can be rolled; add 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 part of accelerator CBS (CZ) and 2 parts of oil-filled sulfur in sequence, and cut the left and right knives three times each; make triangle wrapping and thinning five times when the roller is 0.15-0.25mm; adjust the roller distance to 1.5-2.0mm, unload the sheet and park; Comparative Example 2, one-stage mixing: mixing is performed using an internal mixer; 80 parts of styrene-butadiene rubber and 20 parts of butadiene rubber are added, and the pressing mass is pressed down and maintained for 55 to 65 seconds; the pressing mass is raised, and 10 parts of white carbon black, 2 parts of silane coupling agent, 2.13 parts of resin, 3 parts of zinc oxide, 1.5 parts of paraffin wax, 2.5 parts of stearic acid and 1 part of antioxidant are added, and the pressing mass is pressed down and maintained for 55 to 65 seconds; the pressing mass is raised, and 50 parts of carbon black and 15 parts of rubber operating oil are added, and the pressing mass is pressed down and maintained for 80 to 100 seconds; the pressing mass is raised and cleaned; Second stage mixing: use open mill for mixing; discharge rubber to open mill, adjust the roller distance of double roll open mill to 0.8-1.2mm, so that the rubber compound after internal mixing can be rolled; add 1 part of accelerator DPG (D), 1 part of accelerator DM, 0.5 part of accelerator CBS (CZ) and 2 parts of oil-filled sulfur in sequence, and cut the left and right knives three times each; make triangle wrapping five times when the roller is 0.15-0.25mm; adjust the roller distance to 1.5-2.0mm, unload the sheet, and stop Ingredients Notes: HPR620, JSR product; BR9000, a product of Zhejiang Chuanhua; N220, Cabot Chemical Products; 1165MP, Solvay Fine Chemical Additives (Qingdao) Co., Ltd.; V500, a product of Ningbo Hansheng Co., Ltd.; Stearic acid, a product of Yihai Kerry; Antioxidant 4020 (6PPD), a product of Sinopec Nanjing Chemical Industry Co., Ltd.; Si69, Evonik Chemical Products; C5 / C9 resin, ExxonMobil product; Zinc oxide, a product of Qingdao Haiyan Chemical Co., Ltd.; Microcrystalline wax, a product of Yanggu Huatai; Accelerator DPG (D), a product of Shandong Shangshun Chemical Co., Ltd.; Accelerator DM, a product of Shandong Shangshun Chemical Co., Ltd.; Accelerator CBS (CZ), a product of Shandong Shangshun Chemical Co., Ltd.; Oil-filled sulfur powder, a product of Wuxi Huasheng Rubber New Materials Technology Co., Ltd. Example 6

[0031] See also Figure 2 , a preparation method of a nano-chitin-lignin composite material and its application, the specific steps of the synthesis method of the rubber nano-chitin-lignin composite material; Further, first deacetylation: Usually, NaBH4 (0.3 g) is added to a 33 wt% NaOH (250 mL) solution and stirred evenly, then purified chitin (10 g) is added to the above-mentioned evenly stirred aqueous solution, and finally the above-mentioned mixture is added to a flask under magnetic stirring and stirred at 90°C for about 4 hours. Then, the reaction is terminated by suction filtration through a suction filtration device to remove the alkali, filter, and repeatedly wash with water and ethanol 1:1 (v:v) until the pH value of the slurry reaches 7. Finally, rinse it again with pure ethanol, place the drained solid in a blast drying oven and continue to dry it for about 12 hours to obtain deacetylated chitin.

[0032] Then, 2,2,6,6-tetramethylpiperidin-1-oxyl radical (TEMPO) oxidation: Deacetylated chitin (1 g), TEMPO reagent (0.016 g), sodium chlorite (1.13 g) were added to a flask containing 0.05 mol / L sodium phosphate buffer, and then 14 wt% sodium hypochlorite solution (0.532 g) containing sodium phosphate buffer (10 mL) was added dropwise to the flask, and the flask was sealed and stirred at 60 ° C for about 4 hours. After the reaction was completed, the slurry was washed with deionized water and repeatedly washed and centrifuged (8000 rpm, 15 minutes) until the pH of the slurry was 7. Finally, the pH value of the slurry was adjusted to 11 and dispersed by water bath ultrasound for about 2 hours. After ultrasonic dispersion and centrifugation (7000 rpm, 15 minutes), a light blue suspension was obtained.

[0033] Then, the purified chitin, TEMPO reagent, lignin, water, and NaBr were added to a dry three-necked flask, and magnetically stirred at room temperature for about 10 minutes. Then, sodium hypochlorite solution was added to the flask. The pH of the mixture was measured with a pH meter while stirring at room temperature, and the pH value was maintained at about 10 (±0.01) by dropping 0.5 mol / L NaOH solution into it. After 20 hours, a certain amount of ethanol was added to terminate the oxidation, and the pH of the system was adjusted to 7 with 0.5 mol / L HCl. The obtained suspension was centrifuged (8000 rpm, 15 minutes) and washed with deionized water. This centrifugal washing process was repeated at least five times, and then the suspension was treated with a water bath sonicator for at least 5 hours to finally prepare an aqueous dispersion. Finally, the prepared aqueous dispersion was added to natural rubber latex, and silane coupling agent KH550 was added, and stirred for 1 hour under alkaline conditions (pH=10), and acid was added to precipitate the rubber and chitin lignin complex, and dried in a forced air drying oven for 5 hours to obtain a rubber nano-chitin lignin complex. Example 7

[0034] A preparation method of a nano-chitin-lignin composite material and its application, and performance tests were performed on Examples 1 to 5; Vulcanization characteristics: According to GB / T 9869-1997 standard, the UR-2030 rotorless vulcanizer produced by Taiwan Uni-Tech Co., Ltd. was used to measure the vulcanization curve and vulcanization characteristic parameters at 143°C and a swing angle of 1°.

[0035] Tensile properties: The tensile strength and tear strength of the composite materials are in accordance with GB / T 528-2009 and GB / T 529-2008 standards. The tensile specimen is dumbbell-shaped and the tearing specimen is right-angled. The test is carried out using a U-CAN UT-2060 electronic tensile testing machine at a rate of 500 mm / min.

[0036] Abrasion test: According to GB / T 1689-1998 standard, the wear amount of the material was tested using the GOTECH GT-7012-A Akron abrasion tester produced by the High Speed ​​Rail Company.

[0037] Heat generation performance: The compression fatigue heat generation performance of the material was tested in accordance with GB / T 15584-1995 standard. The testing instrument was U-CAN UD-3801 compression fatigue heating testing machine. The testing conditions were frequency 30Hz, strain double amplitude 5.71mm, load force 24.5Kg, test time 25min, and the test specimen was a cylinder with a height of 25mm and a diameter of 17.8mm.

[0038] Example 1 is the best example with the best comprehensive performance. It can be seen that after adding the rubber nano-chitosan lignin composite, Example 1 has higher strength, higher elongation at break, and higher wear resistance, and especially significantly lower compression heat generation. The main reason is that there is a better network structure between the low-fraction nano-chitosan lignin and the rubber, which is beneficial to the improvement of the rubber network strength, and the internal friction between the fillers themselves is reduced, so the prepared tire has lower fuel consumption and longer service life.

[0039] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. Application of a nano-chitosan-lignin composite material in a rubber composite material, characterized in that: The nano-chitin lignin composite material is a rubber composition of nano-chitin lignin, and the rubber composition comprises a rubber matrix, a reinforcing filler and a rubber nano-chitin lignin composite; The reinforcing filler is precipitated silica, carbon black and nano-chitosan lignin, and the nano-chitosan lignin is a natural substance; The rubber composition comprises the following raw materials based on 100 parts by weight of the raw rubber component: Styrene butadiene rubber 100.0 parts Carbon black 10.0~90.0 parts 1.0~80.0 parts of white carbon black Operating oil 1.0~20.0 parts Silane coupling agent 1.0-8.0 parts; As well as vulcanizing agents, accelerators and activators.

2. The use of a nano-chitosan lignin composite material in a rubber composite material according to claim 1, characterized in that: The rubber composition may further include the following raw materials based on 100 parts by weight of the raw rubber component: Styrene butadiene rubber 0~100.0 parts Butadiene rubber 0~100.0 parts Carbon black 10.0~80.0 parts 1.0~60.0 parts of white carbon black Silane coupling agent 2.0~6.0 parts Anti-aging agent 1.0~4.0 parts 1.0~5.0 parts of active agent Accelerator 1~4.0 parts 1.0 to 5.0 parts of vulcanizing agent.

3. The use of a nano-chitosan lignin composite material in a rubber composite material according to claim 2, characterized in that: The active agent is zinc oxide and stearic acid, with zinc oxide accounting for 1.0-4.0 parts and stearic acid accounting for 1.0-3.0 parts. The vulcanizing agent is sulfur accounting for 1.0-5.0 parts. The accelerators are accelerator DM, accelerator CZ and accelerator DPG, with accelerator DM accounting for 0.2-2.0 parts, accelerator DPG accounting for 0.1-2.0 parts and accelerator CZ accounting for 0.2-2.0 parts.

4. The use of a nano-chitosan lignin composite material in a rubber composite material according to claim 1, characterized in that: The rubber nano-chitin lignin composite comprises nano-chitin, lignin and a solvent; Nano-chitosan is extracted from marine organisms. The crustaceans are deproteinized, chitosan particles are extracted by adding alkali solution, and the chitosan particles are mechanically crushed to obtain nano-scale chitosan particles.

5. The use of a nano-chitosan lignin composite material in a rubber composite material according to claim 4, characterized in that: The lignin is extracted from plant waste, decomposed by sodium hydroxide and calcium chloride alkaline solution, soaked in hot water to remove soluble substances, the raw materials separated initially are added with organic solvent dimethylsulfamide DMF to dissolve, impurities are filtered, washed with deionized water, freeze-dried, and the lignin is dispersed by a high-pressure homogenizer to obtain nano-scale lignin particles.

6. The use of a nano-chitosan lignin composite material in a rubber composite material according to claim 2, characterized in that: The white carbon black is prepared by a precipitation method, and the BET specific surface area is 100 to 200 m 2 / g.

7. The use of a nano-chitosan lignin composite material in a rubber composite material according to claim 1, characterized in that: The carbon black particle size is 20 to 40 nm.

8. The use of a nano-chitosan lignin composite material in a rubber composite material according to claim 2, characterized in that: The rubber matrix comprises natural rubber, styrene-butadiene rubber and cis-1,4-dimethyl-1-butyl rubber; the silane coupling agent is used for surface modification; the operating oil is rubber operating oil; the antioxidant is an organic sulfide antioxidant; and the stabilizer is oil-extended sulfur.

9. A method for preparing a nano-chitosan-lignin composite material, suitable for use of a nano-chitosan-lignin composite material described in any one of 1 to 8 in a rubber composite material, characterized in that: The mixing method of the rubber composition comprises the following steps: (1) One-stage mixing: Use an internal mixer to mix, add rubber, press down and hold for 55 to 65 seconds; Lift the pressed mass, add white carbon black, carbon black, nano-chitin lignin, silane coupling agent, activator and antioxidant; Press down and hold for 55 to 65 seconds; Raise the pressing mass and add carbon black and rubber operating oil; Press down and hold for 80 to 100 seconds; Lift and press the clump, clean it; (2) Second stage mixing: Use an open mill for mixing, discharge the rubber to the open mill, adjust the roller pitch of the two-roll open mill to 0.8-1.2mm, so that the rubber compound after mixing is wrapped around the roller; Add accelerator and vulcanizer in sequence, three times for each left and right cutter; When the roller is 0.15-0.25mm, make a triangle wrap five times; Adjust the roller distance to 1.5-2.0mm, unload the film and stop.

10. The method for preparing a nano-chitosan-lignin composite material according to claim 9, characterized in that: The synthesis method of the rubber nano-chitin lignin composite comprises the following steps: (3) Deacetylation of chitin: First, add NaBH4 to a 33wt% NaOH solution and stir evenly, then add purified chitin to the above-mentioned evenly stirred aqueous solution, and finally add the above-mentioned mixed solution to a flask under magnetic stirring and stir at 90°C for about 4 hours; then filter through a suction filtration device to remove the alkali to terminate the reaction, filter, and repeatedly wash with water and ethanol in a 1:1 ratio until the pH value of the slurry reaches 7; finally, rinse it again with pure ethanol, place the dried solid in a blast drying oven and continue to dry it for about 12 hours to obtain deacetylated chitin; (4) 2,2,6,6-tetramethylpiperidin-1-oxyl free radical oxidation: 1 g of deacetylated chitin, TEMPO reagent, and sodium chlorite were added to a flask containing 0.05 mol / L sodium phosphate buffer, and then a 14 wt% sodium hypochlorite solution containing sodium phosphate buffer was added dropwise to the flask, and the flask was sealed and stirred at 60 °C for about 4 hours; after the reaction was completed, the slurry was washed with deionized water and repeatedly washed and centrifuged until the pH of the slurry was 7; finally, the pH value of the slurry was adjusted to 11 and subjected to water bath ultrasonic dispersion for 2 hours; after ultrasonic dispersion and centrifugation, a light blue suspension was obtained; (5) Purified chitin, TEMPO reagent, lignin, water, and NaBr were added to a dry three-necked flask, respectively, and magnetically stirred at room temperature for 10 minutes; then sodium hypochlorite solution was added to the flask; the pH of the mixture was measured with a pH meter while stirring at room temperature, and the pH value was maintained at 10±0.01 by adding 0.5 mol / L NaOH solution dropwise thereto; after 20 hours, a certain amount of ethanol was added to terminate the oxidation, and the pH of the system was adjusted to 7 with 0.5 mol / L HCl; the obtained suspension was centrifuged and washed with deionized water, and the centrifugal washing process was repeated at least five times, and then the suspension was treated with a water bath sonicator for at least 5 hours to finally prepare an aqueous dispersion; (6) The prepared aqueous dispersion was added to natural rubber latex, and silane coupling agent KH550 was added. The mixture was stirred for 1 hour at pH = 10 under alkaline conditions, and acid was added to precipitate the rubber and chitosan lignin complex. The mixture was dried in a forced air drying oven for 5 hours to obtain a rubber nano-chitosan lignin complex.

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