Dispersing agent for rubber and environment-friendly rubber prepared from dispersing agent

Abstract

The invention relates to the technical field of dispersing agents, in particular to a dispersing agent for rubber and environment-friendly rubber prepared from the dispersing agent. The dispersing agent for rubber comprises the following components in parts by weight: 20-40 parts of fatty alcohol-polyoxyethylene ether, 15-30 parts of modified polyether amine, 10-20 parts of a carrier and 20-30 parts of deionized water. The dispersing agent for the rubber is obtained by mixing the fatty alcohol-polyoxyethylene ether, the modified polyether amine and the deionized water, stirring at 60-70 DEG C for 30-50 minutes, then adding the carrier, uniformly stirring, cooling and pelletizing, and the dispersing agent for the rubber is applied to a preparation process of environment-friendly rubber, so that the dispersity and the uniformity of the rubber can be remarkably improved, and the service life of the rubber is prolonged. The physical property and the processability of the rubber are improved, and meanwhile, the emission of volatile organic compounds is effectively reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of dispersants, in particular to a dispersant for rubber and an environmentally friendly rubber prepared therefrom. Background Art

[0002] With the continuous improvement of the performance requirements of the rubber industry, especially in the reinforcement of rubber composites, traditional inorganic fillers (such as carbon black, white carbon black) and new fillers (such as graphene, clay, etc.) have become the main choices for the reinforcement of rubber composites.

[0003] However, due to the extremely high specific surface area and surface energy of these nanofillers, strong interactions exist between filler particles, which in turn causes the fillers to form aggregates within the rubber matrix. This agglomeration phenomenon significantly reduces the filler's dispersion in the rubber matrix, greatly affecting the nanofiller's reinforcement efficiency and limiting further improvements in the rubber material's performance.

[0004] Currently, the most common method for improving silica dispersibility is to add a silane coupling agent, such as Si69. While Si69 effectively improves silica dispersibility in rubber, its use also presents some challenges. During the mixing process, rubber compounds containing Si69 often require longer mixing times and higher mixing temperatures. This can lead to premature vulcanization of the rubber matrix and the Si69, hindering subsequent processing. Furthermore, the use of Si69 generates volatile organic gases, which pollute the environment and increase safety risks during production.

[0005] Therefore, we propose a dispersant for rubber and an environmentally friendly rubber prepared therefrom. Summary of the Invention

[0006] The purpose of the present invention is to provide a rubber dispersant and an environmentally friendly rubber prepared therefrom, so as to solve the problems raised in the prior art.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A method for preparing a rubber dispersant comprises the following steps:

[0009] Mix fatty alcohol polyoxyethylene ether, modified polyether amine and deionized water, stir at 60-70°C for 30-50 minutes, add carrier, stir evenly, cool and pelletize to obtain rubber dispersant.

[0010] Furthermore, the rubber dispersant includes the following components by weight: 20-40 parts of fatty alcohol polyoxyethylene ether, 15-30 parts of modified polyether amine, 10-20 parts of carrier, and 20-30 parts of deionized water.

[0011] Furthermore, the preparation method of the modified polyetheramine is as follows:

[0012] Step (1): uniformly mix cystamine, oleic acid chloride, potassium carbonate, potassium iodide and anhydrous toluene, introduce nitrogen gas under ice bath conditions, raise the temperature to 70-80° C., react for 22-24 hours, filter, rotary evaporate and dry to obtain an amino compound;

[0013] Step (2): Under nitrogen protection, magnolol, epichlorohydrin and benzyltriethylammonium chloride are mixed uniformly, reacted at 80-90° C. for 3-5 hours, cooled to 50-55° C., sodium hydroxide solution is added, and the reaction is continued for 2-3 hours. After filtering, washing and drying, epoxidized magnolol is obtained;

[0014] Step (3): under nitrogen protection, the amino compound and anhydrous ethanol are mixed uniformly, and a mixed solution of epoxidized magnolol and anhydrous ethanol is added dropwise in an ice bath, the temperature is raised to 30-40° C., the reaction is carried out for 22-24 hours, and the polyetheramine is obtained after rotary evaporation, precipitation, and drying;

[0015] Step (4): Under nitrogen protection, the polyetheramine and ε-caprolactone are mixed uniformly, the temperature is raised to 120-130° C., stannous octoate is added, the mixture is reacted for 6-8 hours, the mixture is cooled to room temperature, and the modified polyetheramine is obtained after dissolution, precipitation, and drying.

[0016] In the above technical scheme, cystamine and oleic acid chloride are used as raw materials, and a compound containing a carbon-carbon double bond and a primary amino group, i.e., an amino-containing compound, which also contains a disulfide bond, is synthesized by substitution reaction. Then, magnolol, a bio-based compound, is reacted with epichlorohydrin to obtain epoxidized magnolol containing two epoxy groups and a carbon-carbon double bond. A polyetheramine is prepared by a ring-opening addition reaction using the amino-containing compound and epoxidized magnolol. Under the action of a catalyst, the hydroxyl and secondary amine groups in the polyetheramine are then used to undergo a ring-opening reaction with ε-caprolactone to finally obtain a hyperdispersant with a tertiary amino group as an anchoring group and a polyester segment as a solvating segment, i.e., a modified polyetheramine. This hyperdispersant can significantly improve the dispersibility of fillers in rubber systems, enhance the interfacial compatibility between fillers and rubber, and thereby enhance the physical properties of the rubber. In addition, the modified polyetheramine contains double bonds and disulfide bonds, which can undergo a cross-linking reaction with the rubber matrix, thereby enhancing the compatibility of the filler in the polymer matrix.

[0017] Furthermore, in step (1), the amino compound comprises the following components by weight: 12-18 parts of cystamine, 18-27 parts of oleic acid chloride, 25-30 parts of potassium carbonate, 0.8-1.2 parts of potassium iodide, and 80-110 parts of anhydrous toluene.

[0018] Furthermore, in the step (2), the mass ratio of magnolol, epichlorohydrin, benzyltriethylammonium chloride and sodium hydroxide solution is 1:(2-3):(0.05-0.08):(0.5-1.0), and the concentration of the sodium hydroxide solution is 30-40wt%.

[0019] Furthermore, in the step (3), the mass ratio of the amino compound to anhydrous ethanol is 1:(3-5).

[0020] Furthermore, in the step (3), the mass of epoxidized magnolol is 2-3 times the mass of the amino compound, and the mass ratio of epoxidized magnolol to anhydrous ethanol is 1:(2-4).

[0021] Furthermore, in the step (4), the mass ratio of polyetheramine, ε-caprolactone and stannous octoate is 1:(5-8):(0.1-0.3).

[0022] Furthermore, the preparation method of the carrier is as follows:

[0023] Step A: chitosan, acetic acid solution and anhydrous ethanol are mixed evenly, deoxycholic acid and ethylenediamine are added, and the mixture is reacted for 22-24 hours. After filtering and drying, deoxycholic acid-grafted chitosan is obtained;

[0024] Step B: The deoxycholic acid grafted chitosan and the 1-hydroxy-benzotriazole aqueous solution are mixed uniformly, and a mixed solution of N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-acetyl-L-cysteine is added, the pH of the system is adjusted to 4-5, and the reaction is carried out at 40-50° C. in the dark for 2-4 hours. After filtering, washing, dialyzing and drying, the modified chitosan is obtained;

[0025] Step C: ultrasonically dispersing graphene oxide in deionized water to obtain a graphene oxide dispersion, adding modified chitosan and mixing evenly, ultrasonically dispersing for 30-50 minutes, centrifuging, and drying to obtain a carrier.

[0026] In the above technical scheme, a new type of amphiphilic chitosan, namely modified chitosan, was synthesized using deoxycholic acid (DA) as a hydrophobic group and N-acetyl-L-cysteine (NAC) as a hydrophilic group. Typical layered graphene oxide and modified chitosan were combined through simple non-covalent self-assembly to obtain an environmentally friendly polymer / inorganic nanohybrid material, namely a carrier.

[0027] Furthermore, in step A, the mass ratio of chitosan, acetic acid solution, anhydrous ethanol, deoxycholic acid and ethylenediamine is 1: (30-40): (30-40): (1-2): (0.1-0.3), and the concentration of the acetic acid solution is 1-2 wt%.

[0028] Furthermore, in step B, the modified chitosan includes the following components by weight: 5-10 parts of deoxycholic acid grafted chitosan, 250-500 parts of 1-hydroxybenzotriazole aqueous solution, 10-20 parts of N-hydroxysuccinimide, 15-30 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20-40 parts of N-acetyl-L-cysteine.

[0029] Furthermore, the concentration of the 1-hydroxy-benzotriazole aqueous solution is 1-2 wt %.

[0030] Furthermore, in step C, the concentration of the graphene oxide dispersion is 1 mg / mL, and the mass of the modified chitosan is 0.2-1.0 times the mass of the graphene oxide.

[0031] An application of a rubber dispersant comprises the following steps:

[0032] Step S1: mixing styrene-butadiene rubber, butadiene rubber, white carbon black, zinc oxide, antioxidant, rubber dispersant, stearic acid, and protective wax at 120-130° C., draining at 145-155° C., and standing for 22-24 hours to obtain a mixed rubber;

[0033] Step S2: adding sulfur and an accelerator to a section of the mixed rubber, mixing them evenly, standing them for 22-24 hours, and performing a vulcanization treatment to obtain an environmentally friendly rubber.

[0034] Furthermore, the environmentally friendly rubber includes the following components by weight: 100-110 parts of styrene-butadiene rubber, 10-20 parts of butadiene rubber, 50-60 parts of white carbon black, 3-5 parts of zinc oxide, 2-5 parts of rubber dispersant, 1-3 parts of stearic acid, 1-2 parts of protective wax, 2-5 parts of accelerator, 2-6 parts of antioxidant, and 1-3 parts of sulfur.

[0035] Furthermore, the process conditions of the vulcanization treatment are: carried out on a flat vulcanizing machine, the vulcanization temperature is 150-160° C., the pressure is 10-15 MPa, and the time is 8-12 minutes.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. A rubber dispersant and the environmentally friendly rubber prepared therefrom of the present invention utilize the hydroxyl and secondary amine groups in a polyetheramine to undergo a ring-opening reaction with ε-caprolactone, ultimately yielding a hyperdispersant with a tertiary amine group as an anchoring group and a polyester segment as a solvating segment, namely a modified polyetheramine. The hyperdispersant exhibits excellent hydrophilicity and hydrophobicity, can interact with fillers, and can also entangle and connect with rubber molecular chains via the molecular chain at the other end, thereby enhancing the bonding between the filler and the rubber, effectively improving the dispersibility of the filler in the rubber material, and reducing the aggregation of the filler in the rubber matrix, thereby improving the mechanical properties of the rubber. Furthermore, the modified polyetheramine contains double bonds and disulfide bonds, which can undergo a cross-linking reaction with the rubber matrix, thereby improving the compatibility of the filler in the polymer matrix.

[0038] A new amphiphilic chitosan, i.e., modified chitosan, was synthesized using deoxycholic acid (DA) as a hydrophobic group and N-acetyl-L-cysteine (NAC) as a hydrophilic group. Typical layered graphene oxide and bio-inspired modified chitosan were combined through facile non-covalent self-assembly to obtain a polymer / inorganic nanohybrid material, i.e., a carrier. The layered structure of graphene oxide can effectively enhance the tensile strength and thermal stability of rubber, while the hydrophilic part of chitosan helps improve the wettability and dispersion of rubber.

[0039] 2. The rubber dispersant of the present invention and the environmentally friendly rubber prepared therefrom, through the synergistic combination of fatty alcohol polyoxyethylene ether and modified polyetheramine, enhance the dispersant's surface activity, further improving the dispersion of fillers in the rubber matrix and achieving a more uniform distribution of fillers within the composite material, thereby improving the overall performance and stability of the rubber. Uniform mixing of the fatty alcohol polyoxyethylene ether, modified polyetheramine, and carrier forms a highly effective rubber dispersant, significantly improving the dispersibility of fillers in the rubber matrix and reducing filler aggregation, thereby enhancing the rubber's physical properties and processing performance. Furthermore, the uniform mixing enhances the rubber's rheological properties, making it easier to form during processing, ultimately resulting in higher-quality rubber products. DETAILED DESCRIPTION

[0040] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0041] In this example, chitosan: Product No. XL180614, sourced from Xi'an Xinlu Biotechnology Co., Ltd.; graphene oxide: Model DN-20DY, average thickness 1-3 nm, diameter 4-7 μm, number of layers 2-5, sourced from Zhejiang Zhiti Nano Micro New Materials Co., Ltd.; white carbon black: Model HL380, sourced from Hubei Huifu Nanomaterials Co., Ltd.; styrene-butadiene rubber:

[0042] Brand SBR-1502, sourced from Dongguan Xin Synthetic Rubber Co., Ltd.; butadiene rubber: brand BR9000, sourced from Jinhua Bojia Plastic Technology Co., Ltd.; zinc oxide: model NZn-1, sourced from Guangzhou Yanrui Chemical Co., Ltd.; accelerator: accelerator CZ; antioxidant: antioxidant 4020; protective wax: model LY-03, sourced from Guangzhou Liben Rubber Raw Materials Trading Co., Ltd.; sulfur: model S-80, sourced from Shanghai Donghu Industrial Co., Ltd.

[0043] In the following examples and comparative examples, 1 part is equal to 1 g.

[0044] Example 1: A method for preparing a rubber dispersant, comprising the following steps:

[0045] 20 parts of fatty alcohol polyoxyethylene ether, 15 parts of modified polyether amine and 20 parts of deionized water were mixed, stirred at 60°C for 30 minutes, and then 10 parts of carrier were added, stirred evenly, cooled and pelletized to obtain a rubber dispersant;

[0046] The preparation method of modified polyetheramine is as follows:

[0047] Step (1): 12 parts of cystamine, 18 parts of oleic acid chloride, 25 parts of potassium carbonate, 0.8 parts of potassium iodide and 80 parts of anhydrous toluene are mixed uniformly, nitrogen is introduced into the mixture under ice bath conditions, the temperature is raised to 70° C., the reaction is carried out for 22 hours, and the mixture is filtered, rotary evaporated and dried to obtain an amino compound;

[0048] Step (2): Under nitrogen protection, 20 parts of magnolol, 40 parts of epichlorohydrin and benzyltriethylammonium chloride were mixed uniformly, reacted at 80°C for 3 hours, cooled to 50°C, added with 10 parts of 30wt% sodium hydroxide solution, and continued to react for 2 hours. After filtering, washing and drying, epoxidized magnolol was obtained;

[0049] Step (3): Under nitrogen protection, 10 parts of an amino compound and 30 parts of anhydrous ethanol were mixed uniformly, and a mixed solution of 20 parts of epoxidized magnolol and 40 parts of anhydrous ethanol was added dropwise in an ice bath, the temperature was raised to 30° C., and the reaction was carried out for 22 hours. After rotary evaporation, precipitation, and drying, a polyetheramine was obtained;

[0050] Step (4): Under nitrogen protection, 20 parts of polyetheramine and 100 parts of ε-caprolactone were mixed uniformly, the temperature was raised to 120° C., 2 parts of stannous octoate were added, the reaction was carried out for 6 hours, and the mixture was cooled to room temperature. After dissolution, precipitation, and drying, a modified polyetheramine was obtained;

[0051] The preparation method of the carrier is as follows:

[0052] Step A: 5 parts of chitosan, 150 parts of 1 wt% acetic acid solution and 150 parts of anhydrous ethanol were mixed evenly, 5 parts of deoxycholic acid and 0.5 parts of ethylenediamine were added, and the mixture was reacted for 22-24 hours. After filtering and drying, deoxycholic acid-grafted chitosan was obtained;

[0053] Step B: 5 parts of deoxycholic acid grafted chitosan and 250 parts of a 1 wt% 1-hydroxybenzotriazole aqueous solution were uniformly mixed, and a mixed solution of 10 parts of N-hydroxysuccinimide, 15 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 20 parts of N-acetyl-L-cysteine was added. The pH of the system was adjusted to 4, and the reaction was carried out at 40° C. in the dark for 2 hours. After filtering, washing, dialyzing, and drying, the modified chitosan was obtained.

[0054] Step C: ultrasonically dispersing 25 parts of graphene oxide in deionized water to obtain a 1 mg / mL graphene oxide dispersion, adding 5 parts of modified chitosan and mixing evenly, ultrasonically dispersing for 30 minutes, centrifuging, and drying to obtain a carrier;

[0055] An application of a rubber dispersant comprises the following steps:

[0056] Step S1: 100 parts of styrene-butadiene rubber, 10 parts of butadiene rubber, 50 parts of white carbon black, 3 parts of zinc oxide, 2 parts of antioxidant, 2 parts of rubber dispersant, 1 part of stearic acid and 1 part of protective wax are mixed at 120° C., discharged at 145° C., and allowed to stand for 22 hours to obtain a mixed rubber;

[0057] Step S2: adding 1 part of sulfur and 2 parts of accelerator to a section of mixed rubber, mixing evenly, standing for 22 hours, and vulcanizing on a flat vulcanizer at a vulcanization temperature of 150° C., a pressure of 10 MPa, and a time of 8 minutes to obtain an environmentally friendly rubber.

[0058] Example 2: A method for preparing a rubber dispersant, comprising the following steps:

[0059] 30 parts of fatty alcohol polyoxyethylene ether, 25 parts of modified polyether amine and 25 parts of deionized water were mixed, stirred at 65°C for 40 minutes, and then 15 parts of carrier were added, stirred evenly, cooled and pelletized to obtain a rubber dispersant;

[0060] The preparation method of modified polyetheramine is as follows:

[0061] Step (1): 16 parts of cystamine, 24 parts of oleic acid chloride, 26 parts of potassium carbonate, 1 part of potassium iodide and 100 parts of anhydrous toluene are mixed uniformly, nitrogen is introduced into the mixture under ice bath conditions, the temperature is raised to 75° C., the reaction is carried out for 23 hours, and the amino compound is obtained after suction filtration, rotary evaporation and drying;

[0062] Step (2): Under nitrogen protection, 25 parts of magnolol, 62.5 parts of epichlorohydrin and 1.5 parts of benzyltriethylammonium chloride were mixed uniformly, reacted at 85°C for 4 hours, cooled to 52°C, added with 20 parts of 35wt% sodium hydroxide solution, and continued to react for 2.5 hours. After filtering, washing and drying, epoxidized magnolol was obtained;

[0063] Step (3): Under nitrogen protection, 10 parts of an amino compound and 40 parts of anhydrous ethanol were mixed uniformly, and a mixed solution of 25 parts of epoxidized magnolol and 75 parts of anhydrous ethanol was added dropwise in an ice bath, and the mixture was heated to 35° C. and reacted for 23 hours. After rotary evaporation, precipitation, and drying, a polyetheramine was obtained;

[0064] Step (4): Under nitrogen protection, 10 parts of polyetheramine and 60 parts of ε-caprolactone were mixed uniformly, the temperature was raised to 125° C., 2 parts of stannous octoate were added, the mixture was reacted for 7 hours, and the mixture was cooled to room temperature. After dissolution, precipitation, and drying, a modified polyetheramine was obtained;

[0065] The preparation method of the carrier is as follows:

[0066] Step A: 8 parts of chitosan, 280 parts of 1.5 wt% acetic acid solution and 280 parts of anhydrous ethanol were mixed evenly, 12 parts of deoxycholic acid and 2.4 parts of ethylenediamine were added, and the mixture was reacted for 23 hours. After filtering and drying, deoxycholic acid-grafted chitosan was obtained;

[0067] Step B: 8 parts of deoxycholic acid grafted chitosan and 400 parts of a 1.5 wt% 1-hydroxybenzotriazole aqueous solution were mixed uniformly, and a mixed solution of 15 parts of N-hydroxysuccinimide, 25 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 30 parts of N-acetyl-L-cysteine was added. The pH of the system was adjusted to 4.5, and the mixture was reacted at 45° C. in the dark for 3 hours. After filtering, washing, dialyzing, and drying, the modified chitosan was obtained.

[0068] Step C: ultrasonically dispersing 16 parts of graphene oxide in deionized water to obtain a 1 mg / mL graphene oxide dispersion, adding 8 parts of modified chitosan and mixing evenly, ultrasonically dispersing for 40 minutes, centrifuging, and drying to obtain a carrier;

[0069] An application of a rubber dispersant comprises the following steps:

[0070] Step S1: 105 parts of styrene-butadiene rubber, 15 parts of butadiene rubber, 55 parts of white carbon black, 4 parts of zinc oxide, 4 parts of antioxidant, 4 parts of rubber dispersant, 2 parts of stearic acid and 1.5 parts of protective wax are mixed at 125° C., discharged at 140° C., and allowed to stand for 23 hours to obtain a mixed rubber;

[0071] Step S2: adding 2 parts of sulfur and 3 parts of accelerator to a section of mixed rubber, mixing evenly, standing for 23 hours, and vulcanizing on a flat vulcanizer at a vulcanization temperature of 155° C., a pressure of 12 MPa, and a time of 10 minutes to obtain an environmentally friendly rubber.

[0072] Example 3: A method for preparing a rubber dispersant, comprising the following steps:

[0073] 40 parts of fatty alcohol polyoxyethylene ether, 30 parts of modified polyether amine and 30 parts of deionized water were mixed, stirred at 70°C for 50 minutes, and then 20 parts of carrier were added, stirred evenly, cooled and pelletized to obtain a rubber dispersant;

[0074] The preparation method of modified polyetheramine is as follows:

[0075] Step (1): 18 parts of cystamine, 27 parts of oleic acid chloride, 30 parts of potassium carbonate, 1.2 parts of potassium iodide and 110 parts of anhydrous toluene were mixed uniformly, nitrogen was introduced into the mixture under ice bath conditions, the temperature was raised to 80° C., the reaction was carried out for 24 hours, and the mixture was filtered, rotary evaporated and dried to obtain an amino compound;

[0076] Step (2): Under nitrogen protection, 30 parts of magnolol, 90 parts of epichlorohydrin and 2.4 parts of benzyltriethylammonium chloride were mixed uniformly, reacted at 90° C. for 5 hours, cooled to 55° C., 30 parts of 40wt% sodium hydroxide solution were added, and the reaction was continued for 3 hours. After filtering, washing and drying, epoxidized magnolol was obtained;

[0077] Step (3): Under nitrogen protection, 10 parts of an amino compound and 50 parts of anhydrous ethanol were mixed uniformly, and a mixed solution of 30 parts of epoxidized magnolol and 120 parts of anhydrous ethanol was added dropwise in an ice bath, and the mixture was heated to 40° C. and reacted for 24 hours. After rotary evaporation, precipitation, and drying, a polyetheramine was obtained;

[0078] Step (4): Under nitrogen protection, 10 parts of polyetheramine and 80 parts of ε-caprolactone were mixed uniformly, the temperature was raised to 130° C., 3 parts of stannous octoate were added, the mixture was reacted for 8 hours, and the mixture was cooled to room temperature. After dissolution, precipitation, and drying, a modified polyetheramine was obtained;

[0079] The preparation method of the carrier is as follows:

[0080] Step A: 10 parts of chitosan, 400 parts of 2 wt% acetic acid solution and 400 parts of anhydrous ethanol were mixed evenly, 20 parts of deoxycholic acid and 3 parts of ethylenediamine were added, and the mixture was reacted for 24 hours. After filtering and drying, deoxycholic acid-grafted chitosan was obtained;

[0081] Step B: 10 parts of deoxycholic acid grafted chitosan and 500 parts of a 2 wt% 1-hydroxybenzotriazole aqueous solution were mixed uniformly, 20 parts of a mixed solution of N-hydroxysuccinimide, 30 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 40 parts of N-acetyl-L-cysteine were added, the pH of the system was adjusted to 5, and the reaction was carried out at 50° C. in the dark for 4 hours. After filtering, washing, dialyzing, and drying, the modified chitosan was obtained;

[0082] Step C: ultrasonically dispersing 10 parts of graphene oxide in deionized water to obtain a 1 mg / mL graphene oxide dispersion, adding 10 parts of modified chitosan and mixing evenly, ultrasonically dispersing for 50 minutes, centrifuging, and drying to obtain a carrier;

[0083] An application of a rubber dispersant comprises the following steps:

[0084] Step S1: 110 parts of styrene-butadiene rubber, 20 parts of butadiene rubber, 60 parts of white carbon black, 5 parts of zinc oxide, 6 parts of antioxidant, 5 parts of rubber dispersant, 3 parts of stearic acid and 2 parts of protective wax are mixed at 130° C., discharged at 155° C., and allowed to stand for 24 hours to obtain a mixed rubber;

[0085] Step S2: adding 3 parts of sulfur and 5 parts of accelerator to a section of mixed rubber, mixing evenly, standing for 24 hours, and vulcanizing on a flat vulcanizer at a vulcanization temperature of 160° C., a pressure of 15 MPa, and a time of 12 minutes to obtain an environmentally friendly rubber.

[0086] Comparative Example 1: A method for preparing a rubber dispersant, comprising the following process:

[0087] Compared with Example 2, the modified polyetheramine was not added in Comparative Example 1, and the other steps were the same as those in Example 2.

[0088] Comparative Example 2: A method for preparing a rubber dispersant, comprising the following process:

[0089] Compared with Example 2, no carrier was added in Comparative Example 2, and other steps were the same as those in Example 2.

[0090] Comparative Example 3: A method for preparing a rubber dispersant, comprising the following process:

[0091] The preparation method of modified polyetheramine is as follows:

[0092] Step (1): 16 parts of cystamine, 24 parts of oleic acid chloride, 26 parts of potassium carbonate, 1 part of potassium iodide and 100 parts of anhydrous toluene are mixed uniformly, nitrogen is introduced into the mixture under ice bath conditions, the temperature is raised to 75° C., the reaction is carried out for 23 hours, and the amino compound is obtained after suction filtration, rotary evaporation and drying;

[0093] Step (2): Under nitrogen protection, 25 parts of magnolol, 62.5 parts of epichlorohydrin and 1.5 parts of benzyltriethylammonium chloride were mixed uniformly, reacted at 85°C for 4 hours, cooled to 52°C, added with 20 parts of 35wt% sodium hydroxide solution, and continued to react for 2.5 hours. After filtering, washing and drying, epoxidized magnolol was obtained;

[0094] Step (3): Under nitrogen protection, 10 parts of an amino compound and 40 parts of anhydrous ethanol were mixed uniformly, and a mixed solution of 40 parts of epoxidized magnolol and 75 parts of anhydrous ethanol was added dropwise in an ice bath, the temperature was raised to 35° C., and the reaction was carried out for 23 hours. After rotary evaporation, precipitation, and drying, a polyetheramine was obtained;

[0095] Step (4): Under nitrogen protection, 10 parts of polyetheramine and 60 parts of ε-caprolactone were mixed uniformly, the temperature was raised to 125° C., 2 parts of stannous octoate were added, the mixture was reacted for 7 hours, and the mixture was cooled to room temperature. After dissolution, precipitation, and drying, a modified polyetheramine was obtained;

[0096] Compared with Example 2, in step (3) of Comparative Example 3, the mass of epoxidized magnolol is 4 times the mass of the amino-containing compound, and the other steps are the same as in Example 2.

[0097] Experiment: The environmentally friendly rubber obtained in Examples 1-3 and Comparative Examples 1-3 was used to prepare samples, and their properties were tested and the test results were recorded:

[0098] The tensile properties were measured in accordance with GB / T 528-2009. The specimens were made into dumbbell-shaped specimens with a thickness of 2 mm and a width of 6 mm, and the tensile speed was 500 mm / min. The Mooney viscosity was measured in accordance with GB / T 1232.1-2016. The specimens consisted of two circular films with a diameter of 50 mm and a thickness of 6 mm. The test temperature was 100°C, the preheating time was 1 min, and the test time was 4 min. The dispersion of the added silica reinforcing filler in the rubber was measured in accordance with ISO 11345:2006. A rapid assessment method based on visual comparison was used to divide the dispersion into 10 grades. The results were expressed on a numerical scale of 1 to 10, with grade 1 being the worst dispersion and grade 10 being the best dispersion.

[0099] The test results are as follows:

[0100] Tensile strength / MPa ML(1+4)100℃ Dispersion / level Example 1 33.8 25 9 Example 2 35.2 23 9 Example 3 34.7 24 9 Comparative Example 1 25.1 75 3 Comparative Example 2 22.6 56 6 Comparative Example 3 29.5 48 7

[0101] According to the data in the above table, we can clearly draw the following conclusions:

[0102] 1. Compared with Examples 1-3, the tensile strength, Mooney viscosity and dispersity of the products obtained in Comparative Examples 1 and 2 are all reduced, indicating that the addition of modified polyetheramine and carrier to the rubber dispersant prepared by the present invention is beneficial to improving the dispersion of the filler in the rubber matrix, thereby enhancing the overall strength and fluidity of the rubber.

[0103] 2. Compared with Examples 1-3, the tensile strength, Mooney viscosity and dispersity of the product obtained in Comparative Example 3 were decreased, which indicates that when an excess of epoxidized magnolol was added, the molecular weight of the modified polyetheramine was larger and the polymer chain was longer, resulting in a deterioration in the dispersibility and Mooney viscosity of the rubber.

[0104] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A method for preparing a rubber dispersant, characterized in that: The steps include: Mix fatty alcohol polyoxyethylene ether, modified polyether amine and deionized water, stir at 60-70°C for 30-50 minutes, add carrier, stir evenly, cool and pelletize to obtain rubber dispersant.

2. The method for preparing a rubber dispersant according to claim 1, wherein: The rubber dispersant comprises the following components by weight: 20-40 parts of fatty alcohol polyoxyethylene ether, 15-30 parts of modified polyether amine, 10-20 parts of carrier, and 20-30 parts of deionized water.

3. The method for preparing a rubber dispersant according to claim 2, wherein: The preparation method of the modified polyetheramine is as follows: Step (1): uniformly mix cystamine, oleic acid chloride, potassium carbonate, potassium iodide and anhydrous toluene, introduce nitrogen gas under ice bath conditions, raise the temperature to 70-80° C., react for 22-24 hours, filter, rotary evaporate and dry to obtain an amino compound; Step (2): Under nitrogen protection, magnolol, epichlorohydrin and benzyltriethylammonium chloride are mixed uniformly, reacted at 80-90° C. for 3-5 hours, cooled to 50-55° C., sodium hydroxide solution is added, and the reaction is continued for 2-3 hours. After filtering, washing and drying, epoxidized magnolol is obtained; Step (3): under nitrogen protection, the amino compound and anhydrous ethanol are mixed uniformly, and a mixed solution of epoxidized magnolol and anhydrous ethanol is added dropwise in an ice bath, the temperature is raised to 30-40° C., the reaction is carried out for 22-24 hours, and the polyetheramine is obtained after rotary evaporation, precipitation, and drying; Step (4): Under nitrogen protection, the polyetheramine and ε-caprolactone are mixed uniformly, the temperature is raised to 120-130° C., stannous octoate is added, the mixture is reacted for 6-8 hours, the mixture is cooled to room temperature, and the modified polyetheramine is obtained after dissolution, precipitation, and drying.

4. The method for preparing a rubber dispersant according to claim 3, wherein: In the step (1), the amino compound comprises the following components by weight: 12-18 parts of cystamine, 18-27 parts of oleic acid chloride, 25-30 parts of potassium carbonate, 0.8-1.2 parts of potassium iodide, and 80-110 parts of anhydrous toluene.

5. The method for preparing a rubber dispersant according to claim 3, wherein: In the step (3), the mass of epoxidized magnolol is 2-3 times the mass of the amino compound.

6. The method for preparing a rubber dispersant according to claim 2, wherein: The preparation method of the carrier is as follows: Step A: chitosan, acetic acid solution and anhydrous ethanol are mixed evenly, deoxycholic acid and ethylenediamine are added, and the mixture is reacted for 22-24 hours. After filtering and drying, deoxycholic acid-grafted chitosan is obtained; Step B: The deoxycholic acid grafted chitosan and the 1-hydroxy-benzotriazole aqueous solution are mixed uniformly, and a mixed solution of N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-acetyl-L-cysteine is added, the pH of the system is adjusted to 4-5, and the reaction is carried out at 40-50° C. in the dark for 2-4 hours. After filtering, washing, dialyzing and drying, the modified chitosan is obtained; Step C: ultrasonically dispersing graphene oxide in deionized water to obtain a graphene oxide dispersion, adding modified chitosan and mixing evenly, ultrasonically dispersing for 30-50 minutes, centrifuging, and drying to obtain a carrier.

7. The method for preparing a rubber dispersant according to claim 6, wherein: In step C, the concentration of the graphene oxide dispersion is 1 mg / mL, and the mass of the modified chitosan is 0.2-1.0 times the mass of the graphene oxide.

8. A rubber dispersant obtained according to the preparation method according to any one of claims 1 to 7.

9. The use of a rubber dispersant according to claim 8, characterized in that: The following steps are involved: Step S1: mixing styrene-butadiene rubber, butadiene rubber, white carbon black, zinc oxide, antioxidant, rubber dispersant, stearic acid and protective wax at 120-130° C., draining at 145-155° C., and standing for 22-24 hours to obtain a mixed rubber; Step S2: adding sulfur and an accelerator to a section of the mixed rubber, mixing them evenly, standing them for 22-24 hours, and performing a vulcanization treatment to obtain an environmentally friendly rubber.

10. The use of a rubber dispersant according to claim 9, characterized in that: The environmentally friendly rubber includes the following components by weight: 100-110 parts of styrene-butadiene rubber, 10-20 parts of butadiene rubber, 50-60 parts of white carbon black, 3-5 parts of zinc oxide, 2-5 parts of rubber dispersant, 1-3 parts of stearic acid, 1-2 parts of protective wax, 2-5 parts of accelerator, 2-6 parts of antioxidant, and 1-3 parts of sulfur.