Preparation method of water environment-friendly polymeric cobalt salt of organic acid

Abstract

The application discloses a water environment-friendly polymeric organic acid cobalt salt preparation method, and the preparation method comprises the following steps of S1, raw material preparation; S2, condensation reaction, adding an oleic acid raw material and slowly dropping an organic acid catalyst; S3, purification; S4, salt formation reaction; S5, antioxidation; S6, granulation and drying; and S7, screening and packaging. Through the process design of using polymeric organic acid as a cobalt ligand, the polymeric organic acid replaces stearic acid and naphthenic acid, has a long-chain high-molecular structure, can form a stable multi-point coordination network with cobalt ions through multiple carboxyl groups, namely a lock cobalt effect, enhances the binding firmness of cobalt ions in the ligand, makes it more difficult to dissociate and dissolve in a water environment, and the prepared polymeric organic acid cobalt salt not only retains the adhesion promotion function of rubber, but also efficiently promotes vulcanization in the rubber vulcanization process due to the special polymeric organic acid structure, and realizes the integration of the two key functions of vulcanization promotion and adhesion promotion.

Description

Technical Field

[0001] This invention relates to the field of preparation technology of polymeric organic acid cobalt salts, and in particular to a water-friendly method for preparing polymeric organic acid cobalt salts. Background Technology

[0002] Cobalt salt rubber additives, especially cobalt salt adhesion promoters, are indispensable key raw materials in the rubber industry, widely used in the bonding systems of steel cord, fiber skeleton materials, and rubber. During rubber vulcanization, cobalt ions catalyze the reaction between rubber molecules and active groups on the surface of the skeleton material, forming strong chemical bonds. This significantly improves the adhesive strength, heat resistance, and durability of the composite material, making it crucial for the manufacture of high-performance rubber products such as tires, hoses, and conveyor belts.

[0003] Currently, most mainstream cobalt salt adhesive accelerators on the market use small-molecule organic acids such as stearic acid and naphthenic acid as ligands for cobalt ions. Although these traditional products have a certain adhesive promoting effect, the coordination bond formed between the small-molecule organic acids and cobalt ions is relatively weak in long-term use. In humid and water-immersed environments, cobalt ions are prone to dissociate from the ligands and dissolve. Since cobalt ions are heavy metals, their dissolution may pose a potential risk to the ecological environment. At the same time, traditional cobalt salts are difficult to balance with vulcanization promotion efficiency. Traditional cobalt salts are mainly used as adhesive accelerators, and their direct promoting effect on rubber vulcanization is limited. To improve vulcanization efficiency, other types of vulcanization accelerators usually need to be added to the rubber formulation, which not only increases the complexity, cost and uncontrollable factors of the formulation, but may also interfere with the stability of the adhesive system. In view of this, this solution proposes a water-friendly method for preparing cobalt salts from polymeric organic acids to solve the above problems. Summary of the Invention

[0004] The purpose of this invention is to provide a water-friendly method for preparing cobalt salts of polymeric organic acids, in order to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing a water-friendly polymeric organic acid cobalt salt, the preparation method comprising the following steps:

[0006] S1, Raw material preparation, preparation of oleic acid raw material, organic acid catalyst, cobalt source, blending agent and auxiliary agent, the blending agent and auxiliary agent are stearic acid, mixed solvent and phosphite antioxidant; S2, condensation reaction: the oleic acid raw material is added to the reactor and preheated to 80-90°C. The organic acid catalyst is slowly added dropwise to produce polymerized organic acid. S3, Purification: Add deionized water to the polymeric organic acid for washing, and allow it to stand for separation. After separation, discard the aqueous phase and retain the oil phase. Repeat the operation until the pH of the washing solution reaches 6.5-7.5. Dehydrate the obtained oil phase to obtain polymeric organic acid with a purity ≥98%. S4, Salt formation reaction: The purified polymeric organic acid is dissolved in the mixed solvent, and the cobalt source is added to induce the reaction. After the induction reaction, the stearic acid is added to allow the polymeric organic acid to undergo a coordination salt formation reaction with the cobalt source. S5, Antioxidant: The phosphite antioxidant is added to the salt-forming reaction system and stirred and dispersed to obtain a high-quality polymeric organic acid cobalt salt; S6, Granulation and Drying: The refined polymeric organic cobalt salt is extruded and granulated to obtain cylindrical particles, and the cylindrical particles are dried to a moisture content of ≤0.5%; S7, sieving and packaging: The dried cylindrical particles are sieved, and qualified cylindrical particles with a particle size of 1-3mm are sealed and packaged.

[0007] Preferably, the oleic acid raw material is selected from unsaturated fatty acids and dimer oleic acid, the organic acid catalyst is selected from formic acid or acetic acid, the cobalt source is selected from cobalt hydroxide, and the cobalt content of cobalt hydroxide is ≥60%.

[0008] Preferably, the stirring speed of the reactor in the condensation reaction is adjusted to 200-300 rpm, the stirring state is maintained, and the temperature inside the reactor is raised to 80-90℃, and the reactor is kept at this temperature for 15-20 minutes for preheating.

[0009] Preferably, the dropping rate of the organic acid catalyst is controlled at 1-2 ml / min. During the dropping process, the stirring device is kept running continuously. After the dropping is completed, the stirring state of the reaction vessel is maintained, and the temperature inside the reaction vessel is raised to 120-140℃. After reaching the set temperature, the reaction is kept at this temperature for 3-5 hours.

[0010] Preferably, the amount of deionized water added is 10% of the total mass of the condensation reaction system. During the feeding process, the reactor is continuously stirred at a speed of 200-300 rpm for a duration of 15-20 minutes.

[0011] Preferably, during the salt formation reaction, the rotation speed of the reactor is adjusted to 300-500 rpm, the temperature inside the reactor is adjusted to 50-60℃, and the mixture is stirred for 30 minutes at this temperature.

[0012] Preferably, the cobalt source is added at a rate of 5-10 ml / min. After the cobalt source is added, the stirring speed of the reactor is maintained at 300-500 rpm and stirring is continued for 30-40 min to induce the reaction.

[0013] Preferably, the amount of stearic acid powder is controlled to be 10%-20% of the mass of the cobalt source. After adding it, stir for 10-15 minutes. After stirring evenly, raise the reaction temperature to 70-85℃. After reaching the set temperature, keep the temperature constant for 2-4 hours to carry out the salt formation reaction.

[0014] Preferably, after the salt formation reaction, the reaction vessel is continuously stirred, and the temperature of the reaction system is reduced to 40-50°C, with the cooling rate controlled at 5-8°C / h.

[0015] Preferably, during the addition of the phosphite antioxidant, the reactor is kept stirred at a speed of 300-500 rpm, and stirring continues for 10-15 minutes after the phosphite antioxidant is added.

[0016] The technical effects and advantages of this invention are as follows: This invention utilizes a process design that uses polymeric organic acids as cobalt ligands to replace stearic acid and naphthenic acid. These polymeric organic acids have a long-chain polymer structure and can form a stable multi-point coordination network with cobalt ions through multiple carboxyl groups, i.e., a cobalt-locking effect. This enhances the binding strength of cobalt ions in the ligand, making them more difficult to dissociate and dissolve in an aqueous environment. Furthermore, the prepared polymeric organic acid cobalt salt not only retains the adhesive-promoting function of rubber, but its special polymeric organic acid structure can also efficiently promote vulcanization during the rubber vulcanization process, thus integrating the two key functions of vulcanization promotion and adhesive promotion. Attached Figure Description

[0017] Figure 1 This is a flowchart illustrating the operational implementation of the preparation method of the present invention. Detailed Implementation

[0018] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] This invention provides, for example Figure 1 The method for preparing a water-friendly polymeric organic acid cobalt salt, as shown, includes the following steps: S1, Raw material preparation, preparation of oleic acid raw material, organic acid catalyst, cobalt source, blending agent and auxiliary agent, the blending agent and auxiliary agent are stearic acid, mixed solvent and phosphite antioxidant; The oleic acid raw materials are unsaturated fatty acids and dimer oleic acid, the organic acid catalyst is formic acid or acetic acid, and the cobalt source is cobalt hydroxide with a cobalt content of ≥60%. It should be noted that the preparation and pretreatment of oleic acid raw materials, organic acid catalysts, cobalt sources, and conditioning agents and additives are carried out. The oleic acid raw materials are selected from unsaturated fatty acids and dimer oleic acid, with the purity of industrial organic oleic acid ≥98% and dimer oleic acid ≥95%. The unsaturated fatty acids and dimer oleic acid are weighed and mixed according to a mass ratio of 3:1-5:1 and placed in a pretreatment tank. The temperature control and stirring devices of the pretreatment tank are activated to slowly raise the temperature inside the tank to 60-70℃ while stirring for 30 minutes to remove trace amounts of moisture from the unsaturated fatty acids and dimer oleic acid, ensuring that the water content in the unsaturated fatty acids and dimer oleic acid is controlled to ≤0.3%. Simultaneously, the unsaturated fatty acids and dimer oleic acid are thoroughly and uniformly mixed. After pretreatment, the unsaturated fatty acids... The mixed raw materials of fatty acids and dimer oleic acid are set aside to stand. If the mixed raw materials of unsaturated fatty acids and dimer oleic acid contain mechanical impurities, they need to be filtered through a 200-mesh sieve to avoid affecting the uniformity of the subsequent condensation reaction. An organic acid catalyst is used to catalyze the condensation reaction of oleic acid raw materials. To meet the core requirement of water-friendly environment, low-toxicity and easily degradable formic acid or acetic acid are selected as the organic acid catalyst. The purity of formic acid or acetic acid is ≥99%. Formic acid or acetic acid is placed in a clean sealed container and left to stand at room temperature for 24 hours to remove the small amount of volatile impurities contained therein through natural evaporation, ensuring that the purity of the organic acid catalyst meets the reaction requirements. After standing, the concentration is calibrated using a precision meter to ensure accurate control of the catalyst amount. The amount of organic acid catalyst used is 0.5%-2% of the total mass of oleic acid raw materials.0%; Cobalt source is cobalt hydroxide with a cobalt content ≥60%. Industrial-grade cobalt hydroxide is fed into an ultrafine pulverizer for pulverization. After pulverization, ultrafine powder with a particle size D50 < 5μm is screened out using precision sieving equipment. Ultrafine powder can increase the contact area with polymeric organic acids and improve the efficiency of subsequent salt formation reactions. The qualified ultrafine powder is placed in a special dispersion tank, and a small amount of deionized water and dispersant are added. The dispersant used is low-toxicity and easily degradable polyethylene glycol 400, which meets environmental protection requirements. A high-speed stirring device is started, and the stirring time is controlled at 15-20 minutes to prepare a cobalt hydroxide suspension with a solid content of 30%-40% to prevent cobalt source agglomeration in subsequent salt formation reactions and improve reaction efficiency. Stearic acid, mixed solvents, and phosphite antioxidants are selected as conditioning agents and additives. Stearic acid is used as a conditioning agent with a purity ≥98%. Stearic acid is placed in Stearic acid is pulverized to 80-100 mesh using a specialized pulverizer. Powdered stearic acid increases the contact area with the reaction system, facilitating rapid dissolution and uniform dispersion during subsequent salt formation reactions. This better allows it to regulate the product's melting point, dispersibility, and rubber compatibility. A mixed solvent is used to dissolve the polymerized organic acid and support the smooth progress of each reaction step. The mixed solvent is prepared by mixing deionized water and ethanol at a volume ratio of 7:3-8:2. After preparation, it is stirred thoroughly beforehand to ensure the stability of the solvent system and prevent stratification or precipitation, which would affect the reaction effect. Phosphite-based antioxidants are selected to prevent the oxidation and deterioration of cobalt ions in the product. They are weighed at 0.1%-0.3% of the total mass of the antioxidant raw materials and immediately placed in a sealed container for later use. Contact with air is strictly avoided to prevent the antioxidant from oxidizing and becoming ineffective, ensuring that subsequent antioxidant treatment achieves the expected results. After all raw materials and additives have undergone pretreatment, they should be placed sequentially into their respective dedicated raw material storage tanks according to the required proportions for subsequent reactions, and clearly labeled. Pretreated raw materials must be used within 24 hours to prevent deterioration and ensure optimal reaction results.

[0020] S2, condensation reaction: the oleic acid raw material is added to the reactor and preheated to 80-90°C. The organic acid catalyst is slowly added dropwise to produce polymerized organic acid. Adjust the stirring speed of the reactor in the condensation reaction to 200-300 rpm, maintain stirring, and raise the temperature inside the reactor to 80-90℃, and keep it at this temperature for 15-20 minutes for preheating. The dropping rate of the organic acid catalyst is controlled at 1-2 ml / min. During the dropping process, the stirring device is kept running continuously. After the dropping is completed, the stirring state of the reaction vessel is maintained, and the temperature inside the reaction vessel is raised to 120-140℃. After reaching the set temperature, the reaction is kept at the temperature for 3-5 hours. It should be noted that the pretreated oleic acid and dimerized oleic acid mixture is added to a reactor equipped with a stirrer, reflux condenser, temperature control, and dropping funnel. The stirrer is then started and adjusted to 200-300 rpm, maintaining a uniform stirring speed to ensure even distribution of the raw materials within the reaction system. The temperature control is then activated, and the reactor temperature is slowly raised to 80-90°C. This temperature is maintained for 15-20 minutes to ensure the raw materials are fully melted and uniformly mixed, eliminating local concentration differences and laying the foundation for the condensation reaction. After preheating, the dropping funnel is opened, and the pretreated organic acid catalyst is slowly added dropwise to the reactor at a rate of 1-2 ml / min. During the addition process, the stirrer is kept running continuously to ensure uniform dispersion of the organic acid catalyst in the reaction system, preventing excessively high local catalyst concentrations that could lead to side reactions. After the addition is complete, the dropping funnel is closed, but stirring is continued. Simultaneously, the reaction temperature is slowly raised to 120-140℃ using a temperature control device. After reaching the set temperature, the reaction is maintained at this temperature for 3-5 hours to carry out the condensation reaction. During the reaction, oleic acid and dimer oleic acid undergo intermolecular condensation polymerization under the action of an organic acid catalyst, gradually forming high molecular weight polymeric organic acids. A small amount of water is generated during the reaction. The generated water is condensed and discharged through a reflux condenser to prevent water accumulation in the reaction system and interference with the forward condensation polymerization reaction. The viscosity of the system is sampled every half hour during the reaction. When the viscosity of the system reaches 200-300 mPa·s at 25℃, and the conversion rate of polymeric organic acids is ≥95% as detected by high performance liquid chromatography, the condensation reaction is considered to have reached its endpoint. After the condensation reaction is completed, the stirring device is kept running to slowly cool the condensation reaction system to 60-70℃ at a cooling rate of 5-10℃ / h to avoid the degradation of polymeric organic acid chains caused by a sudden drop in temperature, which would affect the subsequent cobalt-locking effect. S3, Purification: Add deionized water to the polymeric organic acid for washing, and allow it to stand for separation. After separation, discard the aqueous phase and retain the oil phase. Repeat the operation until the pH of the washing solution reaches 6.5-7.5. Dehydrate the obtained oil phase to obtain polymeric organic acid with a purity ≥98%. The amount of deionized water added is 10% of the total mass of the condensation reaction system. During the addition process, the reactor is continuously stirred at a speed of 200-300 rpm for 15-20 minutes. It should be noted that, in the condensation reaction system cooled to 60-70℃, deionized water should be slowly added for washing. The deionized water must be pre-purified to ensure it is free of impurities and heavy metal ions. The amount of water added should be 10% of the total mass of the current reaction system. During the addition process, the stirring device should be kept running continuously at a speed of 200-300 rpm for 15-20 minutes. During stirring, unreacted small-molecule organic acid catalysts and trace soluble impurities will fully dissolve in the deionized water, forming an aqueous impurity layer. The polymerized organic acid, due to its strong hydrophobicity, will float on top of the aqueous phase, forming an oil-phase crude polymerized organic acid. This method achieves preliminary separation of impurities from the target product. After stirring, the system should be allowed to stand for 20-30 minutes to separate into layers. During this standing period, the ambient temperature must be kept stable to avoid temperature fluctuations that could cause stratification. If the effect is unsatisfactory, the system will naturally separate into two layers due to the density difference between the polymeric organic acid and the impurity solution. The lower layer is an aqueous washing liquid containing small molecule organic acids and trace impurities, and the upper layer is an oil phase of crude polymeric organic acid. After the separation is complete, slowly open the drain valve at the bottom of the reactor to slowly discharge the lower washing liquid containing impurities and discard it, retaining the upper crude polymeric organic acid. To ensure complete removal of unreacted organic acid catalyst, the above washing, settling, separation, and discarding operations need to be repeated 2-3 times. The amount of water added, stirring time, and settling time should be kept consistent each time. After each washing, take a sample to test the pH value of the washing liquid until the pH value of the washing liquid reaches 6.5-7.5. At this point, it can be determined that the unreacted small molecule organic acid catalyst in the system has been completely removed. If trace mechanical impurities still remain in the crude polymeric organic acid after multiple washings, they can be further purified by filtration through a 150-mesh sieve. After filtration and purification, the polymeric organic acid is placed in a vacuum decompression apparatus for dehydration. During the dehydration process, the temperature of the vacuum decompression apparatus is 60-70℃ and the vacuum degree is 0.07-0.08MPa. The dehydration time is 1-2 hours to remove the residual water from the washing process and obtain polymeric organic acid with a purity ≥98%. After cooling to room temperature, it is ready for use. The purified polymeric organic acid must be sealed and stored to prevent moisture absorption. S4, Salt formation reaction: The purified polymeric organic acid is dissolved in the mixed solvent, and a cobalt source is added to induce the reaction. After the induction reaction, the stearic acid is added to allow the polymeric organic acid to undergo a coordination salt formation reaction with the cobalt source. During the salt formation reaction, adjust the speed of the reactor to 300-500 rpm and adjust the temperature inside the reactor to 50-60℃. Stir at this temperature for 30 minutes. The cobalt source is added at a rate of 5-10 ml / min. After the cobalt source is added, the stirring speed of the reactor is kept at 300-500 rpm and stirred continuously for 30-40 min to induce the reaction. The amount of stearic acid powder is controlled to be 10%-20% of the mass of cobalt source. After adding it, stir for 10-15 minutes. After stirring evenly, raise the reaction temperature to 70-85℃. After reaching the set temperature, keep the temperature constant for 2-4 hours to carry out the salt formation reaction. It should be noted that the purified polymeric organic acid is slowly added to a reactor equipped with a stirrer, temperature control, and reflux device. Then, the prepared mixed solvent and dispersant are added, with the dispersant amounting to 1%-3% of the total raw material mass. The stirrer is started, and the reactor speed is adjusted to 300-500 rpm. Simultaneously, the temperature control device is turned on, and the temperature inside the reactor is slowly adjusted to 50-60℃. Stirring is performed at this temperature for 30 minutes to ensure the polymeric organic acid is fully dissolved in the mixed solvent, forming a uniform and transparent solution. After the reaction solution is prepared, the pretreated cobalt hydroxide suspension is slowly added to the reactor using a dropping funnel at a rate of 5-10 ml / min. During the addition process, the stirrer is kept running at high speed to ensure that the cobalt hydroxide suspension is quickly and uniformly dispersed in the reaction system, allowing each cobalt ion to fully contact the carboxyl groups of the polymeric organic acid. After the cobalt hydroxide suspension is added, the stirring speed is maintained at 300-500 rpm for 30-40 minutes to allow the carboxyl groups on the polymeric organic acid molecular chains to react with the cobalt hydroxide. In cobalt hydroxide, cobalt ions initially contact and undergo weak coordination, initiating the induction process of the coordination salt formation reaction and laying the groundwork for the subsequent salt formation reaction. During stirring, the system state is monitored in real time to ensure no significant agglomeration occurs. After the induction reaction is complete, pretreated stearic acid powder is added to the reaction system. The amount of stearic acid is controlled to be 10%-20% of the mass of the cobalt source. After addition, stirring continues for 10-15 minutes to ensure the stearic acid powder is fully dissolved and uniformly dispersed in the reaction system. After uniform stirring, the reaction is controlled by a temperature control device. The temperature should be slowly raised to 70-85℃. After reaching the set temperature, maintain the temperature for 2-4 hours to carry out the salt formation reaction. During the salt formation reaction, the carboxyl groups on the polymeric organic acid molecular chain undergo a stable coordination salt formation reaction with cobalt ions, gradually forming a stable cobalt-polymer complex structure, which exerts a subsequent cobalt-locking effect and effectively reduces the dissolution rate of cobalt ions in the water environment. At the same time, stearic acid is uniformly dispersed in the reaction system, playing a regulatory role, which can optimize the melting point, dispersibility and compatibility with rubber of the product, ensuring that the product can be adapted to subsequent rubber processing scenarios. A small amount of water will be generated during the reaction, which will be condensed and discharged through a reflux device to prevent water accumulation in the system and interference with the forward progress of the coordination salt formation reaction. The system state and performance will be sampled and tested every hour during the reaction, with a focus on observing the appearance of the system and the presence of solid precipitates. At the same time, KSCN reagent will be used to test for free cobalt ions, and high performance liquid chromatography will be used to detect the cobalt conversion rate. When the system in the reactor is a uniform blue-purple viscous liquid with no obvious solid precipitates, no red complexes are formed by KSCN reagent test, and the cobalt conversion rate is ≥96%, the salt formation reaction is judged to have reached the endpoint. At this time, heating is stopped, and the stirring device is kept running to maintain the uniform state of the salt formation reaction system. S5, antioxidant: The phosphite antioxidant is added to the salt-forming reaction system and stirred and dispersed to obtain a high-quality polymeric organic acid cobalt salt; After the salt formation reaction, the reaction vessel is continuously stirred, and the temperature of the reaction system is reduced to 40-50℃, with the cooling rate controlled at 5-8℃ / h. During the addition of phosphite antioxidants, the reaction vessel is kept stirred at a speed of 300-500 rpm. After the phosphite antioxidants are added, stirring is continued for 10-15 minutes. It should be noted that after the salt formation reaction reaches its endpoint and heating is stopped, the stirring device in the reactor should be kept running continuously to maintain the uniformity of the system. The cooling function of the temperature control device should be turned on to slowly reduce the temperature of the reaction system to 40-50℃, with the cooling rate controlled at 5-8℃ / h. This avoids the high temperature from damaging the activity of the antioxidant and ensures that the antioxidant can play its full role. At the same time, it can also prevent the viscosity of the system from rising sharply due to low temperature, which would affect the uniform dispersion of the antioxidant. After the temperature drops to the set range and stabilizes, phosphite antioxidants should be slowly added, with the amount added being 0.5% of the total mass of the raw materials. Add 1%-0.3%, keeping the stirring device running continuously at a speed of 300-500 rpm during the process. This ensures the antioxidant is quickly and evenly dispersed in the system, preventing localized high or low concentrations that could affect its antioxidant effect. The antioxidant forms a stable antioxidant system with cobalt ions. After the antioxidant is added, continue stirring at the same speed for 10-15 minutes to allow the antioxidant to fully combine with the cobalt ions in the system, forming a stable antioxidant complex system. This effectively prevents cobalt ions from being oxidized to high-valence cobalt, avoiding the formation of... The product exhibits discoloration and deterioration, yet it protects the polymeric organic acid chains from oxidative degradation, maintaining their structural stability and ensuring the cobalt-locking effect remains unaffected. During stirring, the system's state is monitored in real-time to ensure no antioxidant agglomeration or undissolved particles remain. If a small amount of undissolved antioxidant remains, the stirring time can be extended by 3-5 minutes until completely dissolved. After the antioxidant treatment is complete, samples are taken to test the product's color and state. If slight oxidative discoloration persists, it indicates insufficient antioxidant dosage; a small amount of antioxidant can be added, not exceeding 0.1% of the total raw material mass. After adding the product, continue stirring for 5-10 minutes until the product color returns to a uniform blue-purple, without any impurities or sediment. This yields a high-purity, high-stability premium polymeric organic acid cobalt salt. By using polymeric organic acid as a cobalt ligand, the binding strength of cobalt ions in the ligand is enhanced, making it more difficult for them to dissociate and dissolve in an aqueous environment. Furthermore, the prepared polymeric organic acid cobalt salt not only retains the adhesive-promoting function of rubber, but its special polymeric organic acid structure can also efficiently promote vulcanization during the rubber vulcanization process, thus achieving the integration of two key functions: vulcanization promotion and adhesive promotion. S6, Granulation and Drying: The high-quality polymeric organic cobalt salt is extruded and granulated to obtain cylindrical particles, and the cylindrical particles are dried to a moisture content of ≤0.5%; It should be noted that the uniformly stirred high-quality polymerized organic acid cobalt salt is slowly fed into an extrusion granulator, the pore diameter of the granulator is adjusted to 1-3mm, the granulation temperature is controlled at 40-50°C, the extrusion rotation speed is adjusted to 50-80r / min, and uniform cylindrical particles are obtained through extrusion molding; during granulation, the particle morphology shall be observed in real time. If caking or adhesion occurs, the granulation temperature may be appropriately lowered by 2-3°C each time until the condition returns to normal, and a small amount of dispersant is added at the same time. The additional amount of the dispersant shall not exceed 0.5% of the total mass of raw materials. After adding the dispersant, the particle morphology shall be continuously observed until uniform, caking-free and adhesion-free cylindrical particles are formed, so as to prevent excessive dispersant from affecting product performance; the granulated particles are sent into a continuous vacuum drying oven, the drying temperature is slowly increased to 60-70°C, the vacuum degree is adjusted to 0.08-0.09MPa, and the drying time is set to 2-3h. To prevent the product from being oxidized due to contact with oxygen in the air during drying, inert nitrogen is continuously fed into the drying oven during the drying process, and the nitrogen flow rate is controlled at 5-10L / min, so as to ensure that nitrogen can fully fill the inside of the drying oven, discharge residual air, provide an oxygen-free drying environment for the product, and avoid oxidative discoloration and performance degradation of the product; during the drying process, samples are taken regularly to detect the water content of the product, and samples are taken once every 30 minutes. When the water content is ≤ 0.5%, the drying is judged as qualified; after drying, the dried particles are taken out and placed in a clean and dry cooling container to be naturally cooled to room temperature. During the cooling process, the particles are prevented from contacting moist air, so as to prevent high-temperature particles from absorbing moisture and causing the water content to rise again.

[0021] S7, sieving and packaging: sieving the dried cylindrical particles, and hermetically packaging the qualified cylindrical particles with a particle size of 1-3mm; It should be noted that the dried particles cooled to room temperature are fed into a vibrating sieving machine, a sieve with a pore size of 1-3mm is selected, the vibrating sieving machine is turned on, the vibration frequency is adjusted to 200-300 times / min, and the sieving time is 10-15min, so as to remove fine particles and caked particles with unqualified sizes, and screen out uniform cylindrical particles with a particle size of 1-3mm. Unqualified particles can be re-crushed and granulated to improve raw material utilization; the sieving-qualified particles are packaged in food-grade sealed packaging bags or sealed barrels, the weight of each bag or each barrel is controlled at 25kg or 50kg, and the product is prevented from contacting air and moisture during the packaging process; the packaged product is stored in a cool, dry and ventilated warehouse, away from fire sources and oxidants, and direct sunlight and humid environment are avoided. The storage temperature is controlled at 5-30°C, and the sealing performance of the package is checked regularly during storage to prevent the product from moisture absorption and oxidative deterioration.

[0022] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a water-friendly polymeric organic acid cobalt salt, characterized in that, The preparation method includes the following steps: S1, Raw material preparation, preparation of oleic acid raw material, organic acid catalyst, cobalt source, blending agent and auxiliary agent, the blending agent and auxiliary agent are stearic acid, mixed solvent and phosphite antioxidant; S2, condensation reaction: the oleic acid raw material is added to the reactor and preheated to 80-90°C. The organic acid catalyst is slowly added dropwise to produce polymerized organic acid. S3, Purification: Add deionized water to the polymeric organic acid for washing, and allow it to stand for separation. After separation, discard the aqueous phase and retain the oil phase. Repeat the operation until the pH of the washing solution reaches 6.5-7.

5. Dehydrate the obtained oil phase to obtain polymeric organic acid with a purity ≥98%. S4, Salt formation reaction: The purified polymeric organic acid is dissolved in the mixed solvent, and the cobalt source is added to induce the reaction. After the induction reaction, the stearic acid is added to allow the polymeric organic acid to undergo a coordination salt formation reaction with the cobalt source. S5, Antioxidant: The phosphite antioxidant is added to the salt-forming reaction system and stirred and dispersed to obtain a high-quality polymeric organic acid cobalt salt; S6, Granulation and Drying: The refined polymeric organic cobalt salt is extruded and granulated to obtain cylindrical particles, and the cylindrical particles are dried to a moisture content of ≤0.5%; S7, sieving and packaging: The dried cylindrical particles are sieved, and qualified cylindrical particles with a particle size of 1-3mm are sealed and packaged.

2. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, The oleic acid raw material is selected from unsaturated fatty acids and dimer oleic acid, the organic acid catalyst is selected from formic acid or acetic acid, the cobalt source is selected from cobalt hydroxide, and the cobalt content of cobalt hydroxide is ≥60%.

3. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, Adjust the stirring speed of the reactor in the condensation reaction to 200-300 rpm, maintain stirring, and raise the temperature inside the reactor to 80-90℃, and keep it at this temperature for 15-20 minutes.

4. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 3, characterized in that, The dropping rate of the organic acid catalyst is controlled at 1-2 ml / min. During the dropping process, the stirring device is kept running continuously. After the dropping is completed, the stirring state of the reaction vessel is maintained, and the temperature inside the reaction vessel is raised to 120-140℃. After reaching the set temperature, the reaction is kept at this temperature for 3-5 hours.

5. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, The amount of deionized water added is 10% of the total mass of the condensation reaction system. During the addition process, the reactor is continuously stirred at a speed of 200-300 rpm for 15-20 minutes.

6. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, During the salt formation reaction, the speed of the reactor is adjusted to 300-500 rpm, the temperature inside the reactor is adjusted to 50-60℃, and the mixture is stirred for 30 minutes at this temperature.

7. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, The cobalt source is added at a rate of 5-10 ml / min. After the cobalt source is added, the stirring speed of the reactor is maintained at 300-500 rpm and stirring is continued for 30-40 min to induce the reaction.

8. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, The amount of stearic acid powder is controlled to be 10%-20% of the mass of the cobalt source. After adding it, stir for 10-15 minutes. After stirring evenly, raise the reaction temperature to 70-85℃. After reaching the set temperature, keep the temperature constant for 2-4 hours to carry out the salt formation reaction.

9. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, After the salt formation reaction, the reaction vessel is continuously stirred, and the temperature of the reaction system is reduced to 40-50℃, with the cooling rate controlled at 5-8℃ / h.

10. The method for preparing a water-friendly polymeric organic acid cobalt salt according to claim 1, characterized in that, During the addition of the phosphite antioxidant, the reactor is kept stirred at a speed of 300-500 rpm. After the phosphite antioxidant is added, stirring is continued for 10-15 minutes.

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