Synthesis method and application of triazinyl cyclic boric acid phenyl ester coupling agent
By introducing aminobutyric acid, dodecanoic ring, benzene ring and triazine ring into the boric acid ester coupling agent, the triazine-based cyclic phenyl boric acid ester coupling agent is solved, the problem of poor structural stability of traditional coupling agents is significantly reduced, the oil absorption value of heavy calcium carbonate powder is improved, its dispersion and fluidity are improved, and its application is more widely used.
Patent Information
- Application Number
- CN202510289673.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-12
- Publication Date
- 2025-06-13
AI Technical Summary
Traditional borate coupling agents have poor structural stability and are extremely easy to decompose, resulting in a large oil absorption value of modified heavy calcium carbonate powders, affecting the quality and performance of downstream products.
A triazine-based cyclic phenyl boric acid ester coupling agent is used, and its molecular structure is introduced with aminobutyric acid, dodecanoic ring, benzene ring and triazine ring to enhance the stability of the molecular structure. The coupling agent is prepared by a specific synthetic method, including the use of raw materials such as diethanolamine, boric acid, phenol, cyanochloride and 4-aminobutyric acid, and obtained through multiple reaction and purification processes.
It significantly reduces the oil absorption value of heavy calcium carbonate powder, improves its dispersion and fluidity, enhances the surface modification effect, has a wider range of applications, and has important economic benefits and promotion value.
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Abstract
Description
Technical Field
[0001] The present invention relates to borate coupling agents, and specifically to a synthesis method and application of triazine-based cyclic phenyl borate coupling agents. Background Art
[0002] Heavy calcium carbonate, as a high-quality filler, is widely used in industries such as rubber, plastics, papermaking, coatings, inks, and pharmaceuticals. However, due to the hydrophilic and oleophobic nature of calcium carbonate powder, it is difficult to disperse uniformly in organic media, resulting in a decline in the mechanical properties of materials. Therefore, it must be surface-modified and activated before filling. The central boron atom of borate coupling agents has a unique valence electron configuration and possesses excellent properties that other surface modifiers do not have. The research on its synthesis and properties has received extensive attention. However, traditional borate coupling agents have poor structural stability and are extremely prone to decomposition, resulting in a large oil absorption value of the modified heavy calcium carbonate powder, seriously affecting the quality and performance of downstream products, and thus greatly limiting their applications. Summary of the Invention
[0003] Traditional borate coupling agents have poor structural stability and are extremely prone to decomposition, resulting in a large oil absorption value of the modified heavy calcium carbonate powder, seriously affecting the quality and performance of downstream products, and thus greatly limiting their applications. The triazine-based cyclic phenyl borate coupling agent provided by the present invention introduces aminobutyric acid, a twelve-membered ring, a benzene ring, and a triazine ring into its molecular structure, increasing the steric hindrance and conjugated system, enhancing the molecular structure stability of the borate coupling agent, greatly improving the application effect, and significantly reducing the oil absorption value of heavy calcium carbonate powder.
[0004] One of the purposes of the present invention is to provide a triazine-based cyclic phenyl borate coupling agent, whose structure is as shown in Formula I.
[0005]
[0006] Another purpose of the present invention is to provide a synthesis method of the above triazine-based cyclic phenyl borate coupling agent.
[0007] Specifically, the triazine-based cyclic phenyl borate coupling agent is synthesized by the following method: Take diethanolamine, boric acid, and toluene, stir, heat to reflux for water separation for 2 h; add phenol and reflux for water separation for 8 h, remove the solvent by vacuum distillation, and purify with ethyl acetate to obtain Intermediate 1. Take cyanuric chloride, 4-aminobutyric acid, and deionized water, stir, react at 0 - 5 °C for 2 h; heat to 40 - 45 °C and react for 4 h, filter by suction, remove the solvent by vacuum distillation, add an appropriate amount of ethanol, stir, and filter by suction to obtain Intermediate 2. Take Intermediate 1, Intermediate 2, anhydrous sodium carbonate, and DMF, stir, and reflux for reaction for 8 h, filter by suction, remove the solvent under reduced pressure to obtain the triazine-based cyclic phenyl borate coupling agent.
[0008] The molar ratio of diethanolamine to boric acid is 1:1.
[0009] The molar ratio of boric acid to phenol is 1:1 to 2.
[0010] The molar ratio of cyanuric chloride to 4-aminobutyric acid is 1:2.
[0011] The molar ratio of intermediate 1 to intermediate 2 is 1:1.
[0012] The third object of the present invention is to provide the application of the above triazinyl cyclic borate phenyl ester coupling agent. Specifically, it relates to the application in the surface modification of heavy calcium carbonate powder.
[0013] Specifically, for the application of the triazinyl cyclic borate phenyl ester coupling agent in the surface modification of heavy calcium carbonate powder, the heavy calcium carbonate powder is placed in a modification machine, heated and stirred, and the triazinyl cyclic borate phenyl ester coupling agent is added, then heavy calcium carbonate powder with excellent dispersibility and fluidity and low oil absorption value can be obtained.
[0014] The addition amount of the triazinyl cyclic borate phenyl ester coupling agent is preferably 1.0 - 2.0% of the mass of the heavy calcium carbonate powder.
[0015] The heating temperature is preferably 100°C.
[0016] The stirring time is preferably 30 min.
[0017] The technical effects of the present invention:
[0018] 1. The triazinyl cyclic borate phenyl ester coupling agent provided by the present invention introduces 4-aminobutyric acid, a twelve-membered ring, a benzene ring and a triazine ring into the molecular structure, increases the steric hindrance and conjugated system, enhances the molecular structure stability of the borate coupling agent, and greatly improves the application effect.
[0019] 2. The triazinyl cyclic borate phenyl ester coupling agent provided by the present invention can significantly reduce the oil absorption value of heavy calcium carbonate powder, improve its dispersibility and fluidity, has a wider application field, and has great economic benefits and promotion value.
[0020] Experiments prove that after using the triazinyl cyclic borate phenyl ester coupling agent to modify heavy calcium carbonate powder with 800 meshes and an oil absorption value of 32.01 g / 100 g, its oil absorption value is reduced to 14.02 - 15.29 g / 100 g, and it has excellent dispersibility and fluidity, and the surface modification effect is very significant. Specific Embodiments
[0021] To make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following will be described in detail with specific embodiments.
[0022] Example 1
[0023] (1) Weigh accurately 0.25 mol of diethanolamine and 0.25 mol of boric acid, add them into a three-necked flask, use 50 mL of toluene as the solvent, stir and reflux for water separation for 2 h.
[0024] (2) Weigh accurately 0.375 mol of phenol, add it into the reaction mixture, stir and reflux for water separation for 8 h.
[0025] (3) Cool the reaction mixture to room temperature, remove toluene by vacuum distillation, add ethyl acetate to the residue for purification to obtain intermediate 1, with a yield of 79.84%.
[0026] (4) Weigh accurately 0.1 mol of cyanuric chloride, 0.2 mol of 4-aminobutyric acid, and 250 mL of deionized water, stir evenly, react at 0 - 5 °C for 2 h; raise the temperature to 40 - 45 °C and react for 4 h, filter by suction and remove the solvent by vacuum distillation, add an appropriate amount of ethanol, stir and filter by suction to obtain intermediate 2, with a yield of 77.28%.
[0027] (5) Take 31 mmol of intermediate 1, 31 mmol of intermediate 2, 16 mmol of anhydrous sodium carbonate, and 250 mL of DMF, stir evenly, reflux and react for 8 h, filter by suction and remove the solvent under reduced pressure to obtain an octadecyltriazinyl cyclic borate coupling agent, with a yield of 80.1%.
[0028] (6) For an octadecyltriazinyl cyclic borate coupling agent surface-modified heavy calcium carbonate powder (800 mesh, oil absorption value is 32.01 g / 100 g), the addition amount is 1.0% of the mass of the calcium carbonate powder, heat at 100 °C and modify for 30 min, then a heavy calcium carbonate powder with excellent dispersibility and fluidity and a low oil absorption value can be obtained, and its oil absorption value is 14.02 g / 100 g.
[0029] Example 2
[0030] (1) Weigh accurately 0.25 mol of diethanolamine and 0.25 mol of boric acid, add them into a three-necked flask, use 50 mL of toluene as the solvent, stir and reflux for water separation for 2 h.
[0031] (2) Weigh accurately 0.25 mol of phenol, add it into the reaction mixture, stir and reflux for water separation for 8 h.
[0032] (3) Cool the reaction mixture to room temperature, remove toluene by vacuum distillation, add ethyl acetate to the residue for purification to obtain intermediate 1, with a yield of 76.85%.
[0033] (4) Weigh accurately 0.1 mol of cyanuric chloride, 0.2 mol of 4-aminobutyric acid, and 250 mL of deionized water, stir evenly, react at 0 - 5 °C for 2 h; raise the temperature to 40 - 45 °C and react for 4 h, filter by suction and remove the solvent by vacuum distillation, add an appropriate amount of ethanol, stir and filter by suction to obtain intermediate 2, with a yield of 76%.
[0034] (5) Take 31 mmol of Intermediate 1, 31 mmol of Intermediate 2, 16 mmol of anhydrous sodium carbonate, and 250 mL of DMF. Stir evenly and reflux for 8 h. Filter by suction and remove the solvent under reduced pressure to obtain an octadecyltriazinyl cyclic borate coupling agent with a yield of 78%.
[0035] (6) For an octadecyltriazinyl cyclic borate coupling agent surface-modified heavy calcium carbonate powder (800 mesh, oil absorption value of 32.01 g / 100 g), with an addition amount of 1.5% of the mass of the calcium carbonate powder, heat at 100 °C and modify for 30 min to obtain a heavy calcium carbonate powder with excellent dispersibility and fluidity and a low oil absorption value. Its oil absorption value is 14.62 g / 100 g.
[0036] Example 3
[0037] (1) Accurately weigh 0.25 mol of diethanolamine and 0.25 mol of boric acid and add them to a three-necked flask. Use 50 mL of toluene as the solvent, stir, and reflux for water separation for 2 h.
[0038] (2) Accurately weigh 0.50 mol of phenol and add it to the reaction mixture. Stir and reflux for water separation for 8 h.
[0039] (3) Cool the reaction mixture to room temperature, remove toluene by distillation under reduced pressure, and purify the residue with ethyl acetate to obtain Intermediate 1 with a yield of 80.27%.
[0040] (4) Accurately weigh 0.1 mol of cyanuric chloride, 0.2 mol of 4-aminobutyric acid, and 250 mL of deionized water. Stir evenly and react at 0 - 5 °C for 2 h; raise the temperature to 40 - 45 °C and react for 4 h. Filter by suction and remove the solvent by distillation under reduced pressure. Add an appropriate amount of ethanol, stir, and filter by suction to obtain Intermediate 2 with a yield of 78%.
[0041] (5) Take 31 mmol of Intermediate 1, 31 mmol of Intermediate 2, 16 mmol of anhydrous sodium carbonate, and 250 mL of DMF. Stir evenly and reflux for 8 h. Filter by suction and remove the solvent under reduced pressure to obtain an octadecyltriazinyl cyclic borate coupling agent with a yield of 79%.
[0042] (6) For an octadecyltriazinyl cyclic borate coupling agent surface-modified heavy calcium carbonate powder (800 mesh, oil absorption value of 32.01 g / 100 g), with an addition amount of 2.0% of the mass of the calcium carbonate powder, heat at 100 °C and modify for 30 min to obtain a heavy calcium carbonate powder with excellent dispersibility and fluidity and a low oil absorption value. Its oil absorption value is 15.29 g / 100 g.
[0043] An octadecyl triazinyl cyclic borate coupling agent provided by the present invention can effectively surface-modify and activate heavy calcium carbonate powder, significantly reduce the oil absorption value, improve the dispersibility and fluidity, enhance the practicability, and expand the application fields.
[0044] It should be noted that the above is the preferred embodiment of the present invention. For those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.
Claims
1. A triazine-based cyclic phenyl borate coupling agent, characterized in that: The synthesis method is as follows: diethanolamine, boric acid, and toluene are taken, stirred, heated, refluxed, and water separated; phenol is added, refluxed, and water separated, the solvent is removed by distillation under reduced pressure, and purified with ethyl acetate to obtain intermediate 1. Cyanuric chloride, 4-aminobutyric acid, and deionized water are taken, stirred, and reacted at 0-5°C; the temperature is raised to 40-45°C, filtered, and the solvent is removed by distillation under reduced pressure, and an appropriate amount of ethanol is added, stirred, and filtered to obtain intermediate 2. Intermediate 1, intermediate 2, anhydrous sodium carbonate, and DMF are taken, stirred, refluxed, filtered, and the solvent is removed under reduced pressure to obtain a triazine-based cyclic phenyl borate coupling agent.
2. The triazine-based cyclic phenyl borate coupling agent according to claim 1, characterized in that: The molar ratio of diethanolamine to boric acid is 1:
1.
3. The triazine-based cyclic phenyl borate coupling agent according to claim 1, characterized in that: The molar ratio of the boric acid to the phenol is 1:1-2.
4. The triazine-based cyclic phenyl borate coupling agent according to claim 1, characterized in that: The molar ratio of cyanuric chloride to 4-aminobutyric acid is 1:
2.
5. The triazine-based cyclic phenyl borate coupling agent according to claim 1, characterized in that: The molar ratio of the intermediate 1 to the intermediate 2 is 1:
1.
6. The method for synthesizing a triazine-based cyclic phenyl borate coupling agent according to claim 1, characterized in that: Take diethanolamine, boric acid, and toluene, stir, heat and reflux to separate water for 2 hours; add phenol and reflux to separate water for 8 hours, remove the solvent by vacuum distillation, and purify with ethyl acetate to obtain intermediate 1. Take cyanuric chloride, 4-aminobutyric acid, and deionized water, stir, react at 0-5°C for 2 hours; heat to 40-45°C to react for 4 hours, filter, remove the solvent by vacuum distillation, add appropriate amount of ethanol, stir, and filter to obtain intermediate 2. Take intermediate 1, intermediate 2, anhydrous sodium carbonate, and DMF, stir, reflux for 8 hours, filter, and remove the solvent by vacuum distillation to obtain a triazine-based cyclic boric acid phenyl ester coupling agent.
7. The use of the triazine-based cyclic phenyl borate coupling agent according to claim 1 in surface modification of heavy calcium carbonate powder, characterized in that: The heavy calcium carbonate powder is placed in a modifier, heated, stirred, and a triazine-based cyclic boric acid phenyl ester coupling agent is added to obtain a high-dispersion heavy calcium carbonate powder with a low oil absorption value.
8. The use of the triazine-based cyclic phenyl borate coupling agent according to claim 7 in surface modification of heavy calcium carbonate powder, characterized in that: The addition amount of the triazine-based cyclic phenyl borate coupling agent is preferably 1.0-2.0% of the mass of the heavy calcium carbonate powder.
9. The use of the triazine-based cyclic phenyl borate coupling agent according to claim 7 in the modification of heavy calcium carbonate powder, characterized in that: The heating temperature is preferably 100° C.; the stirring time is preferably 30 min.