Synthesis method and application of a tricyclic borate coupling agent

Abstract

The application discloses a tricyclic borate coupling agent, which is synthesized by the following method: taking boric acid, diethanolamine and toluene, heating to reflux and water separation for 2 hours; adding phenol to reflux and water separation for 8 hours; removing toluene by vacuum distillation, purifying by ethyl acetate to obtain a bicyclic borate phenyl ester. Taking cyanuric chloride, tetradecylamine and anhydrous THF, reacting at 0 DEG C for 2 hours, continuing to react at 35 DEG C for 4 hours; filtering, removing THF by vacuum distillation, purifying by ethanol to obtain a double long-chain amino triazine compound. Taking the bicyclic borate phenyl ester, the double long-chain amino triazine compound, DMF and sodium carbonate, reacting at 130 DEG C for 8 hours; filtering, removing DMF by vacuum distillation to obtain the tricyclic borate coupling agent. The application further discloses a synthesis method and application of the tricyclic borate coupling agent. The tricyclic borate coupling agent provided by the application introduces a cyclic large steric group and a conjugated aromatic ring on a B-O bond, enhances the molecular structure stability of the tricyclic borate coupling agent, significantly reduces the oil absorption value of heavy calcium carbonate powder and effectively improves practicability.

Description

Technical Field

[0001] This invention relates to borate ester coupling agents, and more specifically to a method for synthesizing a tricyclic borate ester coupling agent and its application. Background Technology

[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 inorganic powders, they are difficult to disperse uniformly in organic media, leading to a decline in the mechanical properties of the materials. Therefore, surface modification is necessary before filling. Boron ester coupling agents, with their unique valence electron configuration at the center boron atom, are more conducive to improving the mechanical properties of calcium carbonate composites, possessing superior characteristics not found in other traditional coupling agents. Their synthesis and performance research have attracted widespread attention. However, the uneven electron distribution within the molecules of traditional short-chain boron ester coupling agents makes them susceptible to attack or bond breakage, limiting their application. Summary of the Invention

[0003] Traditional short-chain borate esters have uneven electron distribution within their molecules, making them susceptible to attack or bond breakage, which limits their applications. This invention provides a tricyclic borate ester coupling agent that introduces sterically hindered cyclic groups and conjugated aromatic rings onto the BO bonds, enhancing the application performance of the borate ester coupling agent, significantly reducing the oil absorption value of heavy calcium carbonate powder, and effectively improving its practicality.

[0004] One of the objectives of this invention is to provide a tricyclic borate ester coupling agent.

[0005] Specifically, a tricyclic borate ester coupling agent is synthesized by the following method: Boric acid, diethanolamine, and toluene are heated and refluxed to remove water for 2 h; phenol is added and refluxed to remove water for 8 h; toluene is removed by vacuum distillation, and the mixture is purified with ethyl acetate to obtain phenyl dicyclic borate. Cyanuric chloride, tetradecylamine, and anhydrous THF are reacted at 0℃ for 2 h; the reaction is continued at 35℃ for 4 h; THF is removed by filtration and vacuum distillation, and the mixture is purified with ethanol to obtain a bis(long-chain) aminotriazine compound. Phenyl dicyclic borate, the bis(long-chain) aminotriazine compound, DMF, and sodium carbonate are reacted at 130℃ for 8 h; DMF is removed by filtration and vacuum distillation to obtain a tricyclic borate ester coupling agent with the structural formula shown in Formula 1:

[0006] Formula 1 The molar ratio of boric acid to diethanolamine is 1:1.

[0007] The molar ratio of boric acid to phenol is 1:1.5-2.0.

[0008] The molar ratio of cyanuric chloride to tetradecylamine is 1:1.8-2.0.

[0009] The molar ratio of phenyl dicycloborate to the bis(long-chain) aminotriazine compound is 1:1.

[0010] The second objective of this invention is to provide a method for synthesizing the aforementioned tricyclic borate coupling agent.

[0011] Specifically, a method for synthesizing a tricyclic borate ester coupling agent involves taking boric acid, diethanolamine, and toluene, refluxing for 2 h to remove water, adding phenol, refluxing for 8 h, removing toluene by vacuum distillation, and purifying with ethyl acetate to obtain phenyl dicyclic borate. Then, cyanuric chloride, tetradecylamine, and anhydrous THF are reacted at 0°C for 2 h, and then at 35°C for another 4 h. The mixture is filtered, THF is removed by vacuum distillation, and the product is purified with ethanol to obtain a bis(long-chain) aminotriazine compound. Finally, phenyl dicyclic borate, the bis(long-chain) aminotriazine compound, DMF, and sodium carbonate are reacted at 130°C for 8 h, and the DMF is removed by filtration and vacuum distillation to obtain a tricyclic borate ester coupling agent.

[0012] The molar ratio of boric acid to diethanolamine is 1:1.

[0013] The molar ratio of boric acid to phenol is 1:1.5-2.0.

[0014] The molar ratio of cyanuric chloride to tetradecylamine is 1:1.8-2.0.

[0015] The molar ratio of phenyl dicycloborate to the bis(long-chain) aminotriazine compound is 1:1.

[0016] A third objective of this invention is to provide an application of the aforementioned tricyclic borate ester coupling agent. Specifically, it relates to its application in the surface modification of heavy calcium carbonate powder.

[0017] Specifically, the application of a tricyclic borate ester coupling agent in the modification of heavy calcium carbonate powder involves placing the calcium carbonate powder in a modifying machine, heating and stirring it, and adding a tricyclic borate ester coupling agent to obtain heavy calcium carbonate powder with excellent dispersibility and flowability, high activation value, and low oil absorption value.

[0018] The preferred amount of the tricyclic borate coupling agent is 1.5-2.0% of the mass of the heavy calcium carbonate powder.

[0019] The preferred heating temperature is 105℃.

[0020] The preferred stirring time is 20 min.

[0021] Technical effects of the present invention: The present invention provides a tricyclic borate ester coupling agent, which introduces a cyclic sterically hindered group and a conjugated aromatic ring on the BO bond, thereby enhancing the molecular structural stability of the borate ester coupling agent.

[0022] 2. The tricyclic borate ester coupling agent provided by this invention can significantly reduce the oil absorption value of heavy calcium carbonate powder, improve its dispersibility and flowability, enhance its practicality, and has significant economic and promotional value.

[0023] According to the inventor's tests, the oil absorption value of heavy calcium carbonate powder is 30.5 g / 100 g. After modification with a tricyclic borate ester coupling agent, the oil absorption value is reduced to 13.8-15.6 g / 100 g, exhibiting excellent dispersibility and flowability, and superior practical performance. Detailed Implementation

[0024] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with specific embodiments.

[0025] Example 1 (1) Accurately weigh 0.25 mol diethanolamine and 0.25 mol boric acid and add them to a three-necked flask. Use 50 mL toluene as solvent, stir, reflux and react for 2 h to separate water.

[0026] (2) Accurately weigh 0.50 mol of phenol, add it to the reaction mixture, stir and reflux to separate water for 8 h.

[0027] (3) Cool the reaction mixture to room temperature, remove toluene under reduced pressure, and purify the residue with ethyl acetate to give phenyl dicycloborate in 82% yield.

[0028] (4) Accurately weigh 0.50 mol cyanuric chloride, 1.00 mol tetradecylamine and 150 mL anhydrous THF, react at 0℃ for 2 h; continue the reaction at 35℃ for 4 h; filter, remove THF by vacuum distillation, and purify with ethanol to obtain a double long-chain aminotriazine compound with a yield of 90%.

[0029] (5) Accurately weigh 0.30 mol of phenyl dicycloborate, 0.30 mol of bis-long-chain aminotriazine compound, 150 mL of DMF and 0.30 mol of sodium carbonate, react at 130℃ for 8 h; filter and remove DMF by vacuum distillation to obtain a tricycloborate coupling agent, a white waxy solid, with a yield of 80%.

[0030] (6) A heavy calcium carbonate powder modified by a tricyclic borate coupling agent (600 mesh, oil absorption value of 30.5 g / 100g), the addition amount is 2.0% of the mass of calcium carbonate powder, heated to 105℃ and modified for 20 min, can obtain a high-activation, low-oil-absorption heavy calcium carbonate powder with excellent dispersibility and flowability, and its oil absorption value is 13.8 g / 100 g.

[0031] Example 2 (1) Accurately weigh 0.25 mol diethanolamine and 0.25 mol boric acid and add them to a three-necked flask. Use 50 mL toluene as solvent, stir, reflux and react for 2 h to separate water.

[0032] (2) Accurately weigh 0.50 mol of phenol, add it to the reaction mixture, stir and reflux to separate water for 8 h.

[0033] (3) Cool the reaction mixture to room temperature, remove toluene under reduced pressure, and purify the residue with ethyl acetate to give phenyl dicycloborate in 81.5% yield.

[0034] (4) Accurately weigh 0.50 mol cyanuric chloride, 0.95 mol tetradecylamine and 150 mL anhydrous THF, react at 0℃ for 2 h; continue the reaction at 35℃ for 4 h; filter, remove THF by vacuum distillation, and purify with ethanol to obtain a double long-chain aminotriazine compound with a yield of 87%.

[0035] (5) Accurately weigh 0.30 mol of phenyl dicycloborate, 0.30 mol of bis-long-chain aminotriazine compound, 150 mL of DMF and 0.30 mol of sodium carbonate, react at 130℃ for 8 h; filter and remove DMF by vacuum distillation to obtain a tricycloborate coupling agent, a white waxy solid, with a yield of 81%.

[0036] (6) A heavy calcium carbonate powder modified by a tricyclic borate coupling agent (600 mesh, oil absorption value of 30.5 g / 100g), the addition amount is 1.7% of the mass of calcium carbonate powder, heated to 105℃ and modified for 20 min, can obtain a heavy calcium carbonate powder with excellent dispersibility and flowability, and a high activation and low oil absorption value, with an oil absorption value of 14.9 g / 100 g.

[0037] Example 3 (1) Accurately weigh 0.25 mol diethanolamine and 0.25 mol boric acid and add them to a three-necked flask. Use 50 mL toluene as solvent, stir, reflux and react for 2 h to separate water.

[0038] (2) Accurately weigh 0.46 mol of phenol, add it to the reaction mixture, stir and reflux to separate water for 8 h.

[0039] (3) Cool the reaction mixture to room temperature, remove toluene under reduced pressure, and purify the residue with ethyl acetate to give phenyl dicycloborate in 82% yield.

[0040] (4) Accurately weigh 0.50 mol cyanuric chloride, 0.80 mol tetradecylamine and 150 mL anhydrous THF, react at 0℃ for 2 h; continue the reaction at 35℃ for 4 h; filter, remove THF by vacuum distillation, and purify with ethanol to obtain a double long-chain aminotriazine compound with a yield of 85%.

[0041] (5) Accurately weigh 0.30 mol of phenyl dicycloborate, 0.30 mol of bis-long-chain aminotriazine compound, 150 mL of DMF and 0.30 mol of sodium carbonate, react at 130℃ for 8 h; filter and remove DMF by vacuum distillation to obtain a tricycloborate coupling agent, a white waxy solid with a yield of 74%.

[0042] (6) A heavy calcium carbonate powder modified by a tricyclic borate coupling agent (600 mesh, oil absorption value of 30.5 g / 100g), the addition amount is 1.5% of the mass of calcium carbonate powder, heated to 105℃ and modified for 20 min, can obtain a heavy calcium carbonate powder with excellent dispersibility and flowability, and a high activation and low oil absorption value, with an oil absorption value of 15.6 g / 100 g.

[0043] The present invention provides a tricyclic borate ester coupling agent that can effectively modify heavy calcium carbonate powder, significantly reduce oil absorption value, improve dispersibility and flowability, and enhance practicality.

[0044] It should be noted that the above description is a preferred embodiment of the present invention. For those skilled in the art, various improvements and modifications can be made without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A tricyclic borate ester coupling agent, characterized in that, The following method was used for synthesis: Boric acid, diethanolamine, and toluene were refluxed for 2 h to remove water; phenol was added and refluxed for 8 h to remove water; toluene was removed by vacuum distillation, and the product was purified with ethyl acetate to obtain phenyl dicycloborate. Cyanuric chloride, tetradecylamine, and anhydrous THF were reacted at 0 °C for 2 h; the reaction was continued at 35 °C for 4 h; THF was removed by filtration and vacuum distillation, and the product was purified with ethanol to obtain a bis(long-chain) aminotriazine compound. Phenyl dicycloborate, the bis(long-chain) aminotriazine compound, DMF, and sodium carbonate were reacted at 130 °C for 8 h; DMF was removed by filtration and vacuum distillation to obtain a tricycloborate coupling agent.

2. The tricyclic borate ester coupling agent according to claim 1, characterized in that, The molar ratio of boric acid to diethanolamine is 1:

1.

3. The tricyclic borate ester coupling agent according to claim 1, characterized in that, The molar ratio of boric acid to phenol is 1:1.5-2.

0.

4. The tricyclic borate ester coupling agent according to claim 1, characterized in that, The molar ratio of cyanuric chloride to tetradecylamine is 1:1.8-2.

0.

5. The tricyclic borate ester coupling agent according to claim 1, characterized in that, The molar ratio of the dicycloborate phenyl ester to the bis(long-chain) aminotriazine compound is 1:

1.

6. The method for synthesizing a tricyclic borate ester coupling agent according to claim 1, characterized in that, Boric acid, diethanolamine, and toluene were refluxed for 2 h to remove water; phenol was added and refluxed for 8 h to remove water; toluene was removed by vacuum distillation, and the mixture was purified with ethyl acetate to obtain phenyl dicycloborate. Cyanuric chloride, tetradecylamine, and anhydrous THF were reacted at 0 °C for 2 h; the reaction was continued at 35 °C for 4 h; THF was removed by filtration and vacuum distillation, and the mixture was purified with ethanol to obtain a bis(long-chain) aminotriazine compound. Phenyl dicycloborate, the bis(long-chain) aminotriazine compound, DMF, and sodium carbonate were reacted at 130 °C for 8 h; DMF was removed by filtration and vacuum distillation to obtain a tricycloborate coupling agent.

7. The application of the tricyclic borate ester coupling agent according to claim 1 in the surface modification of heavy calcium carbonate powder, characterized in that, Heavy calcium carbonate powder is placed in a modifier, heated and stirred, and then the tricyclic borate ester coupling agent is added to obtain heavy calcium carbonate powder with high activation and low oil absorption value.

8. The application of the tricyclic borate ester coupling agent according to claim 5 in the surface modification of heavy calcium carbonate powder, characterized in that, The preferred amount of the tricyclic borate coupling agent is 1.5-2.0% of the mass of the heavy calcium carbonate powder.

9. The application of the tricyclic borate ester coupling agent according to claim 5 in the modification of heavy calcium carbonate powder, characterized in that, The preferred heating temperature is 105℃; the preferred stirring time is 20 min.

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