Synthesis and application of octadecanamide cyclic phenyl borate coupling agent

Abstract

The invention discloses an octadecanamide cyclic boric acid phenyl ester coupling agent, which is synthesized by the following method: taking boric acid, diethanol amine and methylbenzene, heating, refluxing and separating water for 2 hours; adding phenol, refluxing and separating water for 8 hours; adding octadecanoic acid, and refluxing and separating water for 5 hours; and carrying out reduced pressure distillation to remove toluene, and purifying with ethyl acetate to obtain the octadecanamide cyclic boric acid phenyl ester coupling agent. The invention also discloses a synthesis method and application of the octadecanamide cyclic boric acid phenyl ester coupling agent. According to the octadecanamide cyclic boric acid phenyl ester coupling agent provided by the invention, a cyclic large steric hindrance group and a conjugated aromatic ring are introduced on a B-O bond, so that the structural stability and the application performance of the boric acid ester coupling agent are enhanced, the oil absorption value of calcium carbonate powder is remarkably reduced, and the quality and the additional value of the powder are effectively improved.

Description

Technical Field

[0001] The present invention relates to a borate coupling agent, and more particularly to the synthesis and application of an octadecanamide cyclic phenyl borate coupling agent. Background Art

[0002] 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, it is difficult to disperse them uniformly in organic media, resulting in a decrease in the mechanical properties of materials. Therefore, it is necessary to perform surface modification or activation on them before filling. The central boron atom of borate coupling agents has a unique valence electron configuration, which is more conducive to improving the mechanical properties of calcium carbonate composites and has excellent properties that other traditional coupling agents do not have. The research on its synthesis and properties has received extensive attention. However, the internal electron distribution of traditional short-chain borate molecules is uneven, making them easily attacked or broken, which limits the application of borate coupling agents. Summary of the Invention

[0003] The internal electron distribution of traditional short-chain borate molecules is uneven, making them easily attacked or broken, which limits the application of borates. The octadecanamide cyclic phenyl borate coupling agent provided by the present invention introduces a cyclic sterically hindered group and a conjugated aromatic ring on the B-O bond, enhancing the application performance of the borate coupling agent, significantly reducing the oil absorption value of calcium carbonate powder, and effectively improving the quality and added value of the powder.

[0004] One of the objectives of the present invention is to provide an octadecanamide cyclic phenyl borate coupling agent.

[0005] Specifically, an octadecanamide cyclic phenyl borate coupling agent is synthesized by the following method: Take boric acid, diethanolamine, and toluene, heat to reflux and separate water for 2 h; add phenol and reflux to separate water for 8 h; add stearic acid and reflux to separate water for 5 h; remove toluene by vacuum distillation and purify with ethyl acetate to obtain an octadecanamide cyclic phenyl borate coupling agent.

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

[0007] The molar ratio of boric acid to phenol is 1:1.1 - 1.3.

[0008] The molar ratio of boric acid to stearic acid is 1:1.

[0009]

[0010] Structural formula of an octadecanamide cyclic phenyl borate coupling agent

[0011] Another objective of the present invention is to provide a synthesis method for the above-mentioned octadecanamide cyclic phenyl borate coupling agent.

[0012] Specifically, a method for synthesizing an octadecanamide cyclic borate phenyl ester coupling agent is as follows: Take boric acid, diethanolamine, and toluene, heat and reflux to separate water for 2 h; add phenol and reflux to separate water for 8 h; add stearic acid and reflux to separate water for 5 h; remove toluene by vacuum distillation and purify with ethyl acetate to obtain an octadecanamide cyclic borate phenyl ester coupling agent.

[0013] The molar ratio of boric acid to diethanolamine is 1:1.

[0014] The molar ratio of boric acid to phenol is 1:1.1 - 1.3.

[0015] The molar ratio of boric acid to stearic acid is 1:1.

[0016] The third object of the present invention is to provide the application of the above-mentioned octadecanamide cyclic borate phenyl ester coupling agent. Specifically, it relates to the application in the surface modification of calcium carbonate powder.

[0017] Specifically, an application of an octadecanamide cyclic borate phenyl ester coupling agent in the modification of calcium carbonate powder: Place the calcium carbonate powder in a modifier, heat and stir, add an octadecanamide cyclic borate phenyl ester coupling agent, and a calcium carbonate powder with excellent dispersibility and fluidity and low oil absorption value can be obtained.

[0018] The addition amount of the described octadecanamide cyclic borate phenyl ester coupling agent is preferably 1.0 - 1.8% of the mass of the calcium carbonate powder.

[0019] The heating temperature is preferably 100°C.

[0020] The stirring time is preferably 20 min.

[0021] The technical effects of the present invention:

[0022] 1. For the octadecanamide cyclic borate phenyl ester coupling agent provided by the present invention, a cyclic sterically hindered group and a conjugated aromatic ring are introduced on the B - O bond, enhancing the molecular structure stability of the borate ester coupling agent.

[0023] 2. The octadecanamide cyclic borate phenyl ester coupling agent provided by the present invention can significantly reduce the oil absorption value of calcium carbonate powder, improve its dispersibility and fluidity, effectively improve the quality and added value of the powder, and has great economic and promotional value.

[0024] Verified by the inventor's experiments, for calcium carbonate powder with an oil absorption value of 32.6 g / 100 g, after surface modification with an octadecanamide cyclic borate phenyl ester coupling agent, the oil absorption value is reduced to 15.5 - 16.8 g / 100 g, and it has excellent dispersibility and fluidity, and very superior activation performance. Specific Embodiments

[0025] 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 reference to specific embodiments.

[0026] Example 1

[0027] (1) Accurately weigh 0.5 mol of diethanolamine and 0.5 mol of boric acid, add them to a three-necked flask, use 120 mL of toluene as a solvent, stir, and reflux for water separation for 2 h.

[0028] (2) Accurately weigh 0.55 mol of p-phenol, add it to the reaction mixture, stir, and reflux for water separation for 8 h.

[0029] (3) Accurately weigh 0.5 mol of stearic acid, add it to the reaction mixture, stir, and reflux for water separation for 5 h.

[0030] (4) Cool the reaction mixture to room temperature, remove toluene under reduced pressure, add ethyl acetate to the residue for purification, and obtain an octadecanamide cyclic borate phenyl ester coupling agent with a yield of 86%.

[0031] (5) Use an octadecanamide cyclic borate phenyl ester coupling agent to modify calcium carbonate powder (800 mesh, oil absorption value of 32.6 g / 100 g), with an addition amount of 1.0% of the mass of the calcium carbonate powder, heat at 100 °C, and modify for 20 min to obtain calcium carbonate powder with excellent dispersibility and fluidity and a low oil absorption value, and its oil absorption value is 16.8 g / 100 g.

[0032] Example 2

[0033] (1) Accurately weigh 0.5 mol of diethanolamine and 0.5 mol of boric acid, add them to a three-necked flask, use 120 mL of toluene as a solvent, stir, and reflux for water separation for 2 h.

[0034] (2) Accurately weigh 0.6 mol of phenol, add it to the reaction mixture, stir, and reflux for water separation for 8 h.

[0035] (3) Accurately weigh 0.5 mol of stearic acid, add it to the reaction mixture, stir, and reflux for water separation for 5 h.

[0036] (4) Cool the reaction mixture to room temperature, remove toluene under reduced pressure, add ethyl acetate to the residue for purification, and obtain an octadecanamide cyclic borate phenyl ester coupling agent with a yield of 87%.

[0037] (5) Use an octadecanamide cyclic borate phenyl ester coupling agent to modify calcium carbonate powder (800 mesh, oil absorption value of 32.6 g / 100 g), with an addition amount of 1.3% of the mass of the calcium carbonate powder, heat at 100 °C, and modify for 20 min to obtain calcium carbonate powder with excellent dispersibility and fluidity and a low oil absorption value, and its oil absorption value is 16.1 g / 100 g.

[0038] Example 3

[0039] (1) Accurately weigh 0.5 mol of diethanolamine and 0.5 mol of boric acid, add them into a three-necked flask, use 120 mL of toluene as the solvent, stir, and carry out reflux water separation reaction for 2 h.

[0040] (2) Accurately weigh 0.65 mol of phenol, add it into the reaction mixture, stir, and carry out reflux water separation reaction for 8 h.

[0041] (3) Accurately weigh 0.5 mol of stearic acid, add it into the reaction mixture, stir, and carry out reflux water separation reaction for 5 h.

[0042] (4) Cool the reaction mixture to room temperature, remove toluene under reduced pressure, add ethyl acetate to the residue for purification, and obtain an octadecanamide cyclic borate phenyl ester coupling agent with a yield of 89%.

[0043] (5) Use an octadecanamide cyclic borate phenyl ester coupling agent to modify the surface of calcium carbonate powder (800 mesh, oil absorption value of 32.6 g / 100 g), with an addition amount of 1.8% of the mass of the calcium carbonate powder. Heat at 100 °C and modify for 20 min to obtain calcium carbonate powder with excellent dispersibility and fluidity and a low oil absorption value. Its oil absorption value is 15.5 g / 100 g.

[0044] The octadecanamide cyclic borate phenyl ester coupling agent provided by the present invention can not only effectively modify and activate the surface of calcium carbonate powder, significantly reduce the oil absorption value, improve the dispersibility and fluidity, enhance the quality and added value, strengthen the practicability, but also expand the application field.

[0045] 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 described in the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. An octadecyl cyclic boric acid phenyl ester coupling agent, characterized in that: The synthesis method is as follows: taking boric acid, diethanolamine and toluene, heating and refluxing to separate water; adding phenol and refluxing to separate water; adding octadecanoic acid and refluxing to separate water; removing the solvent by vacuum distillation and purifying to obtain an octadecylamide cyclic boric acid phenyl ester coupling agent.

2. The octadecyl amide cyclic boric acid phenyl ester coupling agent according to claim 1, characterized in that: The molar ratio of the boric acid to the diethanolamine is 1:

1.

3. An octadecyl cyclic boric acid phenyl ester coupling agent according to claim 1, characterized in that: The molar ratio of the boric acid to the phenol is 1:1.1-1.

3.

4. The octadecyl amide cyclic boric acid phenyl ester coupling agent according to claim 1, characterized in that: The molar ratio of the boric acid to octadecanoic acid is 1:

1.

5. The method for synthesizing an octadecyl cyclic boric acid phenyl ester coupling agent according to claim 1, characterized in that: Take boric acid, diethanolamine and toluene, heat and reflux to separate water for 2 hours; add phenol and reflux to separate water for 8 hours; add octadecanoic acid and reflux to separate water for 5 hours; remove toluene by vacuum distillation, purify with ethyl acetate, and obtain an octadecylamide cyclic boric acid phenyl ester coupling agent.

6. The use of an octadecyl cyclic boric acid phenyl ester coupling agent as claimed in claim 1 in surface modification of calcium carbonate powder, characterized in that: The calcium carbonate powder is placed in a modifier, heated and stirred, and an octadecyl amide cyclic boric acid phenyl ester coupling agent is added to obtain the calcium carbonate powder with low oil absorption value.

7. The use of an octadecyl cyclic boric acid phenyl ester coupling agent according to claim 6 in surface modification of calcium carbonate powder, characterized in that: The addition amount of the octadecyl cyclic boric acid phenyl ester coupling agent is preferably 1.0-1.8% of the mass of the calcium carbonate powder.

8. The use of an octadecyl cyclic boric acid phenyl ester coupling agent according to claim 6 in the modification of calcium carbonate powder, characterized in that: The heating temperature is preferably 100° C.; the stirring time is preferably 20 min.

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