Synthesis method and application of oleamide cyclic boric acid methyl phenyl ester coupling agent

Abstract

The invention discloses an oleamide cyclic boric acid methyl 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 p-methylphenol, and carrying out reflux water diversion for 7.5 h; adding oleic acid, and refluxing and separating water for 10 hours; and carrying out reduced pressure distillation to remove toluene, and purifying with ethyl acetate to obtain the oleamide cyclic boric acid methyl phenyl ester coupling agent. The invention also discloses a synthesis method and application of the oleamide cyclic boric acid methyl phenyl ester coupling agent. According to the oleamide cyclic boric acid methyl phenyl ester coupling agent provided by the invention, a cyclic large-steric-hindrance group, long-chain amide and a conjugated aromatic ring are introduced on a B-O bond, so that the structural stability and application performance of the boric acid ester coupling agent are enhanced, the oil absorption value of calcium carbonate powder is remarkably reduced, and the application performance of activated calcium carbonate powder is effectively improved.

Description

Technical Field

[0001] The present invention relates to a borate coupling agent, and specifically to a synthesis method and application of an oil amide cyclic borate methyl phenyl ester 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 decline 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. An oil amide cyclic borate methyl phenyl ester coupling agent provided by the present invention introduces a cyclic sterically hindered group, a long-chain amide, and a multi-electron 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 application performance of activated calcium carbonate powder.

[0004] One of the purposes of the present invention is to provide an oil amide cyclic borate methyl phenyl ester coupling agent.

[0005] Specifically, an oil amide cyclic borate methyl phenyl ester coupling agent is synthesized by the following method: Take boric acid, diethanolamine, and toluene, heat to reflux and separate water for 2 h; add p-methylphenol and reflux to separate water for 7.5 h; add oleic acid and reflux to separate water for 10 h; remove toluene by vacuum distillation and purify with ethyl acetate to obtain an oil amide cyclic borate methyl phenyl ester coupling agent.

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

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

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

[0009]

[0010] Structural formula of an oil amide cyclic borate methyl phenyl ester coupling agent

[0011] Another purpose of the present invention is to provide a synthesis method of the above-mentioned oil amide cyclic borate methyl phenyl ester coupling agent.

[0012] Specifically, a method for synthesizing an oleamide cyclic borate methyl phenyl ester coupling agent is as follows: Take diethanolamine, boric acid, and toluene, stir and reflux for water separation for 2 h; add p-methylphenol and reflux for water separation for 7.5 h; add oleic acid and reflux for water separation for 10 h; remove toluene by vacuum distillation, and purify the residue with ethyl acetate to obtain an oleamide cyclic borate methyl phenyl ester coupling agent.

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

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

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

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

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

[0018] The addition amount of the oleamide cyclic borate methyl phenyl ester coupling agent is preferably 1.0 - 2.0% 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. The oleamide cyclic borate methyl phenyl ester coupling agent provided by the present invention introduces a cyclic sterically hindered group, a long-chain amide, and a conjugated aromatic ring on the B-O bond, enhancing the molecular structure stability of the borate coupling agent.

[0023] 2. The oleamide cyclic borate methyl 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 application performance of activated calcium carbonate 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 oleamide cyclic borate methyl phenyl ester coupling agent, the oil absorption value is reduced to 15.1 - 17.8 g / 100 g, and it has excellent dispersibility and fluidity. Detailed implementation mode

[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 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 carry out a reflux water separation reaction for 2 h.

[0028] (2) Accurately weigh 0.55 mol of p-cresol, add it to the reaction mixture, stir, and carry out a reflux water separation reaction for 7.5 h.

[0029] (3) Accurately weigh 0.5 mol of oleic acid, add it to the reaction mixture, stir, and carry out a reflux water separation reaction for 10 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 oleamide cyclic borate methylphenyl ester coupling agent with a yield of 82%.

[0031] (5) Use an oleamide cyclic borate methylphenyl 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 17.8 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 carry out a reflux water separation reaction for 2 h.

[0034] (2) Accurately weigh 0.6 mol of p-cresol, add it to the reaction mixture, stir, and carry out a reflux water separation reaction for 7.5 h.

[0035] (3) Accurately weigh 0.5 mol of oleic acid, add it to the reaction mixture, stir, and carry out a reflux water separation reaction for 10 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 oleamide cyclic borate methylphenyl ester coupling agent with a yield of 82.5%.

[0037] (5) A kind of calcium carbonate powder surface-modified by oleamide cyclic borate methyl phenyl ester coupling agent (800 mesh, oil absorption value is 32.6 g / 100 g), with an addition amount of 1.5% of the mass of the calcium carbonate powder. Heat it at 100 °C and modify it for 20 min, then calcium carbonate powder with excellent dispersibility and fluidity and low oil absorption value can be obtained, and its oil absorption value is 16.5 g / 100 g.

[0038] Example 3

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

[0040] (2) Accurately weigh 0.65 mol of p-methylphenol and add it into the reaction mixture. Stir, and carry out reflux and water separation reaction for 7.5 h.

[0041] (3) Accurately weigh 0.5 mol of oleic acid and add it into the reaction mixture. Stir, and carry out reflux and water separation reaction for 10 h.

[0042] (4) Cool the reaction mixture to room temperature, remove toluene under reduced pressure, and purify the residue with ethyl acetate to obtain an oleamide cyclic borate methyl phenyl ester coupling agent with a yield of 84%.

[0043] (4) A kind of calcium carbonate powder surface-modified by oleamide cyclic borate methyl phenyl ester coupling agent (800 mesh, oil absorption value is 32.6 g / 100 g), with an addition amount of 2.0% of the mass of the calcium carbonate powder. Heat it at 100 °C and modify it for 20 min, then calcium carbonate powder with excellent dispersibility and fluidity and low oil absorption value can be obtained, and its oil absorption value is 15.1 g / 100 g.

[0044] The oleamide cyclic borate methyl phenyl ester coupling agent provided by the present invention can not only effectively surface-modify and activate calcium carbonate powder, significantly reduce the oil absorption value, improve the dispersibility and fluidity, effectively improve the application performance of the activated calcium carbonate powder, and expand the application fields.

[0045] It should be noted that the above is the preferred implementation manner 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 retouches can still be made, and these improvements and retouches should also be regarded as the protection scope of the present invention.

Claims

1. An oleamide cyclic boric acid methylphenyl 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 p-methylphenol to reflux to separate water; adding oleic acid to reflux to separate water; removing the solvent by vacuum distillation, purifying, and obtaining oleamide cyclic boric acid methylphenyl ester coupling agent.

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

1.

3. The oleamide cyclic boric acid methylphenyl ester coupling agent according to claim 1, characterized in that: The molar ratio of the boric acid to p-methylphenol is 1:1.1-1.

3.

4. The oleamide cyclic boric acid methylphenyl ester coupling agent according to claim 1, characterized in that: The molar ratio of boric acid to oleic acid is 1:

1.

5. The method for synthesizing an oleamide cyclic boric acid methylphenyl 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 p-methylphenol and reflux to separate water for 7.5 hours; add oleic acid and reflux to separate water for 10 hours; remove toluene by vacuum distillation, purify with ethyl acetate, and obtain an oleylamide cyclic boric acid methylphenyl ester coupling agent.

6. The use of an oleamide cyclic boric acid methylphenyl 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 oleamide cyclic boric acid methylphenyl ester coupling agent is added to obtain calcium carbonate powder with low oil absorption value.

7. The use of an oleamide cyclic boric acid methylphenyl ester coupling agent according to claim 6 in surface modification of calcium carbonate powder, characterized in that: The addition amount of the oleamide cyclic boric acid methylphenyl ester coupling agent is preferably 1.0-2.0% of the mass of the calcium carbonate powder.

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

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