Reactive high-efficiency calcium carbonate powder surface modifier, synthesis method and application thereof

Abstract

The application discloses a kind of reactive high-efficiency calcium carbonate powder surface modifiers, which is synthesized by the following method: (1) mix boric acid and toluene, stir, drop in diethanolamine, 1h drop is completed;Then warm up and reflux for 6h;(2) cool to room temperature, drop in cyclohexanol, 1h drop is completed;Then warm up and reflux for 12h;(3) cool to room temperature, add succinic anhydride, then react at room temperature for 1.5h, remove the solvent by reduced pressure distillation, to obtain reactive high-efficiency calcium carbonate powder surface modifier.The application also discloses the synthesis method and application of the reactive high-efficiency calcium carbonate powder surface modifier.The reactive high-efficiency calcium carbonate powder surface modifier provided by the application introduces hydrophobic cyclic bulky steric group on B-O bond, which can effectively inhibit the attack of water molecules and slow down the hydrolysis rate;Graft carboxyl group in the parent structure, which can form chemical bond with calcium carbonate surface ions, improve the binding firmness and stability, greatly reduce the oil absorption value, enhance the practicability of borate coupling agent, and significantly improve the quality and performance of activated calcium carbonate.

Description

TECHNICAL FIELD

[0001] The present application relates to a calcium carbonate powder surface modifier, in particular to a synthesis and application of a reactive high-efficiency calcium carbonate powder surface modifier and a synthesis method and application thereof. BACKGROUND

[0002] Calcium carbonate is widely used in rubber, plastics, papermaking, paint, ink, medicine and other industries as a high-quality filler. However, inorganic powder is hydrophilic and oleophobic, and it is difficult to disperse uniformly in organic medium, which leads to the decrease of the mechanical properties of the material, so it must be surface modified or activated before filling. The central boron atom of borate coupling agent has a unique valence electron configuration, which can further improve the mechanical properties of the material, and has excellent properties that other traditional coupling agents or surface modifiers do not have. Its synthesis and performance research has attracted widespread attention. However, the traditional borate coupling agent has poor hydrolytic stability, low binding firmness and is easy to detach, which leads to poor dispersibility and flowability of the activated powder, and seriously affects the mechanical properties of the composite material, so its application is limited to a certain extent. SUMMARY

[0003] The traditional borate coupling agent has poor hydrolytic stability, low binding firmness and is easy to detach, which leads to large oil absorption value of the modified calcium carbonate, poor dispersibility and flowability, and seriously affects the mechanical properties of the composite material. The present application introduces a hydrophobic cyclic steric group on the B-O bond, which can effectively inhibit the attack of water molecules and slow down the hydrolysis rate. The carboxyl group is grafted in the parent structure, which can form a chemical bond with the surface ions of calcium carbonate, improve the binding firmness and stability, greatly reduce the oil absorption value, enhance the practicality of borate coupling agent, and significantly improve the quality and performance of the activated calcium carbonate.

[0004] One of the purposes of the present application is to provide a reactive high-efficiency calcium carbonate powder surface modifier.

[0005] Specifically, a reactive high-efficiency calcium carbonate powder surface modifier is synthesized by the following method:

[0006] (1) Mix boric acid and toluene, stir, and drop in diethanolamine, 1h drop is completed; then warm up and reflux for 6h;

[0007] (2) Cool to room temperature, drop in cyclohexanol, 1h drop is completed; then warm up and reflux for 12h;

[0008] (3) Cool to room temperature, add succinic anhydride, then react at room temperature for 1.5h, remove the solvent by reduced pressure distillation to obtain the reactive high-efficiency calcium carbonate powder surface modifier.

[0009] The molar ratio of boric acid, diethanolamine, cyclohexanol and succinic anhydride is 1:1:1:1.

[0010]

[0011] The structural formula of the reactive high-efficiency calcium carbonate powder surface modifier

[0012] The second object of the present application is to provide a synthesis method of the reactive high-efficiency calcium carbonate powder surface modifier.

[0013] Specifically, the synthesis method of the reactive high-efficiency calcium carbonate powder surface modifier comprises the following steps:

[0014] (1) Take boric acid and toluene, stir, and drop in diethanolamine, 1h drop is completed; then warm up and reflux for 6h;

[0015] (2) Cool to room temperature, drop in cyclohexanol, 1h drop is completed; then warm up and reflux for 12h;

[0016] (3) Cool to room temperature, add succinic anhydride, then react at room temperature for 1.5h, remove the solvent by reduced pressure distillation, and obtain the reactive high-efficiency calcium carbonate powder surface modifier.

[0017] The molar ratio of the boric acid, diethanolamine, cyclohexanol and succinic anhydride is 1:1:1:1.

[0018] The third object of the present application is to provide the application of the reactive high-efficiency calcium carbonate powder surface modifier.

[0019] Specifically, the application of the reactive high-efficiency calcium carbonate powder surface modifier, take heavy calcium carbonate powder in the modification machine, heat, stir, and drop in the melted reactive high-efficiency calcium carbonate powder surface modifier to process, and the low oil absorption value calcium carbonate powder with excellent dispersibility and fluidity can be obtained, and the oil absorption value is 13-15g / 100g calcium carbonate.

[0020] The amount of the dropped reactive high-efficiency calcium carbonate powder surface modifier is preferably 1.5-1.7% of the mass of the calcium carbonate powder.

[0021] The heating temperature is preferably 100-110℃.

[0022] The stirring time is preferably 20-30min.

[0023] The synthesis and application technology of a reactive high-efficiency calcium carbonate powder surface modifier significantly reduces the oil absorption value of the calcium carbonate powder, improves its dispersibility and fluidity, and significantly enhances the hydrolysis stability and binding firmness, improves the processing stability and practicability, and has great economic and popularization value.

[0024] Technical effects of the present application:

[0025] 1.The reaction-type efficient calcium carbonate powder surface modifier provided by the present application introduces a hydrophobic cyclic steric hindrance group on a B-O bond, can effectively inhibit the attack of water molecules, slow down the hydrolysis rate, grafts a carboxyl group in the parent structure, can form a chemical bond with the calcium carbonate surface ions, improve the binding firmness and stability, greatly reduce the oil absorption value, enhance the practicability of boric acid ester coupling agent, and significantly improve the quality and performance of activated calcium carbonate.

[0026] 2.The reaction-type efficient calcium carbonate powder surface modifier provided by the present application has strong hydrolysis stability, and the hydrolysis stability of the reaction-type efficient calcium carbonate powder surface modifier is 816 h, while the hydrolysis stability of ordinary boric acid ester is 8-20 h.

[0027] 3.The yield of the reaction-type efficient calcium carbonate powder surface modifier synthesis method provided by the present application is 85-89%.

[0028] 4.After the reaction-type efficient calcium carbonate powder surface modifier provided by the present application modifies the heavy calcium carbonate powder, the modified heavy calcium carbonate powder is washed with water for 3 times, dried, crushed, and the change of the oil absorption value is small, which proves that the reaction-type efficient calcium carbonate powder surface modifier has strong binding firmness with calcium carbonate. The oil absorption value of the calcium carbonate powder modified by the ordinary boric acid ester surface agent increases by 35% after being washed with water for 3 times, which proves that the ordinary boric acid ester surface agent has poor binding firmness with calcium carbonate and is very easy to be detached. DETAILED DESCRIPTION

[0029] To make the technical problems, technical solutions and advantages of the present application clearer, specific embodiments will be described in detail below.

[0030] Embodiment 1

[0031] (1) Stir 0.2 mol of boric acid and 150 mL of toluene, slowly drop 0.2 mol of diethanolamine, and complete the drop in 1 h; then, increase the temperature to reflux and react for 6 h.

[0032] (2) Slowly drop 0.2 mol of cyclohexanol after cooling to room temperature, complete the drop in 1 h; then, increase the temperature to reflux and react for 12 h.

[0033] (3) After cooling to room temperature, add 0.2 mol of succinic anhydride, and then react at room temperature for 1.5 h. Remove the solvent (recycle and reuse) under reduced pressure to obtain the reaction-type efficient calcium carbonate powder surface modifier, and the yield is 85%.

[0034] (4) Take 800g of heavy calcium carbonate powder (800 mesh, oil absorption value is 33g / 100g), add reactive high-efficiency calcium carbonate powder surface modifier, the addition amount is 1.5% of the mass of heavy calcium carbonate powder, heat to 100°C, stir for 20 min, to obtain low oil absorption value calcium carbonate powder with excellent dispersibility and fluidity, its oil absorption value is 15g / 100g. Take part of the modified heavy calcium carbonate powder, after 3 times of water washing, the oil absorption value only increases by 3%, proving that the reactive high-efficiency calcium carbonate powder surface modifier has strong binding firmness with calcium carbonate. The calcium carbonate powder modified by ordinary borate surface agent increases by 35% after 3 times of water washing, proving that its binding firmness with calcium carbonate is poor and it is very easy to detach.

[0035] Example 2

[0036] (1) Boric acid 0.2mol, toluene 150ml, stirring, slowly drop in cyclohexanol 0.2mol, 1h drop completion; then heat to reflux reaction 6h.

[0037] (2) Cool to room temperature, slowly drop in diethanolamine 0.2mol, 1h drop completion; then heat to reflux reaction 12h.

[0038] (3) Cool to room temperature, add succinic anhydride 0.2mol, then room temperature reaction 1.5h. Remove the solvent (recycle and reuse) under reduced pressure to obtain reactive high-efficiency calcium carbonate powder surface modifier, yield 87%.

[0039] (4) Take 800g of heavy calcium carbonate powder (800 mesh, oil absorption value is 33g / 100g), add reactive high-efficiency calcium carbonate powder surface modifier, the addition amount is 1.6% of the mass of heavy calcium carbonate powder, heat to 105°C, stir for 25 min, to obtain low oil absorption value calcium carbonate powder with excellent dispersibility and fluidity, its oil absorption value is 13g / 100g. Take part of the modified heavy calcium carbonate powder, after 3 times of water washing, the oil absorption value increases by 2.5%, proving that the reactive high-efficiency calcium carbonate powder surface modifier has strong binding firmness with calcium carbonate. The calcium carbonate powder modified by ordinary borate surface agent increases by 35% after 3 times of water washing, proving that its binding firmness with calcium carbonate is poor and it is very easy to detach.

[0040] Example 3

[0041] (1) Boric acid 0.2mol, toluene 150ml, stirring, slowly drop in diethanolamine 0.2mol, 1h drop completion; then heat to reflux reaction 6h.

[0042] (2) Cool to room temperature, slowly drop in cyclohexanol 0.2mol, 1h drop completion; then heat to reflux reaction 12h.

[0043] (3) cooling to room temperature, adding succinic anhydride 0.2 mol, and then reacting at room temperature for 1.5 h. The solvent is removed by distillation under reduced pressure (recovery and reuse), and the yield is 89%.

[0044] (4) Take 800 g of heavy calcium carbonate powder (800 mesh, oil absorption value is 33 g / 100 g), add the reactive high-efficiency calcium carbonate powder surface modifier, the addition amount is 1.7% of the mass of the heavy calcium carbonate powder, heat to 110°C, and stir for 30 min. A low oil absorption value calcium carbonate powder with excellent dispersibility and fluidity is obtained, and the oil absorption value is 14 g / 100 g. Part of the modified heavy calcium carbonate powder is washed with water for 3 times, and the oil absorption value increases by 2.8%, which proves that the reactive high-efficiency calcium carbonate powder surface modifier has strong binding firmness with calcium carbonate. The calcium carbonate powder modified by the common borate surface agent is washed with water for 3 times, and the oil absorption value increases by 35%, which proves that the binding firmness is poor and the calcium carbonate powder is very easy to detach.

[0045] The reactive high-efficiency calcium carbonate powder surface modifier provided by the application not only can effectively modify the surface of the calcium carbonate powder, significantly reduce the oil absorption value, improve the dispersibility and fluidity, but also can effectively solve the defects of easy hydrolysis and low binding firmness of the traditional borate coupling agent, enhance the hydrolysis stability and binding firmness, improve the processing stability and practicability, significantly improve the quality and performance of the calcium carbonate powder, and expand the application field.

[0046] It should be noted that the above is the preferred embodiment of the application. For those skilled in the art, without departing from the principles of the application, a number of improvements and refinements can be made, which should also be considered within the scope of protection of the application.

Claims

1. A reactive high-efficiency calcium carbonate powder surface modifier, characterized in that, Synthesized by the following method: (1) take boric acid 0.2 mol and toluene 150 mL mixed, stirring, drop in diethanolamine 0.2 mol, 1 h drop is completed; then heating reflux reaction 6 h; (2) cooling to room temperature, drop in cyclohexanol 0.2 mol, 1 h drop is completed; then heating reflux reaction 12 h; (3) cooling to room temperature, add succinic anhydride 0.2 mol, then room temperature reaction 1.5 h, remove the solvent under reduced pressure, to obtain the reaction type high efficient calcium carbonate powder surface modifier, yield 85%; The structural formula of the reaction type high efficient calcium carbonate powder surface modifier is: 。 2. The method for synthesizing reactive high-efficiency calcium carbonate powder surface modifier, characterized in that, Including the following steps: (1) take boric acid 0.2 mol and toluene 150 mL mixed, stirring, drop in diethanolamine 0.2 mol, 1 h drop is completed; then heating reflux reaction 6 h; (2) cooling to room temperature, drop in cyclohexanol 0.2 mol, 1 h drop is completed; then heating reflux reaction 12 h; (3) cooling to room temperature, add succinic anhydride 0.2 mol, then room temperature reaction 1.5 h, remove the solvent under reduced pressure, to obtain the reaction type high efficient calcium carbonate powder surface modifier, yield 85%; The structural formula of the reaction type high efficient calcium carbonate powder surface modifier is: 。 3. The use of the reactive high-efficiency calcium carbonate powder surface modifier of claim 1, characterized in that, Take 800 mesh heavy calcium carbonate powder 800 g, the oil absorption value of the heavy calcium carbonate powder is 33 g / 100 g, add the reaction type high efficient calcium carbonate powder surface modifier of claim 1, the adding amount is 1.5% of the mass of the heavy calcium carbonate powder, heat 100 DEG C, stirring 20 min, to obtain low oil absorption value calcium carbonate powder, its oil absorption value is 15 g / 100 g.

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