Preparation method and application of calcium carbonate powder modified whitening integrated additive

Abstract

The invention provides a preparation method and application of a calcium carbonate powder modified whitening integrated auxiliary agent. The preparation method comprises the following steps: slowly dripping DSD acid, water and a saturated Na2CO3 solution into a cyanuric chloride ice-water mixture, controlling the temperature at 3-5 DEG C for reaction, then adding ethanolamine and p-aminobenzoic acid, adjusting the pH value to 8 with a saturated Na2CO3 solution, heating the temperature to 40-45 DEG C for reaction for 3.5 hours; adding diethylaminoethyl methacrylate, maintaining the pH value at 9 with a saturated Na2CO3 solution, heating the temperature to 85-90 DEG C for reaction for 6 hours, and cooling the mixture to room temperature; adding sodium stearate, sodium dodecylbenzene sulfonate and water, heating and stirring the mixture to obtain the modified whitening integrated auxiliary agent. It is applied to calcium carbonate powder with a mesh size of 800-2000, a whiteness (CIE) of 92-94, and an oil absorption value of 33-38 g / 100 g to obtain a high-activity and high-white calcium carbonate powder with an oil absorption value of 11-13 g / 100 g, a whiteness value (CIE) increased to 96-98.5, and a whiteness value (CIE) increased by 4.0-4.5.

Description

Technical Field

[0001] The patent of the present invention relates to an integrated whitening additive for modified calcium carbonate powder, and specifically to a preparation method and application of an integrated whitening additive for modified calcium carbonate powder. Background Art

[0002] Calcium carbonate powder is a high-quality, low-carbon, green and environmentally friendly mineral filler that is widely used in rubber, plastic, papermaking, coatings, inks, pharmaceuticals and other industries. However, due to the hydrophilic and oleophobic nature of calcium carbonate powder, it is difficult to disperse evenly in organic media, resulting in a decrease in the mechanical properties of the material. Therefore, it is necessary to add a surface modifier to modify its surface. Each modifier has its own unique performance characteristics and shows different results after modification of calcium carbonate. Therefore, the structure of a single modifier has limitations. Multi-component composite modifiers can combine the advantages of each modifier to achieve a significant effect of compounding and enhancing synergy. However, existing organic surface modifiers are easily oxidized or decomposed and discolored when modifying calcium carbonate powder, resulting in a decrease in the whiteness value of the activated calcium carbonate powder, which seriously affects the quality and added value of downstream products.

[0003] As the application field of calcium carbonate gradually expands, the market demand is growing rapidly. Although my country's natural stone resources are very rich, with continuous development, high-quality calcium carbonate resources are gradually scarce, and the whiteness and color quality of calcium carbonate are seriously reduced. The current waste phenomenon is alarming. The raw material yield rate is only about 30%. Except for a small amount of utilization, most of the rest is treated as waste stone, causing serious waste of resources and environmental pollution. Improving the utilization rate of low-whiteness calcium carbonate and meeting the company's requirements for the whiteness and color quality of calcium carbonate are effective measures to reduce resource waste and environmental pollution.

[0004] In summary, it is particularly urgent and necessary to research and develop an integrated whitening additive for calcium carbonate powder modification and use it to produce high-activity high-white calcium carbonate powder. After searching, the preparation method and application technology of the integrated whitening additive for calcium carbonate powder modification have not been reported yet, and the market demand is very urgent. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation method and application technology of an integrated whitening additive for calcium carbonate powder modification, which can significantly reduce the oil absorption value of calcium carbonate powder, improve the compatibility of powder with organic materials, and effectively inhibit the decrease in the whiteness value of calcium carbonate powder after activation, significantly improving the quality and added value of the modified calcium carbonate powder; at the same time, the technology is also suitable for the whitening and modification of low-whiteness calcium carbonate powder, improving the utilization rate and added value of low-whiteness calcium carbonate and solid waste calcium carbonate, and is an effective method for wet-process modification to produce high-activity and high-whiteness calcium carbonate powder. The preparation method and application technology of the integrated whitening additive for calcium carbonate powder modification of the present invention are composed of the following steps:

[0006] (1) 1 mmol DSD acid, 10 mL water and saturated Na2CO3 solution were stirred until clear;

[0007] (2) 2mmol of cyanuric chloride and 10mL of ice water, stir in an ice bath, slowly drop (1) into the mixture, and control the temperature at 3-5℃ to react for 1.5h;

[0008] (3) Add 1 mmol of ethanolamine and 1 mmol of p-aminobenzoic acid, adjust the pH to 8 with saturated Na2CO3 solution, raise the temperature to 40-45°C, and react for 3.5 hours;

[0009] (4) Add 2 mmol of diethylaminoethyl methacrylate, maintain pH = 9 with saturated Na2CO3 solution, raise the temperature to 85-90°C, stir and react for 6 hours, and cool to room temperature;

[0010] (5) adding sodium stearate, sodium dodecylbenzene sulfonate and 20 L of water to obtain a modified whitening integrated additive, and stirring evenly at 80-85° C.;

[0011] (6) Add 20 kg of calcium carbonate powder, stir for a period of time, filter and dry to obtain high-activity high-white calcium carbonate powder.

[0012] The mass of the sodium stearate in step (5) is preferably 0.2-0.3 kg;

[0013] The mass of the sodium dodecylbenzene sulfonate described in the above step (5) is preferably 0.2-0.3 kg;

[0014] The temperature in step (5) is preferably 80-85°C;

[0015] The calcium carbonate powder described in the above step (6) preferably has a mesh size of 800 to 2000, a whiteness (CIE) of 92 to 94, and an oil absorption value of 33 to 38 g / 100 g;

[0016] The time of step (6) is preferably 10 to 15 minutes.

[0017] Experimental data show that the oil absorption value of the calcium carbonate powder treated by the technology of the present invention is reduced to 11-13g / 100g, the whiteness value (CIE) is increased to 96-98.5, the whiteness value (CIE) is increased by 4.0-4.5, the oil absorption value is significantly reduced, and the activation performance is significantly improved.

[0018] The preparation method and application technology of the calcium carbonate powder modified whitening integrated auxiliary agent of the present invention can effectively solve the problem of the whiteness value of the modified calcium carbonate powder decreased due to oxidation or decomposition during the processing or heating of the organic surface modifier, greatly reduce the oil absorption value of the calcium carbonate powder, increase the compatibility of the powder, and significantly improve the whiteness of the calcium carbonate powder; the preparation method and application technology of the calcium carbonate powder modified whitening integrated auxiliary agent of the present invention are used to treat low-whiteness calcium carbonate powder, which can achieve the dual effects of whitening and modification, improve the utilization rate and added value of low-whiteness calcium carbonate and solid waste calcium carbonate, and is an effective method for producing high-activity high-whiteness calcium carbonate powder, which has great economic value and promotion value. The present invention is further described below in conjunction with embodiments. DETAILED DESCRIPTION

[0019] Embodiment 1:

[0020] (1) 1 mmol DSD acid, 10 mL water and saturated Na2CO3 solution were stirred until clear;

[0021] (2) 2mmol of cyanuric chloride and 10mL of ice water, stir in an ice bath, slowly drop (1) into the mixture, and control the temperature at 3-5℃ to react for 1.5h;

[0022] (3) Add 1 mmol of ethanolamine and 1 mmol of p-aminobenzoic acid, adjust the pH to 8 with saturated Na2CO3 solution, raise the temperature to 40-45°C, and react for 4 hours;

[0023] (4) Add 2 mmol of diethylaminoethyl methacrylate, maintain pH = 9 with saturated Na2CO3 solution, raise the temperature to 85-90°C, stir and react for 6 hours, and cool to room temperature;

[0024] (5) Add 0.3 kg sodium stearate, 0.2 kg sodium dodecylbenzene sulfonate and 20 L water, stir and heat to 80 ° C;

[0025] (6) Add 20 kg of calcium carbonate powder with 800 mesh, whiteness of 94 (CIE), and oil absorption of 33 g / 100 g, stir for 15 min, filter and dry to obtain high-activity high-white calcium carbonate powder with oil absorption of 11 g / 100 g CaCO3 and whiteness (CIE).

[0026] It is 98.5.

[0027] Embodiment 2:

[0028] (1) 1 mmol DSD acid, 10 mL water and saturated Na2CO3 solution were stirred until clear;

[0029] (2) 2mmol of cyanuric chloride and 10mL of ice water, stir in an ice bath, slowly drop (1) into the mixture, and control the temperature at 3-5℃ to react for 1.5h;

[0030] (3) Add 1 mmol of ethanolamine and 1 mmol of p-aminobenzoic acid, adjust the pH to 8 with saturated Na2CO3 solution, raise the temperature to 40-45°C, and react for 4 hours;

[0031] (4) Add 2 mmol of diethylaminoethyl methacrylate, maintain pH = 9 with saturated Na2CO3 solution, heat to 85-90°C, stir for 6 h, and cool to room temperature;

[0032] (5) Add 0.2 kg sodium stearate, 0.3 kg sodium dodecylbenzene sulfonate and 20 L water, stir and heat to 85 ° C;

[0033] (6) Add 20 kg of calcium carbonate powder with a mesh size of 1000, a whiteness of 92 (CIE), and an oil absorption value of 35 g / 100 g, stir for 20 min, filter, and dry to obtain high-activity, high-white calcium carbonate powder with an oil absorption value of 13 g / 100 g calcium carbonate and a whiteness (CIE).

[0034] It is 96.

[0035] Embodiment 3:

[0036] (1) 1 mmol DSD acid, 10 mL water and saturated Na2CO3 solution were stirred until clear;

[0037] (2) 2mmol of cyanuric chloride and 10mL of ice water, stir in an ice bath, slowly drop (1) into the mixture, and control the temperature at 3-5℃ to react for 1.5h;

[0038] (3) Add 1 mmol of ethanolamine and 1 mmol of p-aminobenzoic acid, adjust the pH to 8 with saturated Na2CO3 solution, raise the temperature to 40-45°C, and react for 4 hours;

[0039] (4) Add 2 mmol of diethylaminoethyl methacrylate, maintain pH = 9 with saturated Na2CO3 solution, heat to 85-90°C, stir for 6 h, and cool to room temperature;

[0040] (5) Add 0.25 kg sodium stearate, 0.25 kg sodium dodecylbenzene sulfonate and 20 L water, stir and heat to 80°C;

[0041] (6) Add 20 kg of calcium carbonate powder with a mesh size of 2000, a whiteness of 93 (CIE), and an oil absorption value of 38 g / 100 g, stir for 15 min, filter, and dry to obtain high-activity, high-white calcium carbonate powder with an oil absorption value of 12 g / 100 g CaCO3 and a whiteness (CIE) of 97.2.

[0042] Through the oil absorption value and whiteness value experimental tests, the calcium carbonate powder modified whitening integrated auxiliary agent of the present invention has the effect of significantly reducing the oil absorption value and improving the whiteness of calcium carbonate powder with a mesh size of 800-2000 and a whiteness of 92-94.

[0043] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. The application of calcium carbonate powder modified whitening integrated additives consists of the following steps: (1) 1 mmol DSD acid, 10 mL water and saturated Na2CO3 solution were stirred until clear; (2) 2mmol of cyanuric chloride and 10mL of ice water, stir in an ice bath, slowly drop (1) into the mixture, and control the temperature at 3-5℃ to react for 1.5h; (3) Add 1 mmol of ethanolamine and 1 mmol of p-aminobenzoic acid, adjust the pH to 8 with saturated Na2CO3 solution, raise the temperature to 40-45°C, and react for 3.5 hours; (4) Add 2 mmol of diethylaminoethyl methacrylate, maintain pH = 9 with saturated Na2CO3 solution, raise the temperature to 85-90°C, stir and react for 6 hours, and cool to room temperature; (5) adding sodium stearate, sodium dodecylbenzene sulfonate and 20 L of water, heating and stirring evenly to obtain a modified whitening integrated additive; (6) Add 20 kg of calcium carbonate powder, stir, filter and dry to obtain high-activity and high-white calcium carbonate powder.

2. The application of the calcium carbonate powder modified whitening integrated auxiliary agent according to claim 1, characterized in that: The amount of sodium stearate in step (5) is 0.2-0.3 kg.

3. The application of the calcium carbonate powder modified whitening integrated auxiliary agent according to claim 1, characterized in that: The amount of sodium dodecylbenzene sulfonate described in step (5) is 0.2-0.3Kg.

4. The application of the calcium carbonate powder modified whitening integrated auxiliary agent according to claim 1, characterized in that: The heating temperature in step (5) is 80-85°C.

5. The application of the calcium carbonate powder modified whitening integrated auxiliary agent according to claim 1, characterized in that: The calcium carbonate powder in step (6) has a size of 800 to 2000 meshes, a CIE whiteness of 92 to 94, an oil absorption value of 33 to 38 g / 100 g, and a stirring time of 10 to 15 min.