Long-chain amide bicyclic borate surface modifier, synthesis method and application thereof

Abstract

The invention discloses a long-chain amide bicyclic borate surface modifier, which is synthesized by the following method: (1) taking octadecanoic acid and toluene, stirring, heating to 80 DEG C, dropping diethanolamine, completing the dropwise addition for 1h, and reflux water separation for 10h; (2) adding boric acid, heating to reflux water separation for 10h; (3) dropping 4 tert-butyl cyclohexanol, completing the dropwise addition for 1h, warming to reflux water separation for 18h, and removing the solvent and the remaining raw materials by vacuum distillation to obtain a long-chain amide bicyclic borate surface modifier. The present invention also discloses a synthetic method and application of a long-chain amide bicyclic borate surface modifier. The long-chain amide bicyclic borate surface modifier provided by the present invention introduces a large sterically hindered bicyclic, tert-butyl and long-chain amide groups on the B-O bond, significantly increases the steric effect, can effectively suppress the attack of water molecules, significantly reduces the oil absorption value of calcium carbonate powder and the influence on the whiteness of activated calcium carbonate, enhances practicality, and significantly improves the quality of activated calcium carbonate powder and the mechanical properties of its composite material.

Description

Technical Field

[0001] The present invention relates to a borate surface modifier, in particular to a long-chain amide bicyclic borate surface modifier and a synthesis method and application thereof. Background Art

[0002] Calcium carbonate powder is a high-quality filler and is widely used in industries such as rubber, plastics, papermaking, coatings, inks, and medicine. However, due to the hydrophilic and oleophobic nature of inorganic powders, they are difficult to disperse evenly in organic media, resulting in a decrease in the mechanical properties of the material. Therefore, a surface modifier must be added to activate it before filling. The central boron atom of the borate surface modifier has a unique valence electron configuration, which is more conducive to improving the mechanical properties of composite materials and has excellent properties that other surface modifiers do not have. However, ordinary borate surface modifiers are easily attacked by water molecules, hydrolyzed, and lose their surface modification effect, resulting in a higher oil absorption value and a lower whiteness value of the modified calcium carbonate powder, causing the dispersibility and fluidity of the activated calcium carbonate powder to deteriorate, seriously affecting the quality and mechanical properties of the calcium carbonate powder and its composite materials. Therefore, the application field of ordinary borate surface modifiers is greatly limited. Summary of the Invention

[0003] Ordinary borate surface modifiers are easily attacked by water molecules, hydrolyzed, and lose their surface modification effect, resulting in a large oil absorption value and a decrease in the whiteness value of the modified calcium carbonate powder, causing the dispersibility and fluidity of the activated calcium carbonate powder to deteriorate, seriously affecting the quality and mechanical properties of the calcium carbonate powder and its composite materials. The present invention introduces a large sterically hindered bicyclic ring, a tert-butyl group, and a long-chain amide group on the BO bond to synthesize a long-chain amide bicyclic borate surface modifier, which significantly increases the steric effect, can effectively inhibit the attack of water molecules, effectively inhibits hydrolysis, greatly reduces the oil absorption value of the calcium carbonate powder and the impact on the whiteness of the activated calcium carbonate, enhances practicality, and significantly improves the quality and mechanical properties of the activated calcium carbonate powder and its composite materials.

[0004] One of the purposes of the present invention is to provide a long-chain amide bicyclic borate surface modifier.

[0005] Specifically, the long-chain amide bicyclic borate surface modifier is synthesized by the following method:

[0006] (1) Stir and heat octadecanoic acid and toluene to 80°C, add diethanolamine dropwise over 1 hour, and reflux for 10 hours to separate the water.

[0007] (2) Add boric acid and heat under reflux to remove water for 10 hours;

[0008] (3) 4-tert-butyl cyclohexanol was added dropwise over 1 hour, and the temperature was raised to reflux for 18 hours to remove water. The solvent and the remaining raw materials were removed by distillation under reduced pressure to obtain a long-chain amide bicyclic borate surface modifier.

[0009] The molar ratio of octadecanoic acid, diethanolamine, boric acid and 4-tert-butyl cyclohexanol is 1:1:1:1-1.5.

[0010] The structural formula of the long-chain amide bicyclic borate surface modifier is Formula 1.

[0011]

[0012] A second object of the present invention is to provide a method for synthesizing the long-chain amide bicyclic borate surface modifier.

[0013] Specifically, the synthesis method of the long-chain amide bicyclic borate surface modifier comprises the following steps:

[0014] (1) Stir and heat octadecanoic acid and toluene to 80°C, add diethanolamine dropwise over 1 hour, and reflux for 10 hours to separate the water.

[0015] (2) Add boric acid and heat under reflux to remove water for 10 hours;

[0016] (3) 4-tert-Butyl cyclohexanol was added dropwise over 1 hour, and the temperature was raised to reflux for 18 hours to remove water. The solvent and the remaining raw materials were removed by distillation under reduced pressure to obtain a long-chain amide bicyclic borate surface modifier.

[0017] The molar ratio of octadecanoic acid, diethanolamine, boric acid and 4-tert-butyl cyclohexanol is 1:1:1:1-1.5.

[0018] A third object of the present invention is to provide an application of the long-chain amide bicyclic borate surface modifier.

[0019] Specifically, the application of long-chain amide bicyclic borate surface modifier is to take heavy calcium carbonate powder and place it in a modifier, heat, stir, and add long-chain amide bicyclic borate surface modifier for modification treatment, so as to obtain highly activated and low oil absorption calcium carbonate powder with excellent dispersibility and fluidity, and the oil absorption value is 13-16g / 100g CaCO3.

[0020] The amount of the added long-chain amide bicyclic borate surface modifier is 1.2-1.8% of the mass of the calcium carbonate powder.

[0021] The heating temperature is 80-90°C.

[0022] The stirring time is 15 to 20 minutes.

[0023] Long-chain amide bicyclic borate surface modifier and its synthesis method and application technology can significantly reduce the oil absorption value of activated calcium carbonate powder and its impact on the whiteness of activated calcium carbonate, improve its dispersibility and fluidity, and significantly enhance its hydrolysis stability, improve the mechanical properties of its composite materials, enhance practicality and expand the application field, and have significant economic and promotion value.

[0024] Technical effects of the present invention:

[0025] 1. The long-chain amide bicyclic borate surface modifier provided by the present invention introduces a large sterically hindered bicyclic ring, a tert-butyl group, and a long-chain amide group on the BO bond, which significantly increases the steric effect, can effectively inhibit the attack and hydrolysis of water molecules, greatly reduces the oil absorption value of calcium carbonate powder and the impact on the whiteness of activated calcium carbonate, enhances practicality, and significantly improves the quality and mechanical properties of activated calcium carbonate powder and its composite material.

[0026] 2. The long-chain amide bicyclic borate surface modifier provided by the present invention has a hydrolysis stability of 1392h tested by the open observation method, while the hydrolysis stability of ordinary borate surface modifiers is 3 to 48h, confirming that the long-chain amide bicyclic borate surface modifier has strong hydrolysis stability.

[0027] 3. The yield of the finished product of the method for synthesizing the long-chain amide bicyclic borate surface modifier provided by the present invention is 86-90%.

[0028] 4. After the long-chain amide bicyclic borate surface modifier provided by the present invention was used to modify the ground calcium carbonate powder, the whiteness value decreased by between 0.2 and 0.4, confirming that it had little effect on the whiteness of the calcium carbonate powder. In contrast, after the conventional borate surface modifier was used to modify the calcium carbonate powder, the whiteness value decreased by more than 1, confirming that it had a greater impact on the whiteness of the calcium carbonate powder. DETAILED DESCRIPTION

[0029] In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, a detailed description will be given below with reference to specific embodiments.

[0030] Example 1

[0031] (1) Octadecanoic acid (0.2 mol) and toluene (80 mL) were placed in a three-necked flask, stirred, and heated to 80°C. Diethanolamine (0.2 mol) was slowly added dropwise over 1 h, and the mixture was refluxed for 10 h to remove water.

[0032] (2) Add boric acid (0.2 mol) and heat under reflux to remove water for 10 h.

[0033] (3) 4-tert-Butyl cyclohexanol (0.2 mol) was slowly added dropwise over 1 h, and the temperature was raised to reflux for 18 h to remove water. The solvent and the remaining raw materials were removed by distillation under reduced pressure to obtain a long-chain amide bicyclic borate surface modifier with a yield of 86%.

[0034] (4) Calcium carbonate powder (1250 mesh, whiteness 95 (CIE), oil absorption value 35g / 100g) was treated with a long-chain amide bicyclic borate surface modifier. The addition amount was 1.2% of the powder mass. After heating to 80°C and stirring for 15 minutes, a highly activated calcium carbonate powder with low oil absorption value and excellent dispersibility and fluidity was obtained. Its oil absorption value was 15g / 100g CaCO3, the whiteness value was 94.7, and the whiteness value was reduced by 0.3.

[0035] (5) The activated calcium carbonate powder was filled into polypropylene in an amount of 28%, and was formed into standard specimens by mixing and injection molding. The tensile strength was measured to be 34.1 MPa and the flexural strength was 47.3 MPa according to the standard method.

[0036] Example 2

[0037] (1) Octadecanoic acid (0.2 mol) and toluene (80 mL) were placed in a three-necked flask, stirred, and heated to 80°C. Diethanolamine (0.2 mol) was slowly added dropwise over 1 h, and the mixture was refluxed for 10 h to remove water.

[0038] (2) Add boric acid (0.2 mol) and heat under reflux to remove water for 10 h.

[0039] (3) Slowly add 4-tert-butyl cyclohexanol (0.25 mol) dropwise for 1 hour, heat and reflux to remove water for 18 hours, and remove the solvent and remaining raw materials by distillation under reduced pressure to obtain a long-chain amide bicyclic borate surface modifier with a yield of 90%.

[0040] (4) Calcium carbonate powder (1250 mesh, whiteness 95 (CIE), oil absorption value 35g / 100g) was treated with a long-chain amide bicyclic borate surface modifier, with an addition amount of 1.6% of the powder mass, heated to 85°C, and stirred for 18 minutes to obtain a highly activated, low-oil-absorption calcium carbonate powder with excellent dispersibility and fluidity. Its oil absorption value was 13g / 100g CaCO3, the whiteness value was 94.8, and the whiteness value was reduced by 0.2.

[0041] (5) The activated calcium carbonate powder was filled into polypropylene in an amount of 28%, and was formed into standard specimens by mixing and injection molding. The tensile strength was measured to be 35.7 MPa and the flexural strength was 48.6 MPa according to the standard method.

[0042] Example 3

[0043] (1) Octadecanoic acid (0.2 mol) and toluene (80 mL) were placed in a three-necked flask, stirred, and heated to 80°C. Diethanolamine (0.2 mol) was slowly added dropwise over 1 h, and the mixture was refluxed for 10 h to remove water.

[0044] (2) Add boric acid (0.2 mol) and heat under reflux to remove water for 10 h.

[0045] (3) Slowly add 4-tert-butyl cyclohexanol (0.3 mol) dropwise for 1 hour, heat and reflux to remove water for 18 hours, and remove the solvent and remaining raw materials by distillation under reduced pressure to obtain a long-chain amide bicyclic borate surface modifier with a yield of 87%.

[0046] (4) Calcium carbonate powder (1250 mesh, whiteness 95 (CIE), oil absorption value 35g / 100g) was treated with a long-chain amide bicyclic borate surface modifier. The addition amount was 1.8% of the powder mass. After heating at 90°C and stirring for 20 minutes, a highly activated calcium carbonate powder with low oil absorption value and excellent dispersibility and fluidity was obtained. Its oil absorption value was 16g / 100g CaCO3, the whiteness value was 94.6, and the whiteness value was reduced by 0.4.

[0047] (5) The activated calcium carbonate powder was filled into polypropylene in an amount of 28%, and was formed into standard specimens by mixing and injection molding. The tensile strength was measured to be 33.9 MPa and the flexural strength was 47.2 MPa according to the standard method.

[0048] After calcium carbonate powder (1250 mesh, whiteness 95 (CIE), oil absorption 35g / 100g) was modified with a common borate surface modifier, the oil absorption was 20g / 100g CaCO3, the whiteness was 93.7, and the whiteness decreased by 1.3.

[0049] The above experimental data proves that the long-chain amide bicyclic borate surface modifier provided by the present invention can not only effectively surface-modify calcium carbonate powder, significantly reduce the oil absorption value and weaken the impact on the whiteness of activated calcium carbonate powder, improve dispersibility and fluidity, but also effectively solve the defect of easy hydrolysis of ordinary borate surface modifiers, improve the mechanical properties of composite materials, enhance practicality, and expand the application field.

[0050] It should be noted that the above is a preferred embodiment of the present invention. For those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be considered as the scope of protection of the present invention.

Claims

1. A long-chain amide bicyclic borate surface modifier, characterized in that: Synthesized by the following method: (1) Stir and heat octadecanoic acid and toluene to 80°C, add diethanolamine dropwise over 1 hour, and reflux for 10 hours to separate the water. (2) Add boric acid and heat under reflux to remove water for 10 hours; (3) 4-tert-Butyl cyclohexanol was added dropwise over 1 hour, and the temperature was raised to reflux for 18 hours to remove water. The solvent and the remaining raw materials were removed by distillation under reduced pressure to obtain a long-chain amide bicyclic borate surface modifier.

2. The long-chain amide bicyclic borate surface modifier according to claim 1, characterized in that: The molar ratio of octadecanoic acid, diethanolamine, boric acid and 4-tert-butyl cyclohexanol is 1:1:1:1-1.

5.

3. A method for synthesizing a long-chain amide bicyclic borate surface modifier, characterized in that: The following steps are involved: (1) Stir and heat octadecanoic acid and toluene to 80°C, add diethanolamine dropwise over 1 hour, and reflux for 10 hours to separate the water. (2) Add boric acid and heat under reflux to remove water for 10 hours; (3) 4-tert-Butyl cyclohexanol was added dropwise over 1 hour, and the temperature was raised to reflux for 18 hours to remove water. The solvent and the remaining raw materials were removed by distillation under reduced pressure to obtain a long-chain amide bicyclic borate surface modifier.

4. The method for synthesizing the long-chain amide bicyclic borate surface modifier according to claim 3, wherein: The molar ratio of octadecanoic acid, diethanolamine, boric acid and 4-tert-butyl cyclohexanol is 1:1:1:1-1.

5.

5. The use of the long-chain amide bicyclic borate surface modifier according to claim 1, characterized in that: Heavy calcium carbonate powder is placed in a modifier, heated and stirred, and a long-chain amide bicyclic borate surface modifier is added for modification to obtain highly activated and low oil absorption calcium carbonate powder.

6. The use of the long-chain amide bicyclic borate surface modifier according to claim 5, characterized in that: The amount of the added long-chain amide bicyclic borate surface modifier is 1.2-1.8% of the mass of the calcium carbonate powder.

7. The use of the long-chain amide bicyclic borate surface modifier according to claim 5, characterized in that: The heating temperature is 80-90°C.

8. The use of the long-chain amide bicyclic borate surface modifier according to claim 5, characterized in that: The stirring time is 15 to 20 minutes.

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