High-yield boron trifluoride monoethylamine complex as well as preparation method and application thereof

Abstract

The invention relates to the technical field of complex preparation, and provides a high-yield boron trifluoride monoethylamine complex as well as a preparation method and application thereof. A preparation method of a high-yield boron trifluoride monoethylamine complex comprises the following steps: S1, charging boron trifluoride into an ethylamine solution, and reacting while charging to obtain a reaction solution; s2, filtering the reaction liquid to obtain a filtered substance, and washing and drying the filtered substance to obtain a boron trifluoride monoethylamine complex; in the ethylamine solution, the solvent comprises ethanol and nitriles. According to the technical scheme, the problems of low purity and low yield of the boron trifluoride monoethylamine complex in the prior art are solved.

Description

Technical Field

[0001] The invention relates to the technical field of complex preparation, and in particular to a high-yield boron trifluoride monoethylamine complex and a preparation method and application thereof. Background Art

[0002] In the context of the rapid development of industrial manufacturing and material application, epoxy resin is widely used in many key industries such as aerospace, automobile manufacturing, and electronic appliances due to its excellent mechanical properties, chemical stability, and good bonding properties. As one of the key factors that determine the final performance of epoxy resin, epoxy resin curing agent plays a vital role.

[0003] Boron trifluoride monoethylamine complex is gradually emerging in epoxy resin curing agent system. In the field of aerospace, aircraft structural parts need to withstand extreme temperatures, pressures and complex mechanical environments. Epoxy resin, as a matrix material, can significantly enhance the strength and toughness of structural parts after being cured with boron trifluoride monoethylamine complex, ensuring reliability under high-altitude and high-speed flight conditions, effectively reducing structural weight and improving fuel efficiency. In automobile manufacturing, engine peripheral parts, body frames, etc. use epoxy resin cured with this complex, which can not only withstand the high temperature generated by the engine, but also resist the impact caused by road bumps, ensuring the high performance and durability of the car. In the field of electronics and electrical appliances, chip packaging, circuit board protection, etc. have extremely high requirements for the insulation and thermal conductivity of materials. Boron trifluoride monoethylamine complex promotes the curing of epoxy resin to form a tight molecular structure, optimize electrical properties, prevent short circuits and leakage, and ensure the stable operation of electronic equipment.

[0004] However, at this stage, there are many problems that need to be solved around the use of boron trifluoride monoethylamine complex as epoxy resin curing agent. On the one hand, the purity of the complex produced by the traditional preparation method is not high, and the impurity components will interfere with the molecular cross-linking reaction during the epoxy resin curing process, resulting in defects such as bubbles and cracks in the cured product, which seriously affects the mechanical strength and insulation properties of the material. On the other hand, low yield means high production costs, which limits its large-scale industrial application. The unstable supply of raw materials and the difficult control of reaction conditions make it difficult to stably obtain sufficient and high-quality boron trifluoride monoethylamine complexes during the production process, which cannot meet the growing industrial needs.

[0005] In summary, the existing preparation methods of boron trifluoride monoethylamine complex have the problems of low purity and low yield. Therefore, studying a high-purity and high-yield preparation method of boron trifluoride monoethylamine complex is of vital importance for promoting the in-depth application of epoxy resin in various key industries, improving product quality and reducing costs. Summary of the invention

[0006] The invention provides a high-yield boron trifluoride monoethylamine complex and a preparation method and application thereof, which solve the problems of low purity and low yield of the boron trifluoride monoethylamine complex in the related art.

[0007] The technical solution of the present invention is as follows: The present invention provides a method for preparing a high-yield boron trifluoride monoethylamine complex, comprising the following steps: S1, charging boron trifluoride into ethylamine solution, reacting while charging, to obtain a reaction solution; S2, filtering the reaction solution to obtain a filtrate, washing the filtrate, and drying the filtrate to obtain a boron trifluoride monoethylamine complex; In the ethylamine solution, the solvent includes ethanol and nitriles.

[0008] As a further technical solution, the concentration of the ethylamine solution is 3-5 mol / L.

[0009] As a further technical solution, the molar ratio of the boron trifluoride to ethylamine is 1.05-1.10:1.

[0010] As a further technical solution, in the solvent, the volume ratio of ethanol to nitrile is 9:2-4; The nitrile includes one of butyronitrile and acetonitrile.

[0011] The present invention further improves the purity and yield of the boron trifluoride monoethylamine complex by adjusting the volume ratio of ethanol to nitrile to 9:2-4.

[0012] As a further technical solution, in the solvent, the volume ratio of ethanol to nitriles is 3:1.

[0013] The present invention further improves the purity and yield of the boron trifluoride monoethylamine complex by adjusting the volume ratio of ethanol to nitrile to 3:1.

[0014] As a further technical solution, the filling rate of the boron trifluoride is 15-25 kg / h.

[0015] As a further technical solution, the reaction temperature is 1~5°C.

[0016] As a further technical solution, the washing specifically comprises: washing with a mixed detergent; The mixed detergent is a mixed detergent of ether and 1,2-propylene glycol; The mass volume ratio of the filtrate to the mixed detergent is 1 g:5-8 mL.

[0017] The invention uses a mixed solvent of ether and 1,2-propylene glycol as a mixed detergent, thereby further improving the purity and yield of the boron trifluoride monoethylamine complex.

[0018] As a further technical solution, the mixed detergent is a mixed detergent of ether and 1,2-propylene glycol in a volume ratio of 5 to 9:2.

[0019] The present invention further improves the purity and yield of the boron trifluoride monoethylamine complex by adjusting the volume ratio of ether to 1,2-propylene glycol to 5-9:2.

[0020] The invention also provides a high-yield boron trifluoride monoethylamine complex, which is prepared by the preparation method of the high-yield boron trifluoride monoethylamine complex.

[0021] The present invention also proposes the boron trifluoride monoethylamine complex prepared by the method for preparing the high-yield boron trifluoride monoethylamine complex or the application of the high-yield boron trifluoride monoethylamine complex in epoxy resin curing agent.

[0022] The working principle and beneficial effects of the present invention are: In the present invention, a mixed solvent of ethanol and nitriles is used as a reaction solvent, and ethanol and nitriles produce a synergistic effect, thereby improving the purity and yield of the boron trifluoride monoethylamine complex. As a curing agent for epoxy resin, the boron trifluoride monoethylamine complex can produce more ether bonds with the epoxy resin, which is very important for the impact resistance of the epoxy resin and the bonding strength with other materials. Therefore, improving the purity and yield of the boron trifluoride monoethylamine complex is very important for improving the performance of the epoxy resin. Using a high-purity boron trifluoride monoethylamine complex reduces the possibility of cracking or falling off of the epoxy resin during use. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] Example 1 A method for preparing a high-yield boron trifluoride monoethylamine complex comprises the following steps: S1. Add boron trifluoride into a 5 mol / L ethylamine solution (10 L) at a rate of 25 kg / h, reacting at 5° C. to obtain a reaction solution; S2, filtering the reaction solution to obtain a filtrate, washing the filtrate with a detergent, and drying to obtain a boron trifluoride monoethylamine complex; In the ethylamine solution, the solvent is a mixed solution of ethanol and butyronitrile in a volume ratio of 3:2; The molar ratio of boron trifluoride to ethylamine is 1.10:1; The detergent was ether; The mass volume ratio of the filtrate to the detergent is 1 g:8 mL.

[0025] Example 2 A method for preparing a high-yield boron trifluoride monoethylamine complex comprises the following steps: S1. Add boron trifluoride into 3 mol / L ethylamine solution (10 L) at a rate of 15 kg / h, reacting at 1°C to obtain a reaction solution; S2, filtering the reaction solution to obtain a filtrate, washing the filtrate with a detergent, and drying to obtain a boron trifluoride monoethylamine complex; In the ethylamine solution, the solvent is a mixed solution of ethanol and acetonitrile in a volume ratio of 10:1; The molar ratio of boron trifluoride to ethylamine is 1.05:1; The detergent was ether; The mass volume ratio of the filtrate to the detergent is 1 g:5 mL.

[0026] Example 3 A method for preparing a high-yield boron trifluoride monoethylamine complex comprises the following steps: S1. Add boron trifluoride into 4 mol / L ethylamine solution (10 L) at a rate of 20 kg / h, reacting at 3°C ​​to obtain a reaction solution; S2, filtering the reaction solution to obtain a filtrate, washing the filtrate with a detergent, and drying to obtain a boron trifluoride monoethylamine complex; In the ethylamine solution, the solvent is a mixed solution of ethanol and acetonitrile in a volume ratio of 9:5; The molar ratio of boron trifluoride to ethylamine is 1.08:1; The detergent was ether; The mass volume ratio of the filtrate to the detergent is 1 g:5 mL.

[0027] Example 4 The only difference between this embodiment and embodiment 3 is that in the ethylamine solution of this embodiment, the solvent is a mixed solution of ethanol and acetonitrile in a volume ratio of 9:1.

[0028] Example 5 The only difference between this embodiment and embodiment 3 is that in the ethylamine solution of this embodiment, the solvent is a mixed solution of ethanol and acetonitrile in a volume ratio of 9:2.

[0029] Example 6 The only difference between this embodiment and embodiment 3 is that in the ethylamine solution of this embodiment, the solvent is a mixed solution of ethanol and acetonitrile in a volume ratio of 3:1.

[0030] Example 7 The only difference between this embodiment and embodiment 3 is that in the ethylamine solution of this embodiment, the solvent is a mixed solution of ethanol and acetonitrile in a volume ratio of 9:4.

[0031] Example 8 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is 1,2-propylene glycol.

[0032] Example 9 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of acetone and 1,2-propylene glycol in a volume ratio of 2:1.

[0033] Example 10 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of ether and chloroform in a volume ratio of 2:1.

[0034] Embodiment 11 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of acetone and chloroform in a volume ratio of 2:1.

[0035] Example 12 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of ether and 1,2-propylene glycol in a volume ratio of 5:1.

[0036] Embodiment 13 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of ether and 1,2-propylene glycol in a volume ratio of 2:1.

[0037] Embodiment 14 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of ether and 1,2-propylene glycol in a volume ratio of 5:2.

[0038] Embodiment 15 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of ether and 1,2-propylene glycol in a volume ratio of 7:2.

[0039] Example 16 The only difference between this embodiment and embodiment 3 is that the detergent in this embodiment is a mixed detergent of diethyl ether and 1,2-propylene glycol in a volume ratio of 9:2.

[0040] Comparative Example 1 The difference between this comparative example and Example 2 is that the solvent in the ethylamine solution of this comparative example is methyl chloride.

[0041] Comparative Example 2 The difference between this comparative example and Example 2 is that the solvent in the ethylamine solution of this comparative example is chloroform.

[0042] Comparative Example 3 The difference between this comparative example and Example 2 is that the solvent in the ethylamine solution of this comparative example is ethanol.

[0043] Comparative Example 4 The difference between this comparative example and Example 2 is that, in the ethylamine solution of this comparative example, the solvent is acetonitrile.

[0044] Comparative Example 5 The difference between this comparative example and Example 2 is that in the ethylamine solution of this comparative example, the solvent is a mixed solution of methyl chloride and ethanol in a volume ratio of 10:1.

[0045] Comparative Example 6 The difference between this comparative example and Example 2 is that in the ethylamine solution of this comparative example, the solvent is a mixed solution of chloroform and acetonitrile in a volume ratio of 10:1.

[0046] Test example The boron trifluoride monoethylamine complexes prepared in Examples 1 to 16 and Comparative Examples 1 to 6 were tested for purity and yield. The test results are shown in Table 1.

[0047] The purity test method is as follows: weigh 1 g of the boron trifluoride monoethylamine complex sample prepared in each example and comparative example and 3 g of sodium fluoride, put them into a 50 mL platinum crucible that has been weighed at 160°C, add 10 mL of pure water to the crucible, crush, stir, evaporate the platinum crucible to dryness, until constant weight, and weigh it.

[0048] a={[(W2-W1-W0) / G]×100%-N}×1.664 a is the purity of boron trifluoride monoethylamine complex; W2 is the mass of the reaction mixture + crucible; W1 is the mass of sodium fluoride; W0 is the mass of the empty crucible; G is the mass of the sample; 1.664 is the coefficient for converting boron trifluoride to boron trifluoride monoethylamine complex; N is the percentage of non-volatile impurities. The calculation method of N is as follows: weigh 3g of the sample by the reduction method into a platinum crucible that has been constant at 600℃, first place it in a fume hood and heat it on an electric furnace until the smoke stops, then move it into a high-temperature furnace and burn it at 600℃ for 30 minutes, take it out, cool it, weigh it, and burn it for another 30 minutes until it reaches constant weight. The non-volatile impurities are calculated as follows: N=(G2-G1) / G×100%, G2 is the non-volatile residue + crucible mass; G1 is the mass of the empty crucible, and G is the mass of the sample; b = (a × m1 / M1) / (ρ × V); b is the yield; a is the measured purity of boron trifluoride monoethylamine complex; m1 is the mass of boron trifluoride monoethylamine complex; M1 is the molar mass of boron trifluoride monoethylamine complex; ρ is the concentration of ethylamine solution; V is the volume of ethylamine solution.

[0049]

[0050] Comparing Example 2 with Comparative Examples 1 to 6, it is shown that in the present invention, by using a mixed solvent of ethanol and nitriles as a reaction solvent, the two solvents produce a synergistic effect, thereby improving the purity and yield of the boron trifluoride monoethylamine complex.

[0051] Comparing Examples 5 to 7 with Examples 3 to 4, it is shown that when the volume ratio of ethanol to nitriles in the ethylamine solution is adjusted to 9:2 to 4 in the present invention, the purity and yield of the boron trifluoride monoethylamine complex are further improved. Comparing Examples 3 and 8 to 11 with Examples 12 to 16, it is shown that the use of a mixed detergent of ether and 1,2-propylene glycol in the present invention further improves the purity and yield of the boron trifluoride monoethylamine complex compared to other detergents. Comparing Examples 12 to 13 with Examples 14 to 16, it is shown that when the volume ratio of ether to 1,2-propylene glycol in the mixed detergent is adjusted to 5 to 9:2 in the present invention, the purity and yield of the boron trifluoride monoethylamine complex are further improved.

[0052] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a high-yield boron trifluoride monoethylamine complex, characterized in that: The following steps are involved: S1, charging boron trifluoride into ethylamine solution, reacting while charging, to obtain a reaction solution; S2, filtering the reaction solution to obtain a filtrate, washing the filtrate, and drying the filtrate to obtain a boron trifluoride monoethylamine complex; In the ethylamine solution, the solvent includes ethanol and nitriles.

2. The method for preparing a high-yield boron trifluoride monoethylamine complex according to claim 1, characterized in that: The concentration of the ethylamine solution is 3-5 mol / L.

3. The method for preparing a high-yield boron trifluoride monoethylamine complex according to claim 1, characterized in that: The molar ratio of the boron trifluoride to ethylamine is 1.05-1.10:

1.

4. The method for preparing a high-yield boron trifluoride monoethylamine complex according to claim 1, characterized in that: In the solvent, the volume ratio of ethanol to nitrile is 9:2-4; The nitrile includes one of butyronitrile and acetonitrile.

5. The method for preparing a high-yield boron trifluoride monoethylamine complex according to claim 1, characterized in that: The filling rate of the boron trifluoride is 15-25 kg / h.

6. The method for preparing a high-yield boron trifluoride monoethylamine complex according to claim 1, characterized in that: The reaction temperature is 1-5°C.

7. The method for preparing a high-yield boron trifluoride monoethylamine complex according to claim 1, characterized in that: The washing specifically comprises: washing with a mixed detergent; The mixed detergent is a mixed detergent of ether and 1,2-propylene glycol; The mass volume ratio of the filtrate to the mixed detergent is 1 g:5-8 mL.

8. The method for preparing a high-yield boron trifluoride monoethylamine complex according to claim 7, characterized in that: The mixed detergent is a mixed detergent of ether and 1,2-propylene glycol in a volume ratio of 5 to 9:

2.

9. A high-yield boron trifluoride monoethylamine complex, characterized in that: The boron trifluoride monoethylamine complex is prepared by the method for preparing a high-yield boron trifluoride monoethylamine complex according to any one of claims 1 to 8.

10. Use of the boron trifluoride monoethylamine complex obtained by the method for preparing a high-yield boron trifluoride monoethylamine complex according to any one of claims 1 to 8 or the high-yield boron trifluoride monoethylamine complex according to claim 9 in an epoxy resin curing agent.

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