Application of boron trifluoride methanol complex_industrial additives

Background and Overview

Boron trifluoride methanol complex, also known as boron trifluoride methanol, is a chemical reagent that can be used as a raw material for organic chemical synthesis.

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1. Used in the synthesis of 2,3,4,4′-tetrahydroxybenzophenone

2,3,4,4′-Tetrahydroxybenzophenone (THBP) is an important organic intermediate that can be used in photoresists, pharmaceutical intermediates, and ultraviolet absorbers in the microelectronic integrated circuit industry. agents, resin stabilizers, dyes, etc. Especially today with the rapid development of the microelectronics industry, the demand for THBP used as an intermediate for UV positive photoresist sensitizer has increased sharply. CN201010171290.8 reports a method for synthesizing 2,3,4,4′-tetrahydroxybenzophenone, using pyrogallic acid and p-hydroxybenzoic acid as raw materials, and performing an acylation reaction in the presence of a catalyst. After the reaction is completed Cool, adjust the pH value to neutral, precipitate crystals, filter, wash and dry to obtain 2,3,4,4′-tetrahydroxybenzophenone crude product, which is then decolorized and refined with activated carbon to obtain 2,3,4, Refined product of 4′-tetrahydroxybenzophenone, the catalyst is boron trifluoride methanol solution, and the mass volume ratio of pyrogallic acid and boron trifluoride methanol solution is 1:4g/mL.

Beneficial effects:

(1) The catalyst boron trifluoride methanol solution selected in the present invention is safer than the boron trifluoride ether that has been reported to be used. Although both are boron trifluoride catalysts, their complexes are methanol and diethyl ether respectively. Methanol has a boiling point of 16°C, a flash point of -45°C, and an explosion limit of 6.0 to 36.5% (volume percentage); while ether has a boiling point of 34.6°C, is highly volatile, and is anesthetic to humans, with a flash point of -45°C and an explosion limit of 1.85 to 48.0%. .

(2) In the synthesis process of the present invention, the methanol solution of boron trifluoride is both a catalyst and a solvent. There is no need to add other solvents such as tetrachloroethane as in the usual use of boron trifluoride ether for catalysis, which greatly reduces The amount of raw materials and waste liquid is reduced, reducing preparation costs and reducing pollution.

(3) The reaction time of the present invention is short. When reacting at 120°C, the reaction can be completed within 2 hours. Compared with the reported method with a reaction time of 10 hours, the reaction time is greatly saved, which is useful in industrial production. It can greatly save energy consumption and improve efficiency. The present invention can complete the reaction at a reaction temperature of 100°C. Compared with the reported method, the reaction temperature is 120°C, which is 20°C lower. This alone will save a lot of energy consumption in actual factory production.

(4) The present invention uses boron trifluoride methanol solution as a catalyst to synthesize 2,3,4,4′-tetrahydroxybenzophenone. The reaction conditions are mild, the process is simple and easy to implement, and consumption and pollution are relatively low.

2. Used to synthesize a fluorine-containing polyether polyol

Fluorinated polyurethane is widely used in antifouling, anticorrosion, medicine and other fields due to its excellent corrosion resistance, biocompatibility, low surface energy and surface fluorine enrichment. CN201410244115.5 Provides a synthesis method of fluorine-containing polyether polyol. The synthesis method adopts a special cationic initiating system, thereby overcoming the high activity of ion pair active species during the cationic polymerization process, the fast reaction rate, and the molecular weight of the reactants. Disadvantages include instability, broadened dispersion index, and many by-products.

Specific steps include the following:

(1). Add a mixture of solvent and tetrahydrofuran to a reactor with a stirring device; the ratio of solvent to tetrahydrofuran, that is, solvent: tetrahydrofuran is 10ml:0.9-1.8g; the solvent is dichloromethane, A mixture of chloroform or dichloromethane and chloroform; the mixture of dichloromethane and chloroform is calculated based on the volume ratio, that is, a mixture of dichloromethane: chloroform of 3:1. Liquid;

(2). Pour in protective gas nitrogen, control the temperature to 33-39°C, add a cationic initiator system, stir and age at a speed of 300-500r/min for 10-30min to obtain the intermediate product;

The above-mentioned cationic initiating system is a mixed alcohol formed by the volume ratio of co-initiator ethylene glycol and cationic initiator boron trifluoride methanol, that is, the ratio of ethylene glycol: boron trifluoride methanol is 1:2.08 ;

(3). Use a constant pressure dropping funnel to dropwise add 3-(2,2,3,3-tetrafluoropropoxy to the intermediate product obtained in step (2) at a speed of 0.05-0.1ml/s. base)-1,2-Epoxypropane, control the temperature to 39°C, stir the reaction for 6 hours, the reaction liquid is clear and viscous; the added 3-(2,2,3,3-tetrafluoropropoxy)-1, The amount of 2-epoxypropane is calculated according to the molar ratio to tetrahydrofuran, that is, the molar ratio of 3-(2,2,3,3-tetrafluoropropoxy)-1,2-epoxypropane:tetrahydrofuran is 1: 0.6;

(4). Add deionized water 3-4 times the amount of the reaction solution to the reaction solution obtained in step (3) to terminate the polymerization reaction, and then wash the reaction solution with distilled water of the same volume as the reaction solution to remove unreacted The substance is allowed to stand for layering, and the lower layer of milky white viscous solution is removed. At 110°C, the stirring speed is controlled to 300-500r/min and vacuum dehydration is carried out for 3 hours while stirring. During the vacuum dehydration process, the vacuum degree is controlled to 10kp, and then naturally After cooling to room temperature, a colorless and transparent viscous liquid, namely fluorinated polyether polyol, is finally obtained.

The preparation method of the above-obtained fluorine-containing polyether polyol, because the obtained fluorine-containing polyether polyol has the characteristics of controllable molecular weight and narrow molecular weight distribution, it will become the first choice for low-fluorine high-performance fluorine-containing polyurethane (FPU). Key raw materials.

3. Used to prepare a biodegradable color printing ink additive

CN201611214763.1 provides a biodegradable color printing ink additive to solve the problems raised in the above background technology. In order to achieve the above purpose, the present invention provides the following technical solution: a biodegradable color printing ink additive, the main raw materials in parts by weight are: 5-10 parts of menthol, 2-6 parts of blue calyxin, and Chasmanlin 17-22 parts, 13-dehydroxyaplastine 20-30 parts, gomisin G 8-17 parts, anacardiin 15-25 parts, scopolamine 11-14 parts, 2-chloro-6-fluorophenol 5-9 parts, 7-12 parts of chloromethyl methyl ether, 0.5-0.8 parts of boron trifluoride methanol, 2-4 parts of pentobarbital sodium salt, 2-aminophenol-4-(2-carboxy)sulfonyl 2-4 parts of aniline, 2-4 parts of cis-dichlorobis(diethyl sulfide) platinum. The beneficial effects of the present invention are: the ink additive is environmentally friendly, harmless, safe, stable in nature, and has good printing effect; when recycling waste products, under the action of the decolorizing agent, the ink can be quickly decolored, which eliminates the It solves the problem of volatilization of organic solvents in oil-based inks, and also solves the problems of difficulty in deinking waste paper and serious sewage discharge.

Main reference materials

[1] CN201010171290.8 A method of synthesizing 2,3,4,4′-tetrahydroxybenzophenone

[2] CN201410244115.5 Synthesis method of fluorine-containing polyether polyol

[3] CN201611214763.1 A biodegradable color printing ink additive