Preparation method of tetrahydrofurfuryl alcohol acrylate monomer

Abstract

The invention discloses a preparation method of a tetrahydrofurfuryl alcohol acrylate monomer, which comprises the following steps of: reacting tetrahydrofurfuryl alcohol and acryloyl chloride serving as raw materials to synthesize tetrahydrofurfuryl alcohol acrylate, and finally neutralizing and distilling under reduced pressure to obtain a high-purity product. The method has the advantages of mild reaction conditions, high conversion rate (greater than or equal to 98%), product purity greater than or equal to 98%, no need of complex post-treatment process, reduction of wastewater generation, greenness and no pollution. The obtained tetrahydrofurfuryl alcohol acrylate can be used as a reactive diluent or a crosslinking monomer of photocureable coating and printing ink, and has low viscosity, high reaction activity and excellent wettability.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of tetrahydrofurfuryl alcohol acrylate monomer and belongs to the field of organic synthesis. BACKGROUND

[0002] Tetrahydrofurfuryl alcohol acrylate is an acrylate monomer containing a furan ring structure, has low viscosity, high reactivity and good pigment wetting property, and is widely applied to the fields of UV coatings, inks, electronic packaging materials and the like. Traditional preparation methods mostly adopt direct esterification of tetrahydrofurfuryl alcohol and acrylic acid, but problems such as high reaction temperature (more than 100 DEG C is needed), easy occurrence of self-polymerization of acrylic acid, low product purity, strong hydrophilicity and low material yield after water washing exist. In addition, strong acid catalysts (such as concentrated sulfuric acid) are often used in the existing process, which leads to equipment corrosion and wastewater treatment difficulty. SUMMARY

[0003] The application significantly improves the reaction efficiency and product purity by optimizing the reaction path and adopting reaction of acryloyl chloride and tetrahydrofurfuryl alcohol under low-temperature conditions.

[0004] Technical advantages thereof include: low-temperature high efficiency: the reaction temperature is less than or equal to 60 DEG C, and side reactions caused by high temperature are avoided; High selectivity: the reaction of acyl chloride and hydroxyl group is fast, and side reactions are few; Green and environmental protection: no strong acid catalyst is needed, wastewater pollution is reduced, and equipment damage is reduced; Product is easy to purify: high-purity monomer can be obtained through simple reduced pressure distillation.

[0005] The technical scheme adopted by the application is as follows: A preparation method of tetrahydrofurfuryl alcohol acrylate monomer comprises the following steps: (1) adding activated carbon, tetrahydrofurfuryl alcohol, an organic solvent and a catalyst into a flask; (2) slowly adding a certain mass of acryloyl chloride into step (1); (3) after the addition is completed, adding a certain amount of a polymerization inhibitor, and heating and reacting for a period of time; (4) after the reaction is completed, supplementing a certain amount of solvent into the material, neutralizing the PH of the material to 6-7 by using an alkaline aqueous solution, removing the water phase by liquid separation, and distilling the organic phase under reduced pressure, collecting the distillate under a certain temperature and vacuum degree, and obtaining a colorless transparent liquid product.

[0006] As a preferred scheme, the preparation method of tetrahydrofurfuryl alcohol acrylate monomer comprises the following steps: (1) adding activated carbon, tetrahydrofurfuryl alcohol, an organic solvent and a catalyst into a flask; (2) slowly add a certain mass of acryloyl chloride to step (1), the dropwise time is 2-5 h, and the molar ratio of tetrahydrofurfuryl alcohol to acryloyl chloride is 1:1-1.1; (3) after the dropwise addition is completed, a certain amount of a polymerization inhibitor is added, the temperature is increased to 20-60 DEG C, and the reaction is continuously carried out for 1-6 h; (4) after the reaction is completed, a certain amount of a solvent is added to the material, the material is neutralized to a pH of 6-7 by using an alkaline aqueous solution, the water phase is removed by liquid separation, the organic phase is distilled under reduced pressure, and the distillate under a certain temperature and vacuum degree is collected, so that a colorless transparent liquid product is obtained.

[0007] As a preferred scheme, in the preparation method of the tetrahydrofurfuryl acrylate monomer, the organic solvent in step (1) is at least one or a mixture of several of toluene, dichloromethane, dichloroethane, dimethylbenzene, propylene glycol methyl ether acetate, cyclohexane and DMF.

[0008] As a preferred scheme, in the preparation method of the tetrahydrofurfuryl acrylate monomer, the catalyst in step (1) is triethylamine, pyridine or 4-dimethylaminopyridine.

[0009] As a preferred scheme, in the preparation method of the tetrahydrofurfuryl acrylate monomer, the polymerization inhibitor in step (3) is at least one or a mixture of several of p-hydroxyanisole, hydroquinone, copper chloride, copper sulfate, copper nitrate or the above-mentioned copper salts with crystal water.

[0010] As a preferred scheme, in the preparation method of the tetrahydrofurfuryl acrylate monomer, the solvent in step (4) is the same as the solvent used in step (1), and the added amount is 20-50% of the total mass.

[0011] As a preferred scheme, in the preparation method of the tetrahydrofurfuryl acrylate monomer, the alkaline aqueous solution in step (4) is at least one or a mixture of several of a 5-20% mass fraction sodium carbonate aqueous solution and a 2-30% mass fraction sodium hydroxide aqueous solution.

[0012] As a preferred scheme, in the preparation method of the tetrahydrofurfuryl acrylate monomer, the distillate collected in step (4) has a temperature of 90-120 DEG C and a vacuum degree of 100-500 Pa.

[0013] The present application has the following beneficial effects: The present application creatively uses tetrahydrofurfuryl alcohol and acryloyl chloride as raw materials to synthesize tetrahydrofurfuryl acrylate in an organic solvent, and finally obtains a high-purity product through neutralization and reduced-pressure distillation. The method has mild reaction conditions, does not require high-temperature reaction, has a short reaction time, has a high product conversion rate (≥98%), has a product purity of ≥98%, does not require a complex post-treatment process, reduces the generation of waste water, and is green and pollution-free. Attached Figure Description

[0014] Figure 1 The image shows the GC chromatogram of the tetrahydrofurfuryl acrylate monomer prepared in Example 1.

[0015] Figure 2 The GC chromatogram of the tetrahydrofurfuryl acrylate monomer prepared in Comparative Example 1 is shown. Detailed Implementation

[0016] The present invention will be further described below with reference to embodiments, but the embodiments do not constitute a limitation on the scope of protection of the present invention.

[0017] Example 1 A method for preparing tetrahydrofurfuryl acrylate monomer includes the following steps: (1) Add 1g activated carbon, 408g tetrahydrofurfuryl alcohol, 256g xylene and 28g pyridine to a three-necked flask equipped with a stirring device.

[0018] (2) Slowly add 369g of acryloyl chloride to step (1) for 2 hours.

[0019] (3) After the addition is complete, add 0.3g of copper chloride and 0.2g of p-hydroxyanisole, heat to 30℃, and continue the reaction for 3h.

[0020] (4) After the reaction is complete, 400g of toluene is added to the material, and the pH of the material is neutralized to 7 with a 15% sodium carbonate aqueous solution. The aqueous phase is removed by separation, and the organic phase is distilled under reduced pressure. The fractions at 95℃~110℃ and 400Pa vacuum are collected to obtain a colorless and transparent liquid product with a yield of 99.1%.

[0021] (5) The GC diagram of the product is shown below. Figure 1 As shown, the purity is 98.3115%.

[0022] Example 2 A method for preparing tetrahydrofurfuryl acrylate monomer includes the following steps: (1) Add 1g activated carbon, 408g tetrahydrofurfuryl alcohol, 260g xylene and 35g pyridine to a three-necked flask equipped with a stirring device.

[0023] (2) Slowly add 379g of acryloyl chloride to step (1) for 3 hours.

[0024] (3) After the addition is complete, add 0.3g of copper chloride and 0.2g of p-hydroxyanisole, heat to 50℃, and continue the reaction for 3h.

[0025] (4) After the reaction is completed, 600 g of toluene is added to the material, the PH of the material is neutralized to 7 by using a 15% by mass sodium carbonate aqueous solution, the water phase is removed by liquid separation, the organic phase is distilled under reduced pressure, the fraction under 95-110 ℃ and 400 Pa vacuum is collected, and a colorless transparent liquid product is obtained. The yield is 98.9%.

[0026] Comparative Example 1: The esterification of tetrahydrofurfuryl alcohol and acrylic acid at 110 ℃ is carried out, and the results are compared. (1) A three-necked flask with a stirring device is added with 1 g of activated carbon in total, 408 g of tetrahydrofurfuryl alcohol, 256 g of dimethylbenzene, and 28 g of methyl sulfonic acid.

[0027] (2) 369 g of acrylic acid is slowly added dropwise to step (1) for 2 h.

[0028] (3) After the dropwise addition is completed, 0.3 g of copper chloride and 0.2 g of p-hydroxyanisole are added, the temperature is increased to 110 ℃, and the reaction is continued for 6-8 h.

[0029] (4) After the reaction is completed, 400 g of toluene is added to the material, the PH of the material is neutralized to 6-7 by using a 15% by mass sodium carbonate aqueous solution, the water phase is removed by liquid separation, the organic phase is distilled under reduced pressure, the fraction under 95-110 ℃ and 400 Pa vacuum is collected, and a colorless transparent liquid product is obtained. The yield is 87.2%.

[0030] (5) The GC chart of the product is shown in Figure 2 . The purity is 92.1792%.

[0031] The GC charts of the products of Comparative Example (1) and Comparative Example 1: The purity of the tetrahydrofurfuryl alcohol acrylic acid ester product prepared by the present application is higher, and the impurities are less. Moreover, the reaction conditions are more moderate, and good technical progress is achieved.

[0032] The embodiments described above are part of the embodiments of the present application, rather than all the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but only represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor are within the scope of protection of the present application.

Claims

1. A method for preparing tetrahydrofurfuryl acrylate monomer, characterized in that, Includes the following steps: (1) Add activated carbon, tetrahydrofurfuryl alcohol, organic solvent, and catalyst to the flask; (2) Slowly add a certain mass of acryloyl chloride to step (1); (3) After the addition is complete, add a certain amount of polymerization inhibitor and heat the mixture for a period of time. (4) After the reaction is completed, a certain amount of solvent is added to the material, and the pH of the material is neutralized to weak acidity with an alkaline aqueous solution. The aqueous phase is removed by separation, and the organic phase is distilled under reduced pressure. The fraction under a certain temperature and vacuum is collected to obtain a colorless and transparent liquid product.

2. The method for preparing tetrahydrofurfuryl acrylate monomer according to claim 1, characterized in that, Includes the following steps: (1) Add 1-5‰ of activated carbon, tetrahydrofurfuryl alcohol, 15-25% organic solvent, and 2-5% catalyst to the flask; (2) Slowly add a certain mass of acryloyl chloride to step (1) for 2-5 hours, with a molar ratio of tetrahydrofurfuryl alcohol to acryloyl chloride of 1:1-1.1; (3) After the addition is complete, add a certain amount of polymerization inhibitor, heat to 20~60℃, and continue the reaction for 1~6 h; (4) After the reaction is complete, a certain amount of solvent is added to the material, and the pH of the material is neutralized to 6-7 with an alkaline aqueous solution. The aqueous phase is removed by separation, and the organic phase is distilled under reduced pressure. The fraction under a certain temperature and vacuum is collected to obtain a colorless and transparent liquid product.

3. The method for preparing tetrahydrofurfuryl acrylate monomer according to claim 1, characterized in that, The organic solvent in step (1) is at least one or a mixture of several of the following: toluene, dichloromethane, dichloroethane, xylene, propylene glycol methyl ether acetate, cyclohexane, and DMF.

4. The method for preparing tetrahydrofurfuryl acrylate monomer according to claim 1, characterized in that, The catalyst in step (1) is triethylamine, pyridine, or 4-dimethylaminopyridine.

5. The method for preparing tetrahydrofurfuryl acrylate monomer according to claim 1, characterized in that, In step (3), the polymerization inhibitor is: p-hydroxyanisole, hydroquinone, copper chloride, copper sulfate, copper nitrate, or a mixture of at least one or more of the above-mentioned copper salts containing water of crystallization.

6. The method for preparing tetrahydrofurfuryl acrylate monomer according to claim 1, characterized in that, The solvent used in step (4) is the same as the solvent used in step (1), and the amount added is 20-50% of the total mass.

7. The method for preparing tetrahydrofurfuryl acrylate monomer according to claim 1, characterized in that, Step (4) The alkaline aqueous solution is a mixture of at least one or more of the following: a sodium carbonate aqueous solution with a mass fraction of 5-20% and a sodium hydroxide aqueous solution with a mass fraction of 2-30%.

8. The method for preparing a tetrahydrofurfuryl acrylate monomer according to claim 1, characterized in that, Step (4) Collect the fraction at a temperature of 90~120℃ and a vacuum of 100~500Pa.

9. A method for preparing tetrahydrofurfuryl acrylate monomer, characterized in that, Includes the following steps: (1) Add 1g activated carbon, 408g tetrahydrofurfuryl alcohol, 256g xylene and 28g pyridine to the flask; (2) Slowly add 369g of acryloyl chloride to step (1) over a period of 2 hours; (3) After the addition is complete, add 0.3g of copper chloride and 0.2g of p-hydroxyanisole, heat to 30℃, and continue the reaction for 3 h; (4) After the reaction is complete, 400g of toluene is added to the material, and the pH of the material is neutralized to 6-7 with a 15% sodium carbonate aqueous solution. The aqueous phase is removed by separation, and the organic phase is distilled under reduced pressure. The fractions at 95℃-110℃ and 400Pa vacuum are collected to obtain a colorless and transparent liquid product.

10. A method for preparing tetrahydrofurfuryl acrylate monomer, characterized in that, Includes the following steps: (1) Add 1g activated carbon, 408g tetrahydrofurfuryl alcohol, 260g xylene and 35g pyridine to a three-necked flask equipped with a stirrer; (2) Slowly add 379g of acryloyl chloride to step (1) over a period of 3 hours; (3) After the addition is complete, add 0.3g of copper chloride and 0.2g of p-hydroxyanisole, heat to 50℃, and continue the reaction for 3 h; (4) After the reaction is complete, 600g of toluene is added to the material, and the pH of the material is neutralized to 6-7 with a 15% sodium carbonate aqueous solution. The aqueous phase is removed by separation, and the organic phase is distilled under reduced pressure. The fractions at 95℃-110℃ and 400Pa vacuum are collected to obtain a colorless and transparent liquid product.

Images