CN118851906A - A preparation method of perfluoroalkane hydroxypropyl acrylate - Google Patents

Abstract

The present invention relates to a method for preparing perfluoroalkane hydroxypropyl acrylate, and belongs to the technical field of organic chemistry. The method for preparing perfluoroalkane hydroxypropyl acrylate of the present invention comprises the following steps: dissolving a perfluoroalkyl epoxy compound in an organic solvent, cooling to 0°C to 5°C, slowly adding acrylic acid and a polymerization inhibitor to mix, and obtaining a mixed solution; after heating, dripping a base catalyst into the mixed solution, and after the dripping is completed, stirring and reacting at 68°C to 72°C for 3h to 18h to obtain the perfluoroalkane hydroxypropyl acrylate; after the reaction is completed, collecting the product, and distilling under reduced pressure to obtain perfluoroalkane hydroxypropyl acrylate. The present invention solves the problem of not reacting by microwave mode, with high yield, and can produce a single configuration product by feeding mode and programmed temperature rising mode.

Description

A preparation method of perfluoroalkane hydroxypropyl acrylate

Technical Field

The invention relates to the technical field of organic chemistry, in particular to a method for preparing perfluoroalkane hydroxypropyl acrylate.

Background Art

When the thickness of the conductive pattern formed on the substrate is very thin, an insulating film is required to protect the conductive pattern. The insulating film can prevent the extremely thin conductive pattern from being physically damaged, such as scratches, abrasion, etc., during subsequent processing, transportation or use, thereby maintaining the stability of the conductive performance; it can isolate external chemicals and pollutants to prevent them from chemically reacting with the conductive pattern and causing corrosion or performance degradation. It also helps to reduce the interference and crosstalk of electrical signals and ensure the accuracy and integrity of the electrical signals transmitted by the conductive pattern. In addition, the insulating film can also adjust the surface properties of the substrate, such as flatness and roughness, to a certain extent, providing better conditions for subsequent assembly or integration. When the raw material of the protective film is a perfluoroalkane hydroxypropyl acrylate compound, the protective film is less likely to cause the conductive pattern to migrate; the perfluoroalkane hydroxypropyl acrylate compound has the following advantages as a raw material for the insulating film: (1) Excellent chemical corrosion resistance: The presence of fluorine-containing groups makes it highly resistant to many chemicals and can maintain stable insulating properties in a harsh chemical environment. (2) Low surface energy: This helps to improve the surface properties of the insulating film, such as waterproof and anti-fouling properties. (3) Good heat resistance: It can maintain its insulation performance and physical properties at higher temperatures and is suitable for some high-temperature working environments. (4) Good electrical insulation performance: It can effectively isolate current and provide reliable insulation protection.

However, the synthesis method of perfluoroalkane hydroxypropyl acrylate compounds in the prior art mostly adopts microwave irradiation to heat the reaction. The disadvantage is that the use of microwave irradiation to heat the reaction is limited by the existing technology, equipment and cost in large-scale production, resulting in high production costs. In addition, the synthesized compound has a certain proportion of chiral isomers, which makes it difficult to purify the product to a single configuration.

Therefore, it is urgent to develop a method for preparing perfluoroalkane hydroxypropyl acrylate with high yield without microwave reaction.

Summary of the invention

In order to solve the above technical problems, the present invention provides a method for preparing perfluoroalkane hydroxypropyl acrylate. The present invention solves the problem of not reacting by microwave, has high yield, and can produce a single configuration product by feeding and programmed temperature rising.

The present invention is achieved through the following technical solutions:

The object of the present invention is to provide a method for preparing perfluoroalkane hydroxypropyl acrylate, comprising the following steps:

Dissolving a perfluoroalkyl epoxy compound in an organic solvent, cooling the temperature to 0°C to 5°C, slowly adding acrylic acid and a polymerization inhibitor to mix, and obtaining a mixed solution;

After the temperature is raised, a base catalyst is added dropwise to the mixed solution. After the addition is complete, the mixture is stirred and reacted at 68° C. to 72° C. for 3 h to 18 h to obtain the perfluoroalkane hydroxypropyl acrylate;

After the reaction is completed, the product is collected and distilled under reduced pressure to obtain perfluoroalkane hydroxypropyl acrylate.

In one embodiment of the present invention, the structural formula of the perfluoroalkyl epoxy compound is:

Here, n is any integer selected from 3 to 7.

In one embodiment of the present invention, the organic solvent is selected from one or more of toluene, N,N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.

In one embodiment of the present invention, the molar ratio of the perfluoroalkyl epoxy compound to the acrylic acid is 1:1.25-1.35.

In one embodiment of the present invention, the polymerization inhibitor is selected from one or more of tert-butylcatechol, hydroquinone, p-benzoquinone and 2,5-di-tert-butylhydroquinone.

In one embodiment of the present invention, the base catalyst is selected from triethylamine and/or N,N-diisopropylethylamine.

In one embodiment of the present invention, during the process of adding the alkali catalyst dropwise, the temperature of the mixed solution is controlled to be 62° C. to 68° C., and the time is controlled within 6 hours.

In one embodiment of the present invention, the molar ratio of the perfluoroalkyl epoxy compound to the base catalyst is 1:0.2-10.

In one embodiment of the present invention, the molar ratio of the perfluoroalkyl epoxy compound to the polymerization inhibitor is 1:0.01-0.05.

In one embodiment of the present invention, the mass volume ratio of the perfluoroalkyl epoxy compound to the organic solvent is 1:1-50.

In one embodiment of the present invention, the reduced pressure distillation collects a fraction at 60° C. to 82° C.

The above technical solution of the present invention has the following advantages compared with the prior art:

The present invention provides a method for preparing perfluoroalkane hydroxypropyl acrylate. The present invention uses materials that are easily available on the market as starting materials, and uses a relatively safe solvent for reaction, obtains perfluoroalkyl hydroxypropyl acrylate through simple operation and purification process, obtains a higher reaction yield and a higher product purity, and the obtained product is a single isomer. The process flow of the present invention is simple to operate and has no harsh reaction conditions, so it is more likely to be used in industrial production.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:

FIG1 is a reaction process diagram for preparing perfluoroalkane hydroxypropyl acrylate according to the present invention;

FIG2 is a ¹ H-NMR nuclear magnetic resonance spectrum in Example 1 of the present invention;

FIG3 is a ¹⁹ F-NMR nuclear magnetic resonance spectrum in Example 1 of the present invention;

FIG4 is a ¹ H-NMR nuclear magnetic resonance spectrum in Example 2 of the present invention;

FIG5 is a ¹⁹ F-NMR nuclear magnetic resonance spectrum in Example 2 of the present invention;

FIG6 is a gas chromatogram in Example 2 of the present invention;

Fig. 7 is a gas chromatogram of Comparative Example 1 of the present invention;

FIG8 is a gas chromatogram of Comparative Example 2 of the present invention.

DETAILED DESCRIPTION

The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

The present invention provides a method for preparing perfluoroalkane hydroxypropyl acrylate, which specifically comprises the following steps:

Dissolving a perfluoroalkyl epoxy compound in an organic solvent, cooling the temperature to 0°C to 5°C, slowly adding acrylic acid and a polymerization inhibitor to mix, and obtaining a mixed solution;

After the temperature is raised, a base catalyst is added dropwise to the mixed solution. After the addition is complete, the mixture is stirred and reacted at 68° C. to 72° C. for 3 h to 18 h to obtain the perfluoroalkane hydroxypropyl acrylate;

After the reaction is completed, the product is collected and distilled under reduced pressure to obtain perfluoroalkane hydroxypropyl acrylate.

Furthermore, the structural formula of the perfluoroalkyl epoxy compound is:

Here, n is any integer selected from 3 to 7.

When n=3, it is (2,2,3,3,4,4,5,5,5-nonafluoropentyl)ethylene oxide; when n=7, it is 3-(perfluoro-n-octyl)-1,2-propylene oxide.

Furthermore, the organic solvent is selected from one or more of toluene, N,N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.

Furthermore, the molar ratio of the perfluoroalkyl epoxy compound to the acrylic acid is 1:1.25-1.35.

Furthermore, the polymerization inhibitor is selected from one or more of tert-butylcatechol, hydroquinone, p-benzoquinone and 2,5-di-tert-butylhydroquinone.

Furthermore, the base catalyst is selected from triethylamine and/or N,N-diisopropylethylamine.

Furthermore, during the process of adding the alkali catalyst dropwise, the temperature of the mixed solution was controlled at 62° C. to 68° C., and the time was controlled within 6 hours.

Furthermore, the molar ratio of the perfluoroalkyl epoxy compound to the base catalyst is 1:0.2-10.

Furthermore, the molar ratio of the perfluoroalkyl epoxy compound to the polymerization inhibitor is 1:0.01-0.05.

Furthermore, the mass volume ratio of the perfluoroalkyl epoxy compound to the organic solvent is 1:1-50.

Furthermore, the reduced pressure distillation collects a fraction at 60° C. to 82° C.

Furthermore, the preparation method of the perfluoroalkane hydroxypropyl acrylate is specifically as follows:

Under nitrogen protection, add organic solvent, inhibitor, and perfluoroalkyl epoxy compound, stir and dissolve at room temperature, add acrylic acid at 0℃～5℃, raise the temperature to 30℃～120℃, slowly drop the base catalyst, keep the temperature at 68℃～72℃ for 3h～18h, and obtain perfluoroalkyl hydroxypropyl acrylate by simple distillation. This method obtains a single configuration product, and the gas phase detection DB-1 column is used.

Furthermore, the reaction process of the perfluoroalkyl epoxy compound and acrylic acid to generate perfluoroalkyl hydroxypropyl acrylate by base-catalyzed heating is shown in FIG1 ; wherein n is selected from any integer in the range of 3 to 7.

Embodiment 1:

This embodiment provides a method for preparing perfluoroalkane hydroxypropyl acrylate, and the specific steps are as follows:

Under nitrogen protection, 20g (1eq.) of (2,2,3,3,4,4,5,5,5-nonafluoropentyl) ethylene oxide and 120mL (6V) of N,N-dimethylformamide were stirred at room temperature to dissolve and mix, cooled to about 0°C, and 6.79g (1.3eq.) of acrylic acid and 5mg of tert-butyl catechol were slowly added, and the temperature was slowly raised to 65±3°C. The time was controlled within 6h, and 2.57g (0.35eq.) of triethylamine was added dropwise. After the addition was completed, the temperature was kept at 70±2°C, and the reaction was stirred for 3h to 18h. The raw materials were completely consumed, and the reaction liquid was distilled under reduced pressure with a vacuum oil pump to collect the 60°C to 64°C fraction to obtain 24g, with a yield of 95% and a gas chromatography purity of 99% (gas phase detection DB-1 column).

The product was characterized by NMR, as shown in Figures 2 and 3. The NMR data are as follows:

¹ H NMR (400MHz, Chloroform-d) δ6.47 (ddd, J＝17.3, 3.8, 1.3Hz, 1H), 6.16 (ddd, J＝17.3, 13.3, 10.5Hz, 1H), 5.91 (ddd, J＝ 10.5,2.8,1.3Hz,1H),4.47–4.39(m,1H),4.30(dd,J＝11.6,3.9Hz,1H),4.20(dd,J＝11.6,6.1Hz,1H),2.44–2.28 (m,2H).

¹⁹ F NMR (376MHz, Chloroform-d) δ-81.08(td,J＝9.6,4.8Hz),-112.86–-113.25(m),-124.51(q,J＝9.7Hz),-125.93(td,J =13.0,4.0Hz).

Embodiment 2:

This embodiment provides a method for preparing perfluoroalkane hydroxypropyl acrylate, and the specific steps are as follows:

Under nitrogen protection, 20g (1eq.) of 3-(perfluorooctyl)-1,2-propylene oxide and 120mL (6V) of N,N-dimethylformamide were stirred at room temperature to dissolve and mix, cooled to about 0°C, slowly added 2.1g (1.3eq.) of acrylic acid and 5mg of tert-butyl catechol, slowly heated to 65±3°C, and added 1.48g (0.35eq.) of triethylamine within 6h. After the addition was completed, the temperature was kept at 70±2°C, and stirred for 3h to 18h. The raw materials were completely consumed, and the reaction liquid was distilled under reduced pressure with a vacuum oil pump to collect the 78°C-82°C fraction to obtain 22g, with a yield of 95% and a gas chromatography purity of 99.84%.

The product was characterized by NMR, as shown in Figures 4 and 5. The NMR data are as follows:

¹ H NMR (400MHz, Chloroform-d) δ6.47 (ddd, J＝17.4, 3.9, 1.3Hz, 1H), 6.22–6.13 (m, 1H), 5.91 (ddd, J＝10.4, 2.9, 1.3Hz, 1H),4.46–4.40(m,1H),4.31(dd,J＝11.6,3.8Hz,1H),4.20(dd,J＝11.6,6.2Hz,1H),2.49–2.23(m,2H).

¹⁹ F NMR(376MHz,Chloroform-d)δ-80.79(t,J＝10.1Hz),-112.59–-112.95(m),-121.40–-122.08(m),-122.51–-122.86(m),- 123.50(t,J=15.1Hz),-125.95–-126.30(m).

The gas chromatogram is shown in FIG6 , from which it can be seen that the obtained product is of a single configuration, with a gas chromatographic purity of 99.84% and an isomer content of 0.04%.

Embodiment 3:

This embodiment provides a method for preparing perfluoroalkane hydroxypropyl acrylate, and the specific steps are as follows:

Under nitrogen protection, 20g (1eq.) of (2,2,3,3,4,4,5,5,5-nonafluoropentyl) ethylene oxide and 120mL (6V) of toluene were stirred at room temperature to dissolve and mix, cooled to about 0°C, slowly added 6.79g (1.3eq.) of acrylic acid and 5mg of tert-butyl catechol, slowly heated to 65±3°C, and added 2.97g (1.05eq.) of N,N-diisopropylethylamine dropwise within 6h, and kept warm to 70±2°C after the addition was completed, and stirred for 3h to 18h. The raw materials were completely consumed, and the reaction liquid was distilled under reduced pressure with a vacuum oil pump to collect the 60-64°C fraction to obtain 24g, with a yield of 95% and a gas chromatography purity of 99%.

The product was characterized by NMR, as shown in Figures 2 and 3. The NMR results are as follows:

¹ H NMR (400MHz, Chloroform-d) δ6.47 (ddd, J＝17.3, 3.8, 1.3Hz, 1H), 6.16 (ddd, J＝17.3, 13.3, 10.5Hz, 1H), 5.91 (ddd, J＝ 10.5,2.8,1.3Hz,1H),4.47–4.39(m,1H),4.30(dd,J＝11.6,3.9Hz,1H),4.20(dd,J＝11.6,6.1Hz,1H),2.44–2.28 (m,2H).

¹⁹ F NMR (376MHz, Chloroform-d) δ-81.08(td,J＝9.6,4.8Hz),-112.86–-113.25(m),-124.51(q,J＝9.7Hz),-125.93(td,J =13.0,4.0Hz).

Comparative Example 1

Under nitrogen protection, 20g (1eq.) of 3-(perfluorooctyl)-1,2-propylene oxide and 120mL (6V) of N,N-dimethylformamide were stirred at room temperature to dissolve and mix, cooled to about 0°C, slowly added 2.1g (1.3eq.) of acrylic acid and 5mg of tert-butyl catechol, slowly heated to 65±3°C, and added 1.48g (0.35eq.) of triethylamine within 6h. After the addition was completed, the temperature was kept at 80±2°C, and stirred for 3h to 18h. The raw materials were completely consumed, and the reaction liquid was distilled under reduced pressure with a vacuum oil pump to collect the 78°C-82°C fraction to obtain 22g, with a yield of 95%, a gas chromatographic purity of 60% (the gas chromatogram is shown in Figure 7), and 30.73% of isomers.

Comparative Example 2

Under nitrogen protection, 20g (1eq.) of 3-(perfluoro-n-octyl)-1,2-propylene oxide and 120mL (6V) of N,N-dimethylformamide were stirred at room temperature to dissolve and mix, cooled to about 0°C, and 6.05g (2eq.) of acrylic acid and 5mg of tert-butyl catechol were slowly added, and the temperature was slowly raised to 65±3°C. The time was controlled within 6 hours, and 1.48g (0.35eq.) of triethylamine was added dropwise. After the addition was completed, the temperature was kept at 70±2°C, and the reaction was stirred for 3h to 18h. The raw materials were completely consumed, and the reaction liquid was distilled under reduced pressure with a vacuum oil pump to collect the 78°C-82°C fraction to obtain 22g, with a yield of 95%, a gas chromatographic purity of 77% (the gas chromatogram is shown in Figure 8), and an isomer of 14.75%.

Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims (10)

1. A method for preparing perfluoroalkane hydroxypropyl acrylate, characterized in that it comprises the following steps: Dissolving a perfluoroalkyl epoxy compound in an organic solvent, cooling the temperature to 0°C to 5°C, slowly adding acrylic acid and a polymerization inhibitor to mix, and obtaining a mixed solution; After the temperature is raised, a base catalyst is added dropwise to the mixed solution. After the addition is complete, the mixture is stirred and reacted at 68° C. to 72° C. for 3 h to 18 h to obtain the perfluoroalkane hydroxypropyl acrylate; After the reaction is completed, the product is collected and distilled under reduced pressure to obtain perfluoroalkane hydroxypropyl acrylate. 2. The preparation method according to claim 1, characterized in that the structural formula of the perfluoroalkyl epoxy compound is: Here, n is any integer selected from 3 to 7. 3. The preparation method according to claim 1, characterized in that the organic solvent is selected from one or more of toluene, N,N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. 4 . The preparation method according to claim 1 , wherein the molar ratio of the perfluoroalkyl epoxy compound to the acrylic acid is 1:1.25-1.35. 5. The preparation method according to claim 1, characterized in that the polymerization inhibitor is selected from one or more of tert-butylcatechol, hydroquinone, p-benzoquinone and 2,5-di-tert-butylhydroquinone. 6. The preparation method according to claim 1, characterized in that the base catalyst is selected from triethylamine and/or N,N-diisopropylethylamine. 7. The preparation method according to claim 1, characterized in that during the process of dropwise adding the alkali catalyst, the temperature of the mixed solution is controlled to be 62°C to 68°C and the time is controlled within 6 hours. 8 . The preparation method according to claim 1 , wherein the molar ratio of the perfluoroalkyl epoxy compound to the base catalyst is 1:0.2-10. 9 . The preparation method according to claim 1 , characterized in that the molar ratio of the perfluoroalkyl epoxy compound to the polymerization inhibitor is 1:0.01-0.05. 10 . The preparation method according to claim 1 , wherein the mass volume ratio of the perfluoroalkyl epoxy compound to the organic solvent is 1:1 to 50.