JPH0313208B2 - - Google Patents

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to diacrylate or dimethacrylate (hereinafter referred to as di(meth)acrylate) of a novel fluorine-containing bisphenol compound represented by the following general formula (). ]Regarding.

(In the formula, R represents a hydrogen atom or a methyl group.) The di(meth)acrylate of the novel fluorine-containing bisphenol compound represented by the above general formula () provided by the present invention can be polymerized by itself. mosquito,
Alternatively, by copolymerizing with various compounds having olefinic double bonds, di(meth)acrylate polymers of various useful fluorine-containing bisphenol compounds can be obtained, resulting in thermal and chemical stability, water repellency, and lubricity. It is expected to be used in various fields of application as a polymeric material with excellent properties.

<Conventional technology> Conventionally, di(meth)acrylate, a bisphenol compound that does not contain ordinary fluorine, has been used in a wide range of application fields as a functional polymer material, such as optical materials, dental materials, and crosslinking agents for various polymers. However, in recent years, higher functions such as higher heat resistance, chemical stability, lubricity, and water repellency have been required. However, the reality is that ordinary di(meth)acrylates of bisphenol compounds that do not contain fluorine do not necessarily satisfy these requirements.

A method for producing a di(meth)acrylate of a fluorine-containing bisphenol compound represented by the general formula () according to the present invention has not been reported at all so far. on the other hand,
Conventionally known methods for synthesizing di(meth)acrylates of bisphenol compounds that do not contain fluorine include, for example, bisphenol compounds and acrylic acid halide or methacrylic acid halide [hereinafter referred to as (meth)acrylic acid Halide. ], a method using an alkaline aqueous solution as a dehydrohalogenating agent (USSR Patent No. 759504, JP-A No. 55-33424), a method using an organic base such as pyridine or tributylamine (JP-A No. 48 -18264, U.S. Pat. No. 4,068,082), a method using an alkali metal hydroxide in the presence of a quaternary ammonium halide in a substantially water-free system (Japanese Patent Application Laid-open No. 55-33429), and bisphenol. A method of using hydrogen chloride as a reaction aid in the reaction between a compound and methacrylic acid (Japanese Patent Application Laid-Open No. 48-48453)
etc.

<Problems to be solved by the present invention> The present invention provides functional polymer materials such as optical materials, dental materials, and various polymer crosslinking agents that have higher heat resistance, chemical stability, lubricity, water repellency, etc. The object of the present invention is to provide a novel di(meth)acrylate of a fluorine-containing bisphenol compound that is extremely useful as a monomer component.

<Means and effects for solving the problems> The present inventors have conducted intensive studies to solve the physical property problems of di(meth)acrylates of ordinary bisphenol compounds as described above, and have developed a new method. Di(meth), a new fluorine-containing bisphenol compound represented by the general formula (), as a high-performance monomer component
They discovered acrylate and completed the present invention.

The present invention is a di(meth)acrylate of a fluorine-containing bisphenol compound represented by the following general formula ().

(In the formula, R represents a hydrogen atom or a methyl group.) As a result of studying a method for producing di(meth)acrylate of a novel fluorine-containing bisphenol compound represented by the above general formula (), the present inventors found that 1 ,1,1,
3,3,3-hexafluoro-2,2-bis(4
- In the reaction of (hydroxyphenyl)propane and (meth)acrylic acid chloride, a method using an aqueous sodium hydroxide solution as a dehydrochlorination agent, a method using an aqueous sodium hydroxide solution in the presence of a quaternary ammonium halide, a method using an aqueous sodium hydroxide solution as a dehydrochlorination agent, a method using an aqueous sodium hydroxide solution in the presence of a quaternary ammonium halide, etc. 1, by a method using a tertiary amine, etc.
1,1,3,3,3-hexafluoro-2,2-
Bis[4-(meth)acryloyloxyphenyl]
It was discovered that propane can be easily produced.

It goes without saying that the method for producing the compound () of the present invention is not limited to the above method.

Hereinafter, the method for producing the novel substances of the present invention will be specifically explained with reference to Examples, and the results of analysis for determining the structure of these novel substances obtained will also be shown at the same time.

Example 1 In a 1-volume glass flask equipped with a stirrer, addition funnel, Dimroth condenser, and thermometer, 1.
1,1,3,3,3-hexafluoro-2,2-
Bis(4-hydroxyphenyl)propane 50.0g
(0.149 mol), 16.7 g (0.417 mol) of sodium hydroxide, and 330 ml of water were charged, the internal temperature was maintained at 20°C, and the mixture was stirred for 30 minutes. Additionally, 330 ml of dichloromethane and 1.44 g of tetra-n-butylammonium bromide.
(4.5 mmol) and 0.05 g of methoquinone were added. The internal temperature was cooled to 10° C., and 32.3 g (0.357 mol) of acrylic acid chloride was added dropwise over 60 minutes while vigorously stirring the inside of the reaction vessel. After the dropwise addition was completed, stirring was continued for an additional 60 minutes. During the reaction, the internal temperature was kept below 15°C. When the stirring was stopped, two layers formed, so the aqueous layer was removed, and the organic layer was washed with 100 ml of a 5.0% by weight aqueous sodium hydroxide solution and then with 200 ml of water. Dichloromethane in the obtained organic layer was distilled off, and 1,1,
1,3,3,3-hexafluoro-2,2-bis(4-acryloyloxyphenyl)propane
60.8g (yield 91.8g) was obtained. This product was further purified by recrystallization from methanol.

The analytical results for determining the structure of this new substance obtained are shown below.

Γ Melting point 81.9℃ Γ Elemental analysis value C (%) H (%) F (%) Theoretical value 56.77 3.18 25.65 Analysis value 56.16 3.17 25.7 Γ ¹ HNMR (solvent: CDCl ₃ , internal standard material:
TMS) δ=6.04ppm (doublet 2H) δ=6.32ppm (multiplet 2H) δ=6.62ppm (doublet 2H) δ=7.18ppm (doublet 4H) δ=7.44ppm (doublet 4H) Γ ¹⁹ FNMR (Solvent: CDCl ₃ , internal standard:
CF ₃ CO ₂ H) δ = 11.92ppm (singlet 6F) Γ Mass spectrometry spectrum EI m/e = 444 (M ⁺ ) Γ Infrared absorption spectrum (KBr tablet) 3100, 3050 cm ^-1 (Aromatic C-H) 1727 cm ^-1 (C=O) 1630cm ^-1 (Olefin C=C) 1603, 1508cm ^-1 (Aromatic C=C) This infrared absorption spectrum is shown in FIG.

Example 2 In a reactor similar to Example 1, 1, 1, 1, 3,
3,3-hexafluoro-2,2-bis(4-hydroxyphenyl)propane 49.8g (0.148mol), sodium hydroxide 16.6g (0.415mol), water
330 ml was charged, the internal temperature was kept at 20°C, and the mixture was stirred for 30 minutes. Additionally, 330 ml of dichloromethane, methoquinone
Added 0.05g. Cool the internal temperature to 10℃ and add acrylic acid chloride while vigorously stirring the inside of the reaction vessel.
32.1 g (0.355 mol) was added dropwise over 60 minutes, and after the addition was completed, stirring was continued for an additional 90 minutes. During the reaction, the internal temperature was kept below 15°C. After the reaction, the reaction mixture was treated as in Example 1 to give 1,1,1,3,3,3-
Hexafluoro-2,2-bis(4-acryloyloxyphenyl)propane 52.6g (yield 80.0
%) was obtained. This product was further purified by recrystallization from methanol.

The analysis results for determining the structure of the obtained new substance were the same as in Example 1.

Example 3 In a reactor similar to Example 1, 1, 1, 1, 3,
Charge 50.0 g (0.149 mol) of 3,3-hexafluoro-2,2-bis(4-hydroxyphenyl)propane and 500 ml of dichloromethane, and add 39.3 g (0.388 mol) of triethylamine under ice cooling while stirring.
was added dropwise over 30 minutes. Further, 0.05 g of methoquinone was added, the internal temperature was cooled to 10° C., and 32.4 g (0.358 mol) of acrylic acid chloride was added dropwise over 60 minutes while stirring. After the dropwise addition was completed, stirring was continued for another 60 minutes. The internal temperature was kept below 15°C during the reaction. Filter the white solid produced after the reaction and add 200ml of dichloromethane.
After washing the solid with water, the liquid and washing solution were mixed together and washed with 200 ml of water. Dichloromethane and triethylamine in the obtained organic layer were distilled off, and 1,1,1,3,3,3-hexafluoro-
57.0 g (yield: 86.1%) of 2,2-bis(4-acryloyloxyphenyl)propane was obtained. This product was further purified by recrystallization from methanol.

The analysis results for determining the structure of the obtained new substance were the same as in Example 1.

Example 4 In a 1 capacity glass flask equipped with a stirrer, addition funnel, Dimroth condenser, and thermometer, 1,1,
1,3,3,3-hexafluoro-2,2-bis(4-hydroxyphenyl)propane 50.0g
(0.149 mol), 16.7 g (0.417 mol) of sodium hydroxide, and 330 ml of water were charged, the internal temperature was maintained at 20°C, and the mixture was stirred for 30 minutes. Additionally, 330 ml of dichloromethane and 1.44 g of tetra-n-butylammonium bromide.
(4.5 mmol) and 0.05 g of methoquinone were added. The internal temperature was cooled to 10° C., and 37.3 g (0.357 mol) of methacrylic acid chloride was added dropwise over 60 minutes while vigorously stirring the inside of the reaction vessel. After completion of the dropwise addition, stirring was continued for an additional 60 minutes. During the reaction, the internal temperature was kept below 15°C. When the stirring was stopped, two layers formed, so the aqueous layer was removed, and the organic layer was washed with 100 ml of a 5.0% by weight aqueous sodium hydroxide solution and then with 200 ml of water. Dichloromethane in the obtained organic layer was distilled off, and 1,1,
1,3,3,3-hexafluoro-2,2-bis(4-methacryloyloxyphenyl)propane
66.5g (yield 94.5%) was obtained. This product was further purified by recrystallization from benzene.

The analytical results for determining the structure of this new substance obtained are shown below.

Γ Melting point 110.6℃ Γ elemental analysis value C (%) H (%) F (%) Theoretical value 58.48 3.48 24.13 Analysis value 58.75 3.87 24.3 Γ ¹ HNMR (solvent: CDCl ₃ , internal standard substance:
TMS) δ=2.07ppm (singlet 6H) δ=5.78ppm (singlet 2H) δ=6.36ppm (singlet 2H) δ=7.17ppm (doublet 4H) δ=7.44ppm (doublet 4H) Γ ¹⁹ FNMR (Solvent: CDCl ₃ , internal standard:
CF ₃ CO ₂ H) δ = 11.89ppm (singlet 6F) Γ Mass spectrometry spectrum EI m/e = 472 (M ⁺ ) Γ Infrared absorption spectrum (KBr tablet) 3111, 3050 cm ^-1 (Aromatic C-H) 1723 cm ^-1 (C=O) 1631cm ^-1 (Olefin C=C) 1602, 1508cm ^-1 (Aromatic C=C) This infrared absorption spectrum is shown in FIG.

Example 5 In a reactor similar to Example 4, 1, 1, 1, 3,
3,3-hexafluoro-2,2-bis(4-hydroxyphenyl)propane 50.0g (0.149mol), sodium hydroxide 16.5g (0.413mol), water
330 ml was charged, the internal temperature was kept at 20°C, and the mixture was stirred for 30 minutes. Additionally, 330 ml of dichloromethane, methoquinone
Added 0.05g. The internal temperature was cooled to 10° C., and 37.0 g (0.354 mol) of methacrylic acid chloride was added dropwise over 60 minutes while vigorously stirring the inside of the reaction vessel. After completion of the dropwise addition, stirring was continued for an additional 90 minutes. During the reaction, the internal temperature was kept below 15°C. After the reaction, the reaction mixture was treated as in Example 4 and 1,1,1,3,3,3
-hexafluoro-2,2-bis(4-methacryloyloxyphenyl)propane 58.4g (yield
83.0%). This product was further purified by recrystallization from benzene.

The analysis results for determining the structure of the obtained new substance were the same as in Example 4.

Example 6 In a reactor similar to Example 4, 1, 1, 1, 3,
Charge 50.2 g (0.149 mol) of 3,3-hexafluoro-2,2-bis(4-hydroxyphenyl)propane and 500 ml of dichloromethane, and add 39.2 g (0.387 mol) of triethylamine under ice cooling while stirring.
was added dropwise over 30 minutes. Furthermore, 0.05 g of methoquinone was added, the internal temperature was cooled to 10° C., and 36.6 g (0.350 mol) of methacrylic acid chloride was added dropwise over 60 minutes while stirring. After the dropwise addition was completed, stirring was continued for an additional 60 minutes. During the reaction, the internal temperature was kept below 15°C. After the reaction, the white solid produced was filtered and dichloromethane was added.
After washing the solid with 200 ml, the liquid and washing solution were mixed together and washed with 200 ml of water. Dichloromethane and triethylamine in the obtained organic layer were distilled off to obtain 63.2 g of 1,1,1,3,3,3-hexafluoro-2,2-bis(4-methacryloyloxyphenyl)propane (yield 89.8). %) was obtained. This product was further purified by recrystallization from benzene.

The analysis results for determining the structure of the obtained new substance were the same as in Example 4.

[Brief explanation of the drawing]

Figure 1 shows 1, 1, 1, 3,
Figure 2 shows the infrared absorption spectrum of 3,3-hexafluoro-2,2-bis(4-acryloyloxyphenyl)propane, and Figure 2 shows the infrared absorption spectrum of 1,1,1,3,3,3-propane obtained in Example 4. hexafluoro-2,
2-bis(4-methacryloyloxyphenyl)
This shows the infrared absorption spectrum of propane.

Claims (1)

[Scope of Claims] 1. A diacrylate or dimethacrylate of a fluorine-containing bisphenol compound represented by the following general formula (). (In the formula, R represents a hydrogen atom or a methyl group.)