JPH02138152A - Fluorine-containing aromatic compound - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I (R<1> is H, acryloyl or methacryloyl; R<2> is H or methyl). EXAMPLE:2-(3-Acryloyloxy-2-hydroxypropoxy)-1,1,1,3,3,3-hexafluoro-2- phenylpropane. USE:A raw material for synthesis of a compound having excellent functions such as heat resistance, weather resistance, low friction, water and oil repellency, low refractive index, transparency and oxygen permeability. Usable as a dental material, an optical material and a biofunctional material such as a contact lens material without purification. PREPARATION:2-(2,3-Epoxypropoxy)-1,1,1,3,3,3-hexafluoro-2-phenyl-propane of formula II is reacted with acrylic acid of formula III in the presence of a quaternary ammonium salt such as choline chloride in a solvent such as toluene at the reflux temperature to obtain the objective compound of formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention is directed to the use of one radically polymerizable unsaturated bond in one molecule and a highly reactive hydroxyl group, or two radically polymerizable unsaturated bonds in one molecule. The present invention relates to a novel fluorine atom-containing aromatic compound that has unsaturated bonds and is useful as a chemical raw material in various industrial fields.

[Conventional technology and its issues]

Aromatic compounds that do not have fluorine atoms in their molecules have long been used as dental resins, optical materials, crosslinking agents in various polymers, and biofunctional polymer materials such as contact lens materials, or as precursors thereof. It is used as a material in a wide range of application fields.

However, aromatic compounds that do not have a fluorine atom in their molecules and are used for the above purposes have poor heat resistance, chemical resistance,
Weather resistant, low friction, water repellent, IΩ oil resistant.

These properties have not always been fully satisfied in terms of performance such as low refractive index, transparency, and oxygen permeability.

In view of the current situation, this invention has higher heat resistance.

It is useful as a raw material for the synthesis of new compounds with high functionality such as chemical resistance, weather resistance, low friction, tθ water/1B oil resistance, low refractive index, transparency, and oxygen permeability. The object of the present invention is to provide a fluorine atom-containing aromatic compound that functions as a fluorination agent that can be converted into a fluorine atom-containing compound.

[Means to solve the problem]

This invention provides a fluorine atom-containing aromatic compound (hereinafter simply referred to as "the present compound") represented by the above-mentioned form (I),
It has one radically polymerizable unsaturated bond in one molecule and a highly reactive water M group, or two radically polymerizable unsaturated bonds in the molecule.

[Method of synthesizing this compound]

The present compounds (1a) to (1f) have the chemical structural formulas shown below, and any of them can be easily synthesized, for example, by the reactions shown in the following formulas.

■ 2-(3-acryloyloxy-2-hydroxypropoxy)-1, where R1 and R2 are both hydrogen atoms;
1,1,3,3,3-hexafluoro-2-phenylpropane (hereinafter referred to as "the present compound (1a)") is as shown in the following formula (1).

2-(2,3-epoxypropoxy)-1,Ll,3
゜3.3-hexafluoro-2-phenyl-propane (
(hereinafter referred to as "compound (a)") and acrylic acid (hereinafter referred to as "compound (a)").
Compound (b)'') can be easily produced by reacting the compound (b) in the presence of a quaternary ammonium salt such as choline chloride.

2 [I) ■ 11.1 where R1 is a hydrogen atom and R2 is a methyl group
,3,3.3-hexafluoro-2-((2-hydroxy-3-methacryloyloxy)propoxy-2-phenylpropane (hereinafter referred to as "the present compound (lb)J)" is represented by the following formula (II) It can be easily produced by reacting compound (a) with methacrylic acid (hereinafter referred to as "compound (C)") in the presence of a quaternary ammonium salt such as choline chloride.

Formula (III) It can be easily produced by reacting with chloroyl chloride (hereinafter referred to as "compound (d)").

Formula (1) 0-CC-CHr ■ R1 is an acryloyl group and R1 is a hydrogen atom 2
-[2,3-bis(acryloyloxy)propoxy)
-1,1,1,3,3,3-hexafluoro-2-phenylpropane (hereinafter referred to as the present compound (IC) J),
As shown in the following formula (III), the present compound (1a) obtained by the above formula (1) is a) where R1 is a methacryloyl group.
2-(3-acryloyloxy-) in which Bt is a hydrogen atom
2-methacryloyloxy)propoxy) -1,1,
1,3゜3.3-hexafluoro-2-phenylpropane (hereinafter referred to as "the present compound (ld) J") is produced by the following 2 (
As shown in IV), the present compound (l) obtained by the above formula (1)
a) with methacryloyl chloride (hereinafter referred to as "compound (e)")
It can be easily produced by reacting with

Formula (■) Formula % Formula % ■ 2-(2-acryloyloxy-3-methacryloyloxy)propoxy-1,1,1,3,3,3-hexafluoro where R' is an acryloyl group and R2 is a methyl group -2-phenylpropane (hereinafter [this compound (1e
) J) is represented by the formula 1 (I
This compound (1b) obtained in step f) can be easily produced by reacting with compound (d).

■ 1,1.1.3.3.3-hexafluoro-2゛-[2 where R1 is a methacryloyl group and RZ is a methyl group
,3-bis(methacryloyloxy)propoxy]-2
-Phenylpropane (hereinafter referred to as r the present compound (if) J) is represented by the formula (II) as shown in the following formula [VI].
It can be easily produced by reacting the present compound (1b) obtained in ) with compound (e).

[Margin below] 2 (VI) 0-C-C-CHI Sea urchin, commercially available 1.1.1.3,3.3-hexafluoro-2-phenyl-2-propatol (hereinafter referred to as "compound (y
)" and chloromethyloxirane (hereinafter referred to as "compound (2)") in the presence of sodium hydroxide or the like.

2 [■] The method for producing the compounds (1a) to (1f) will be explained in more detail below.

First, in the production of nine compounds (1a) to (1''), the compounds (a) used as starting materials in formula (1) and formula (II) include 2 such as S, A, Re1n.
es, J., R., Griffith and J.

Known epoxy compounds reported by G, O"Rear (Am, Chem, Sos, , Div, Coa
tings Plast, Chem, Pap,
, 30 (2) 263 268 (1970)) can be used.

This compound (a) is expressed by the following formula [■].
Engineering L) Compound (z) To explain the production of compound (1a) and compound (lb), a catalytic amount of triethylamine, tributylamine, picoline, N,N-dimethyl- In the presence of a tertiary amine such as p-toluidine or a quaternary ammonium salt such as choline chloride.

Further, in the presence of a small amount of a polymerization inhibitor such as hydroquinone, methoxyhydroquinone, p-benzoquinone, t-butylcatechol, or phenothiazine, the above compound (a) and the above compound (b) or the compound are mixed at reflux temperature with stirring. By reacting with (C),
The desired viscous liquid compound (1a) or (1b)
can be obtained.

Note that 1 reaction is completed within 9 hours, but after 5 reactions are completed, 9 reaction solutions are mixed with diethyl ether, ethyl acetate, dichloromethane, chloroform, and benzene.

Dilute sodium carbonate with an organic solvent such as toluene.

Repeated washing with basic aqueous solutions such as potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. and water.

The present compound (la ) or (1b) can be isolated.

Since this reaction proceeds so selectively, it can be used as it is for dental materials, optical materials, contact lens materials, etc. without purification.

If necessary, it may be purified by means such as column chromatography.

Then one compound (lc), (ld), (le
) and (1f) will be explained.

The present compound (1a) or (1b), dichloromethane,
Triethylamine or tributylamine in an equal or excess amount relative to the two compounds (1a) or (1b) in an organic solvent such as chloroform, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, Hensen, toluene, pyridine, or ethanol. , picolin,
In the presence of a tertiary amine such as N,N-dimethyl-p-toluidine or a base such as sodium hydroxide or potassium hydroxide, at a temperature of 50°C or less, preferably at a temperature of 20 to 30°C.
In C, add compound (d) or compound +J while stirring.
j! React with IJ(e).

Dichloromethane is suitable as reaction medium.

This compound (1a) or (1b), which is a starting material, has a molecular weight of 20
After the specified time has passed, the reaction solution is diluted with an organic solvent such as diethyl ether, ethyl acetate, dichloromethane, chloroform, Hensen, toluene, etc., and washed with water repeatedly. Anhydrous sodium sulfate, anhydrous magnesium sulfate , dried in the presence of a desiccant such as calcium chloride, filtered off the desiccant, and concentrated the filtrate under normal pressure and further under reduced pressure to obtain the desired viscous liquid compound (1c).

(1d), (1e) and (1f) can be isolated.

Each of the reactions of formulas (1) to (Vl) described above proceed selectively, so the resulting compounds can be used as they are for dental materials, optical materials, contacts, etc., without being purified. It can be used for lens materials, etc., but if necessary, it may be purified by means such as column chromatography.

□ In these reactions, at the end of one reaction, the remaining amount of the starting material can be checked using thin layer chromatography (11) (-nuclear magnetic resonance spectrum, '3C ~ nuclear magnetic resonance spectrum, etc.) to confirm the completion of the reaction. is desirable.

[Uses of this compound]

The present compounds (1a) to (1f) in this invention can be homopolymerized themselves or copolymerized with various polymerizable monomers having olefinic double bonds, for example, by radical polymerization means. By this method, polymers of fluorine-containing bisphenol derivatives having various useful properties can be easily obtained.

Examples of monomers radically polymerizable with the present compounds (1a) to (1f) include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate ratio propyl acrylate, propyl methacrylate, and 2-methylpropyl acrylate.
2-methylpropyl methacrylate butyl acrylate, butyl methacrylate, 1.1-dimethylethyl acrylate), 1.1-dimethylethyl methacrylate,
N-vinyl-2-pyrrolidone, 2-vinylpyridine, 4
-Vinylpyridine, N-vinylpyridine, N-
Examples include vinyl caprolactam, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like.

[Margin below]

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 50 with dropping funnel, ball cooling tube and thermometer installed
45.1g (0゜15mo
+) compound (a) and 54 g (0.74 mo 1)
Compound (b) and 100mj! of toluene was added, followed by 0.43 g (3 mmol) of choline chloride and a small amount of hydroquinone.

This reaction solution was gradually heated to a temperature of 110°C to cause a reaction.

The residual amount of compound (a) in the first reaction solution was monitored by gas chromatography, and 6 hours after the reaction was completed, heating was stopped and the second reaction solution was cooled to room temperature.

Thereafter, one reaction solution was diluted with 500 mβ of ethyl acetate, and washed with 7% aqueous sodium carbonate solution (300 ml x 5 times) and water (300 ml x 3 times).

After drying this ethyl acetate solution in the presence of anhydrous magnesium sulfate, the desiccant was filtered off, and the filtrate was concentrated to obtain 50 g of a product. (Yield: 90%) It was confirmed that the obtained product was the present compound (1a) by 1) (-nuclear magnetic resonance spectrum and 13C-nuclear magnetic resonance spectrum.

The results are shown in Tables 1 and 2.

Table 1: Chemical shift values of 'H-nuclear magnetic resonance spectra of products and their assignments (CDCI, 100 MHz, tetramethylsilane) Table 2: Chemical shift values of 130-nuclear magnetic resonance spectra of products and their assignments (CDCI, 25MHz, tetramethylsilane) [
Blank space below] h Phenyl group: C, d, f *: j, 1 Example 2 50 with a dropping funnel, ball-filled cooling tube, and thermometer attached
45.3 g (0°1
5mo +) of compound (a) and 65g (0,75mo
After adding compound (C) in l) and 100 ml of toluene, 0.42 g (3 mmol) of choline chloride and a small amount of hydroquinone were added. 1. The temperature of the reaction solution was gradually raised and the reaction was carried out at a reflux temperature of 110°C. I let it happen.

The residual amount of compound (a) in the reaction solution was monitored by gas chromatography, and 6 hours after the completion of the reaction, heating was stopped and the reaction solution 9 was cooled to room temperature.

This reaction solution was mixed with 400mj of ethyl acetate! After diluting with 7% sodium carbonate aqueous solution (300ml x 5 times),
Washed with water (300 m!! x 3 times) in this order.

After drying this ethyl acetate solution in the presence of anhydrous magnesium sulfate, the desiccant was filtered off, and the filtrate was concentrated to obtain 58 g of a product. (Yield: 90%) It was confirmed that the obtained tangential proboscis was the present compound (1b) by IH-nuclear magnetic resonance spectrum and 13C-nuclear magnetic resonance spectrum.

The results are shown in Tables 3 and 4.

[Margin below]

Table 3 Product I) (-Chemical shift value of nuclear magnetic resonance spectrum and its assignment (CDCI, 100 MHz, tetramethylsilane) Table 4 Product 130-Chemical shift value of nuclear magnetic resonance spectrum and its assignment (CDCI, 25MHz, tetramethylsilane) [
Blank space below] Phenyl group: c, d, f *: j, 1 fruit 1 rough 1 dropping funnel, condensing tube with beads and thermometer attached 3 0
18.7g (0゜05m
o l) of the present compound (1a) and 50mj! of dichloromethane and 6.1 g (0.06 mol) of triethiamine were added, followed by a small amount of hydroquinone.

Then, add 5゜4g to 20ml of dichloromethane at room temperature.
A solution containing (0.06 mol) of compound (d) was slowly added dropwise.

After the dropwise addition, the reaction was continued for an additional 19.5 hours at a temperature of 25° C., and then one reaction solution was diluted with 100 ml of dichloromethane, transferred to a separatory funnel, and washed three times with 200 m# of water.

After drying this dichloromethane solution in the presence of a desiccant consisting of anhydrous sodium sulfate.

The drying agent is filtered off, and the filtrate is concentrated by heating to a temperature of 60° C. under normal pressure or further under reduced pressure to obtain product 17.
6g was obtained. (Yield: 81%) It was confirmed that the obtained product was the present compound (1c) by IH-nuclear magnetic resonance spectroscopy and 3C-nuclear magnetic resonance spectroscopy.

The results are shown in Tables 5 and 6.

Table 5: Chemical shift values of 1H-nuclear magnetic resonance spectra of products and their attributions (CD CI, 100 MHz, tetramethylsilane) [blank space below] / CH=CH2 Table 6: lffC-nuclear magnetic resonance of products Chemical shift value of spectrum and its attribution (CDCI, 25MHz, tetramethylsilane)☆
: a or b # : C or d Phenyl group : e, f, h * : ni, l, m Example 4 30 with a dropping funnel, a ball cooling tube and a thermometer attached
18.7g (0゜05mo
l) of the present compound (1a) and dichloromethane 50ml
and 6.1 g (0.06 mol) of triethiamine, and a small amount of hydroquinone.

After that, 20mj of dichloromethane was added at room temperature. 6゜3
A solution containing compound (e) of g (0.06 mo t) was slowly added dropwise.

After the dropwise addition, the reaction was continued for another 12 hours at a temperature of 25°C, and then the reaction solution was diluted with 100 mj2 of dichloromethane, transferred to a separatory funnel, and diluted with 200 mj! Washed three times with water.

Next, this dichloromethane solution was dried in the presence of a desiccant consisting of anhydrous sodium sulfate, the desiccant was filtered off, and the obtained filtrate was heated at a temperature of 60°C under normal pressure or further under reduced pressure.
Heating to °C and concentration yielded 17.5 g of product. (
(Yield: 79%) The obtained product was confirmed to be the present compound (1d) by IH-nuclear magnetic resonance spectrum and 1
Performed by 3C-nuclear magnetic resonance spectroscopy.

The results are shown in Tables 7 and 8.

Table 7 Chemical shift values of lH-nuclear magnetic resonance spectra of products and their attributions (CD CI, 100 MHz, tetramethylsilane) Table 8 Chemical shift values of lH-nuclear magnetic resonance spectra of products and their attributions (CDCI, 25MHz, tetramethylsilane)
[Margin below] Margin below c] #: a or b Phenyl group: e, f, g or h * Hlm, n Example 5 30 with a dropping funnel, ball cooling tube and thermometer attached
15.0g (0°9
5 mol) of this compound (1b) and dichloromethane 50
m1 and triethiamine 6.2 g (0,061 mol
) was added, and a small amount of hydroquinone was added.

Thereafter, a solution prepared by dissolving 5.6 g (0.06 mol) of compound (d) in 10 ml of dichloromethane was slowly added dropwise while magnetically stirring the solution at room temperature.

After continuing the reaction for 18 hours at a temperature of 25°C, the two reaction solutions were mixed with 100mj of dichloromethane! The mixture was diluted with water, transferred to a separatory funnel, and washed three times with 300 mJ of water.

After drying this dichloromethane solution in the presence of a desiccant consisting of anhydrous sodium sulfate, the desiccant was filtered off,
The obtained filtrate was concentrated by heating to a temperature of 60° C. under normal pressure and further under reduced pressure to obtain 17° of a product. (Yield is 78
%) It was confirmed that the obtained product was the present compound (1e) by IH-nuclear magnetic resonance spectroscopy and 3C-nuclear magnetic resonance spectrum.

The results are shown in Tables 9 and 10.

[Margin below]

Table 9 Chemical shift values of 'H-nuclear magnetic resonance vectors of products and their attributions (CDCI, 100 MHz, tetramethylsilane) [Margins below] [Margins below] Table 10 13C-Nuclear magnetic resonance of products Chemical shift value of spectrum and its attribution (CDCI, 25MHz, tetramethylsilane) [
Margin below] Fenino exposure: e, f, i*
: m, n, .

Example 6 30 with dropping funnel, bead condenser and thermometer installed
18.7 g (0
This compound (1b) of
of) was added, followed by a small amount of hydroquinone.

After that, 20mj of dichloromethane was added at room temperature. 6゜3
G (0.06 mol) of a solution of compound (e) was slowly added dropwise, and the reaction was continued for 15 hours at a temperature of 25°C. One reaction solution was poured into 100 m7 of dichloromethane! The mixture was diluted with water, transferred to a separatory funnel, and washed three times with 200 mE water.

After drying this dichloromethane solution in the presence of a desiccant consisting of anhydrous sodium sulfate, the desiccant was filtered off,
The obtained filtrate was concentrated by heating to a temperature of 60° C. under normal pressure and further under reduced pressure to obtain 21.6 g of product. (Yield is 95
%) It was confirmed that the obtained product was the present compound (1f) by 1H-nuclear magnetic resonance spectrum and 130-nuclear magnetic resonance spectrum.

The results are shown in Tables 11 and 12.

[Margin below]

Table 11 Product 1) (-Chemical shift value of nuclear magnetic resonance spectrum and its assignment (CDC 1,100 MHz, tetramethylsilane)
[Margins below] Table 12 Chemical shift values of 130-nuclear magnetic resonance spectra of products and their attributions (CDCI, 25 MHz, tetramethylsilane) #
: a or b phenyl group : d, e, f☆ :
h or i*: l, m, n Reference Example For the products obtained in Examples 3 to 6, the sensitizer 2-
Hydroxy-2-methyl-1-phenylpropane-1-
3 to 4 mol % of On was added and stirred thoroughly to make it uniform.

After casting it onto a glass plate, it is irradiated with ultraviolet rays and cured to produce a polymer with an arbitrary thickness.The refractive index, water contact angle, glass transition point, and decomposition temperature are determined by the following method. It was measured.

Refractive index: The refractive index at a temperature of 25° C. was measured by a conventional method using an Atago New Model Anne refractometer manufactured by Atago Optical Machinery Works.

Water contact angle: Measured by a conventional method using an Elma goniometer type contact angle measuring device.

Glass transition point: The viscoelastic spectrum (VES) of the heavy metal material was measured, and the maximum value of tan δ was regarded as the glass transition point.

Decomposition temperature: The rise temperature and peak temperature of a large endothermic peak appearing in differential scanning calorimetry (DSC) were regarded as the decomposition temperature.

In addition, the amount measured in this way At the melting temperature, more than 10% of the weight A decrease was observed.

The measurement results are shown in Table 13.

[Margin below]

It is a polymeric material with excellent physical properties such as surface abrasion resistance, ↑Ω water/TΩ oil resistance, low refraction, transparency, and oxygen permeability.

It is useful as a chemical material in a variety of industrial fields, including the fact that it can be used as it is for dental materials, optical materials, contact lens materials, etc. without being purified.

〔Effect of the invention〕

The fluorine atom-containing aromatic compound of the present invention has one radically polymerizable unsaturated bond and one highly reactive hydroxyl group in one molecule, or two radically polymerizable unsaturated bonds in one molecule. Therefore, it is possible to polymerize various useful fluorinated bisphenol derivatives by homopolymerizing itself or copolymerizing it with various monomers having a polymerizable olefinic double bond. You can get things easily.

Claims (1)

[Claims] A fluorine atom-containing aromatic compound represented by the following general formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) In the above formula, R^1 is a hydrogen atom, an acryloyl group, or a methacryloyl group, and R^2 is a hydrogen atom or a methyl group.