JPH0774178B2 - Perfluoroalkenyloxyphenol and its derivatives - Google Patents

Description

TECHNICAL FIELD The present invention relates to perfluoroalkenyloxyphenol and its derivatives.

(Prior Art) Conventionally, a phenol novolac resin made from a fluorine-containing phenol such as trifluoromethylphenol is known from U.S. Pat. No. 3,658,758 and the like, but these are insufficient in water resistance and heat resistance. Is.

(Problems to be Solved by the Invention) An object of the present invention is to provide a fluorine-containing phenol and a derivative thereof as a raw material of a fluorine-containing fluorine-containing novolak resin or a fluorine-containing epoxy resin having excellent water resistance and heat resistance. Especially.

(Means for Solving Problems) The present invention provides a general formula (R ¹ is OH or R ² is H, OH, an alkyl group having 1 to 4 carbon atoms, or X represents a perfluoroalkenyl group having 6 to 14 carbon atoms)
The present invention relates to a perfluoroalkenyloxyphenol or a derivative thereof.

In the present invention, R ¹ ═OH, R ² ═H or perfluoroalkenyloxyphenols having an alkyl group having 1 to 4 carbon atoms can be obtained, for example, by the following formula.

That is, monoalkoxy (or acyloxy) phenol or its alkyl derivative (R ²¹ is H or an alkyl group having 1 to 4 carbon atoms, R ³ is an alkoxy group having 1 to 8 carbon atoms or 1 carbon atom).
~ 8 acyloxy group) (2) and perfluoroalkene XF
By reacting with to synthesize perfluoroalkenyloxymonoalkoxy (or acyloxy) benzene or its alkyl derivative (3), and then reacting this with hydrogen halide HZ to give perfluoroalkenyloxyphenol or its alkyl. The derivative (4) is obtained.

Similarly, a perfluoroalkenyloxy-hydroxyphenol in which R ¹ = R ² = OH is obtained by the following formula.

Here, R ³ and R ⁴ are respectively an alkoxy group having 1 to 8 carbon atoms or an acyloxy group having 1 to 8 carbon atoms, and the reaction type is the same as above. Examples of the perfluoroalkenyl group having 6 to 14 carbon atoms represented by X include those represented by the formula (R ⁵ , R ⁶ and R ⁷ are each a C 1-6 perfluoroalkyl group or one of them is an F atom, and the other is a C 1-6 perfluoroalkyl group, and R ⁸ is a carbon number. 1 to 5 perfluoroalkyl group), and particularly preferred are hexafluoropropene dimer or trimer and tetrafluoroethylene 4 to 7 Examples thereof include groups formed by elimination of one fluorine atom, and examples of the structural formulas are as follows.

As the perfluoroalkene represented by the formula XF, for example, the formula (R ⁵ , R ⁶ and R ⁷ have the same meanings as described above), and particularly preferable are dimers and trimers of hexafluoropropene, and tetrafluoroethylene of 4 -7-mer is mentioned, and when it illustrates by a structural formula, it is as follows.

(CF ₃ ) ₂ C = CF (C ₂ F ₅ ), Examples of the hydrogen halide represented by HZ include hydroiodic acid and hydrobromic acid.

The perfluoroalkenyloxylation reaction for obtaining compound (3) or (6) from compound (2) or (5) above is preferably carried out in a solvent in the presence of a base. As the base, amines such as triethylamine, trimethylamine, tripropylamine and the like, alkali metals or hydroxides thereof and the like, and as the solvent, aprotic polar solvents such as acetonitrile, dimethylformamide and dimethylsulfoxide can be preferably used. Regarding the ratio of the compound (2) or (5) to the perfluoroalkene, it is usually preferable to use the latter in an amount of about 1 to 10 mol per 1 mol of the former. The reaction temperature can be appropriately selected, but it is preferably in the range of about 0 to 40 ° C, particularly about 0 to 20 ° C. The base is preferably used in the range of about 1-20 mol per 1 mol of the compound (2) or (5).
The target compound (3) or (6) can be separated and recovered by a known method usually used for separation of an organic compound mixed system such as distillation and recrystallization, or can be directly used in the next step.

Among the compounds represented by the formula (8) XF, as well as The compounds represented by are included.

From now on, Is generated.

More specifically, for example Is generated.

It is preferable to carry out the dealkylation (or deacylation) reaction in the presence of a hydrogen halide from the above compound (3) or (6) in the presence of a solvent. As the solvent, formic acid, acetic acid, trifluoroacetic acid, methanol, ethanol, n-propanol, isopropanol, n-butanol or the like can be used. It is preferable to use the hydrogen halide in an amount of about 2 to 100 times the molar amount of the compound (3) or (6). The reaction temperature can be appropriately selected, but it is preferably in the range of about 50 to 200 ° C. A dealkylation (deacylation) reaction with a Lewis acid such as aluminum chloride can also be performed.
The target compound (4) or (7) is separated by an ordinary method, for example, extraction, concentration, distillation, recrystallization or the like,
It can be purified.

In the deacylation reaction of the above reactions, for example, alkali metal and / or alkaline earth metal hydroxide is used, and after saponification with water or alcohols such as methanol and ethanol as a medium, the reaction system is acidified. You can also do this. . It is preferable to use an alkali metal and / or alkaline earth metal hydroxide in an amount of about 2 to 30 times that of the compound (3) or (6). The reaction temperature can be appropriately selected, but a range of about 20 to 100 ° C is preferable.

Next in the present invention (Hereinafter abbreviated as O-Gly), R ² = H or carbon number 1 to 4
The perfluoroalkenyloxyphenyl glycidyl ethers of the above alkyl group can be obtained by the etherification reaction of the compound (4) with epichlorohydrin (hereinafter abbreviated as ECH). Further, the perfluoroalkenyloxyphenyl diglycidyl ether of R ¹ ═R ² ═O-Gly is a compound (7)
Obtained by etherification reaction with ECH. The reaction does not necessarily require a solvent, but methyl ethyl ketone (ME
K), methyl isobutyl ketone (MIBK) and the like can also be used. EC for compound (4) or (7)
It is preferable to use about 2 to 100 times mol of H. Also NaOH,
Compound (4) with alkali such as KOH, LiOH, Ca (OH) ₂
Alternatively, it is preferable to use about 1 to 20 equivalents relative to the OH equivalent of (7). A catalyst is not always necessary, but a quaternary ammonium salt such as trimethylbenzylammonium chloride or tetramethylammonium bromide can be used in a proportion of about 0.01 to 10% by weight based on the reaction system. The reaction temperature can be appropriately selected, but it is preferably in the range of about 50 to 200 ° C. Perfluoroalkenyloxyphenyl mono (or di) glycidyl ethers, which are the target compounds, can be prepared by a conventional method such as extraction, concentration, distillation or recrystallization.
It can be separated and purified.

(Effect of the Invention) Among the compounds of the present invention, perfluoroalkenyloxyphenol reacts with formaldehyde similarly to phenol to form novolac or resole, which are cured by heating or by a curing agent such as hexamethylenetetramine. To do. The cured product is a material having excellent heat resistance and water resistance, and is used as an electrical material such as an insulating plate. The perfluoroalkenyloxyphenyl glycidyl ether is polymerized with a curing catalyst or a curing agent such as a Lewis acid, a tertiary amine, imidazole, an acid anhydride or a polyamine to produce a cured product, like the epoxy compound. The cured product is a material having excellent heat resistance and water resistance, and is used as an electrical material such as an insulating plate.

(Examples) Examples will be described in detail below.

Example 1 130 g of p-methoxyphenol, 900 ml of dimethylformamide and 318 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, and cooled to 20 ° C or lower.
To this, 450 g of hexafluoropropene trimer was added dropwise over 10 minutes while maintaining the temperature at 20 ° C or lower, and the mixture was stirred for 2 hours while maintaining the temperature at 20 ° C or lower. After the reaction, the reaction solution was poured into a large amount of dilute hydrochloric acid, the precipitated yellow oily matter was recovered, and the washing with water was repeated until the aqueous layer showed no acidity. The obtained oily substance was distilled to obtain 443 g of 4-perfluorononenyloxyphenyl methyl ether. bp86-87 ℃, / 4mmHg.

This compound (388 g) was dissolved in acetic acid (1300 ml), and 57% hydroiodic acid aqueous solution (1300 ml) was added, and the mixture was heated under reflux for 24 hr with stirring. After cooling, the liquid product was poured into a 5% sodium sulfite aqueous solution and extracted twice with chloroform 2. The chloroform solution was concentrated, and the obtained crude crystals were dissolved in chloroform and recrystallized to obtain 311 g of 4-perfluorononeneroxyphenol. mp 105 ° C.

¹⁹ F-NMR (external standard CF ₃ COOH, in CDCl ₃ , δppm) Shows chemical shift (δppm) with a value positive on the high magnetic field side (same below).

-5.1,6F -6.4,6F -21.4,3F 89.2,1F 91.4,1F Example 2 Instead of p-methoxyphenol in Example 1, m-
The procedure of Example 1 was repeated except that methoxyphenol was used to obtain 423 g of 3-perfluorononeneroxyphenyl methyl ether. bp83-86 ℃ / 4mmHg. This compound 38
8 g was dissolved in 1300 ml of acetic acid, 1300 ml of 57% hydroiodic acid was added, and the mixture was heated under reflux for 57 hours with stirring. After allowing to cool, the reaction solution was poured into a 5% sodium sulfite aqueous solution and extracted twice with chloroform 2. Distill off chloroform under reduced pressure,
The residue was distilled to obtain 282 g of 3-perfluorononenyloxyphenol. bp94-96 ℃ / 4mmHg.

¹⁹ F-NMR (external standard CF ₃ COOH, in CDCl ₃ , δ ppm) −5.2,6F −6.5,6F −21.3,3F 89.4,1F 91.3,1F Example 3 Substitution of hexafluoropropene trimer in Example 2 The same procedure as in Example 2 was carried out except that 300 g of hexafluoropropene dimer was used to obtain 235 g of 3-perfluorohexenyloxyphenyl methyl ether. 283g of this compound
Was dissolved in 1300 ml of acetic acid, 1300 ml of 57% hydroiodic acid was added, and the mixture was heated under reflux for 60 hours with stirring. After allowing to cool, the reaction solution is poured into a 5% sodium sulfite aqueous solution, and chloroform 2 is added.
It was extracted with. Chloroform was distilled off under reduced pressure, and the residue was distilled to give 3-perfluorohexenyloxyphenol 13
I got 9g. bp83-84 ℃ / 4mmHg.

¹⁹ F-NMR (external standard CF ₃ COOH, in CDCl ₃ , δppm) 4.1,3F 35.1,2F −18.0,3F −21.4,3F Example 4 3.5-Dimethoxyphenol 30.8 g was dissolved in dimethylformamide 190 ml, triethylamine 60.6. 20 g with addition of g
While keeping the temperature below, 10 g of hexafluoropropene trimer (86 g) was added dropwise over 10 minutes. After stirring for 4 hours, the reaction solution was poured into dilute hydrochloric acid and the precipitated oily matter was recovered and recrystallized from chloroform to obtain 71 g of 1-perfluorononenyloxy-3,5-dimethoxybenzene.

¹ H-NMR (in CDCl ₃ , TMS standard, δppm) 3.8, s, 6H 6.0, s, 2H 6.2, s, 1H 70 g of the above compound, 300 ml of acetic acid and 300 ml of 57% hydroiodic acid were mixed and heated under reflux for 60 hours. Let After allowing to cool, the reaction was poured into a 5% aqueous solution of sodium sulfite and extracted twice with 500 ml of chloroform, the chloroform was distilled off under reduced pressure, and the residue was recrystallized from chloroform to give 5-perfluorononenyloxybenzene-1. 34 g of 3,3-diol was obtained.

¹⁹ F-NMR (external standard CF ₃ COOH, in CDCl ₃ , δ ppm) −6.1,6F − 7.4,6F −22.3,3F 88.7,1F 90.5,1F Example 5 22.5 g of resorcinol monobenzoate was dissolved in 100 ml of dimethylformamide. , 32g of triethylamine was added,
Cooled to: Hexafluoropropene 3
The polymer was added dropwise over 10 minutes, and the mixture was stirred for 3 hours while maintaining the temperature below 20 ° C. The reaction solution was poured into dilute hydrochloric acid to collect a precipitate, which was washed with water and dried to recrystallize a crude product, which was recrystallized from chloroform to obtain 62 g of 3-perfluorononenyloxyphenyl benzoate.

60 g of this compound was added to 100 ml of methanol and sodium hydroxide 4.
The mixture was refluxed with heating while stirring with 7 g and 40 ml of water.
After 2 hours, hydrochloric acid was added to the reaction solution to make it acidic, and the reaction solution was separated into two layers. Extract the upper layer with chloroform,
The extract was combined with the lower layer, washed with water until it did not show acidity, the chloroform was distilled off, and the residue was distilled under reduced pressure to obtain 1-perfluorononenyloxy-3-hydroxybenzene (29 g). The boiling point and ¹⁹ F-NMR measurement results were the same as those of the compound obtained in Example 2.

Example 6 10.8 g of 4-perfluorononenyloxyphenol obtained in Example 1 was dissolved in 37 g of epichlorohydrin with heating. 0.2 g of water was added, and 1.1 g of atomized sodium hydroxide was gradually added while stirring with heating. 40 with stirring
Heating under reflux was continued for hours. After completion of the reaction, 200 ml of toluene was added, the produced sodium chloride was separated, and the solution was washed with water repeatedly until the aqueous layer showed no alkalinity. After the toluene solution was dried over anhydrous sodium sulfate, toluene and unreacted epichlorohydrin were distilled off under reduced pressure. Distill the residue under reduced pressure and collect a fraction of 135-136 ℃ / 5mmHg to 6.2g.
4 m-perfluorononenyloxyphenyl glycidyl ether was obtained.

¹ H-NMR (TMS standard in CCl ₄ , δppm) 2.6, m, 2H 3.2, m, 1H 3.8, m, 2H 6.8, s, 4H

Claims (1)

[Claims] 1. A general formula (R ¹ is OH or R ² is H, OH, an alkyl group having 1 to 4 carbon atoms, or X represents a perfluoroalkenyl group having 6 to 14 carbon atoms)
A perfluoroalkenyloxyphenol or a derivative thereof represented by: