JP3035672B2 - Fluorine-containing aromatic ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water and oil repellent, a release agent,
Useful as antifouling agents, plasticizers, and surface modifiers for resins, metals, wood, etc., and can be derived into other esters, amides, salts, etc. by having a reactive residue in the molecule. The present invention relates to a novel fluorine-containing aromatic ester useful as a synthetic intermediate.

[0002]

2. Description of the Related Art Esters derived from alcohols having a perfluoroalkyl group or a perfluoroalkenyl group have been known to have excellent water and oil repellency, weather resistance, low friction, slidability and releasability. It is known to have such characteristics (Japanese Patent Application Laid-Open Nos. 1-265061 and 2-282347). However, these fluorinated esters have only one perfluorocarbon chain in the molecule, and have insufficient properties such as water and oil repellency, low friction properties, slidability, and mold release properties. When surface treating
There has been a problem that adhesion to a resin or the like is insufficient.

[0003]

Means for Solving the Problems The present inventor has made intensive studies to solve the problems of the prior art as described above.
As a result, when a carboxylic acid having an aromatic ring is used as a raw material, the number of fluorocarbon chains can be freely changed, and the introduction rate of stable and highly branched fluorocarbon chains is higher than that of a conventional fluorinated ester. Found that a novel fluorinated aromatic ester having excellent water and oil repellency, low friction properties, sliding properties, releasability, etc., and also having properties such as durability and adhesion can be obtained. Was. Further, the fluorinated aromatic ester can be used to convert a reactive residue (eg, a carboxyl group) in the molecule into another ester, amide,
It can be guided to salts, etc., and is highly compatible with base materials.
It has also been found that various required performances can be satisfied, and that they are also useful as synthetic intermediates.

That is, the present invention provides a compound represented by the general formula (I):

[0005]

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[0006] (wherein, Rf is each the same or different C ₆
R ₁₁ represents a perfluoroalkenyl group represented by F ₁₁ or C ₉ F ₁₇ , R represents the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Ar represents a benzene ring which may have a substituent. Or a naphthalene ring which may have a substituent. n represents an integer of 1 to 8;
And n + m ≦ 8. )).

In the general formula (I), Rf represents a perfluoroalkenyl group represented by C ₆ F ₁₁ or C ₉ F ₁₇ , and when two or more are present, they are the same or different. This group is generally derived from a dimer or trimer of hexafluoropropene. Examples of such a perfluoroalkenyl group include those represented by the following structure.

[0008]

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In the general formula (I), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when two or more are present, they are the same or different. Examples of such an alkyl group include a methyl group, an ethyl group, and a propyl group.

Ar represents a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. Examples of the substituent include a methyl group, an ethyl group, a halogen atom (F,
Cl, Br, I), a nitrile group, a nitro group, a hydroxyl group and the like. The number of these substituents is preferably 1 or 2.

N is an integer of 1 to 8, preferably 1 to
Indicates an integer of 6. m represents an integer of 0 to 7, preferably 0 to 6. Further, n and m satisfy n + m ≦ 8.

The method for producing the fluorine-containing aromatic ester represented by the general formula (I) is not particularly limited, but examples of the simple method include the following production methods.

The first production method has the general formula (II):

[0014]

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(In the formula, Rf is the same as described above.) A fluorinated alcohol represented by the general formula (II) in the presence of an acid catalyst:
I): reacting with an aromatic carboxylic acid or ester represented by Ar (CO ₂ R) _l (III) (wherein R and Ar are the same as above, and l represents an integer of 1 to 8) Is the way.

Examples of the fluorinated alcohol of the general formula (II) include p- (perfluorononenyloxy) phenylethyl alcohol, p- (perfluorohexenyloxy) phenylethyl alcohol and the like. The fluorinated alcohol, for example, in the case of p- (perfluorononenyloxy) phenylethyl alcohol, can be obtained in a higher yield than the reaction of p-hydroxyphenylethyl alcohol with a trimer of hexafluoropulpene under basic conditions. can get.

Examples of the aromatic carboxylic acid or its ester represented by the general formula (III) include benzoic acid, methyl benzoate, ethyl benzoate, propyl benzoate, phthalic acid, dimethyl isophthalate, diethyl terephthalate,
Triethyl trimellitate, trimesic acid, pyromellitic acid, hexamethyl melitate, benzenetetracarboxylic acid, toluenehexacarboxylic acid, naphthalic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and the like,
Among these, the carboxylic acid can also be used in the form of a C _1-3 alkyl ester.

According to the above-mentioned production method, the compound of the present invention is
0.1 to 20 mol, preferably 0.1 to 10 mol, of the fluorinated alcohol represented by the general formula (II) is added to 1 mol of the aromatic carboxylic acid or ester represented by the general formula (III). In the presence of an acid catalyst such as hydrogen chloride, concentrated sulfuric acid, p-toluenesulfonic acid, a strongly acidic ion exchange resin,
1 at a temperature of 50-200 ° C, preferably 60-150 ° C.
It is obtained by reacting for about 48 hours. At this time, if desired, an inert solvent such as benzene or toluene may be used.

More specifically, the compound obtained by the above-mentioned process is represented by p- (perfluorononenyloxy) phenylethyl alcohol and benzoic acid (or an ester thereof).

[0020]

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Are synthesized.

From trimellitic acid (or its ester), for example, the following compounds are synthesized.

[0023]

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From toluenepentacarboxylic acid (or an ester thereof), a compound of the following formula wherein n is up to 5 can be obtained.

[0025]

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From naphthalic acid (or its ester), the following are synthesized.

[0027]

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(Where Rf and R are the same as described above) A second process for preparing the compound of the present invention is represented by the general formula (II):

[0029]

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(Wherein, Rf is as defined above) is reacted with a fluorinated alcohol represented by the general formula (IV): Ar (COX) p (IV) (where X is A halogen atom, and p represents an integer of 1 to 8. Ar is the same as defined above, or a carboxylic acid halide represented by the general formula (V): (ROCO) r-Ar-((CO) ₂ O) q (V) (wherein, R is the same as above. R represents an integer of 0 to 6;
Represents an integer of 1 to 4, and r + p ≦ 8. Ar is the same as above. )).

Examples of the aromatic carboxylic acid halide represented by the general formula (IV) include benzoyl chloride, terephthalic acid dibromide, trimesic acid trichloride and the like.
Examples of the carboxylic anhydride represented by the general formula (V) include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride and the like.

[0032] The second production method is carried out in the range of 0.1 to 20 mol per mol of the aromatic carboxylic acid halide or carboxylic anhydride represented by the general formula (IV) or (V).
Mol, preferably 0.1 to 10 mol, of the fluorinated alcohol represented by the general formula (II) in the presence of a basic compound such as pyridine, triethylamine, potassium carbonate, or a basic ion exchange resin. C., preferably at a temperature of -10 to 80C for about 30 to 180 minutes. At this time, if desired, an inert solvent such as benzene, toluene, acetone, hexane,
Diethyl ether or the like may be used.

The product obtained by the above production method is
If desired, it may be purified by distillation, recrystallization, column chromatography or the like.

[0034]

The present invention will be described below with reference to examples.

[0035]

Example 1 In a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, 57.0 g (0.1 mol) of p-perfluorononenyloxyphenylethyl alcohol and 13.9 g (0.1 mol) of methyl benzoate were added. Mol) and 0.8 g of p-toluenesulfonic acid, and the mixture was heated and stirred at 105-110 ° C for 9 hours.

The reaction product was dissolved in 300 ml of benzene, and the solution was washed with an aqueous sodium hydrogen carbonate solution and then with a saturated saline solution. The organic layer was separated, and the solvent was removed by heating under reduced pressure.

The obtained crude product was subjected to distillation under reduced pressure to obtain 34.6 g of a compound I represented by the following formula (yield: 51%).

The physical properties of Compound I are shown in Table 1 below.

Compound I:

[0040]

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[0041]

Example 2 56.8 g (0.1 mol) of p-perfluorononenyloxyphenylethyl alcohol and 10.1 g of terephthalic acid dichloride were placed in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel. 0.05
Mol), acetone (30 ml) and benzene (100 ml), and a solution of 13.5 g of triethylamine dissolved in 30 ml of benzene was added dropwise to the mixture while cooling to 10 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours.

The reaction product was dissolved in 300 ml of benzene, and the solution was washed with 5% diluted hydrochloric acid, an aqueous solution of sodium hydrogencarbonate, and then with a saturated saline solution. The organic layer was separated, and the solvent was removed by heating under reduced pressure.

The obtained crude product was subjected to silica gel column chromatography to obtain 36.7 g of a compound II represented by the following formula (yield: 58%). The physical properties of Compound II are shown in Table 1 below.

Compound II:

[0045]

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[0046]

Example 3 In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a dropping funnel, 22.7 g (0.04 mol) of p-perfluorononenyloxyphenylethyl alcohol and 4.4 g of pyromellitic anhydride ( 0.02 mol), and 10.5 g of pyridine was added dropwise to the mixture at room temperature. After completion of the dropwise addition, the mixture was stirred at 50 to 55 ° C. for 4.5 hours.

The reaction product was dissolved in diethyl ether (300 ml).
, And the solution was washed with 5% diluted hydrochloric acid, an aqueous solution of sodium hydrogen carbonate and then with a saturated saline solution. The organic layer was separated, and the solvent was removed by heating under reduced pressure.

The obtained crude product was subjected to silica gel column chromatography to obtain 12.4 g of a mixture of a compound III-a and a compound III-b represented by the following formula (yield: 45%).
Table 1 shows the physical properties of Compound III-a and Compound III-b.

Compound III-a

[0050]

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Compound III-b

[0052]

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[0053]

Example 4 14.8 g (0.03 mol) of p-perfluorononenyloxyphenylethyl alcohol and 10.6 g (0.02 mol) of hexamethyl melitate were placed in a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser. Mol), 20 ml of toluene and 1 ml of concentrated sulfuric acid.
The mixture was heated and stirred at 15 ° C for 5 hours.

The reaction product was dissolved in 300 ml of benzene, the solution was washed with an aqueous solution of sodium hydrogencarbonate and then with a saturated saline solution, the organic layer was separated, and the solvent was removed by heating under reduced pressure.

The obtained crude product was extracted with hexane-benzene (9: 1) and then washed with methanol to obtain 5.2 g of a compound IV represented by the following formula. The physical properties of Compound IV are shown in Table 1 below.

Compound IV:

[0057]

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[0058]

[Table 1]

[0059]

The fluorine-containing aromatic ester provided by the present invention can freely change the fluorocarbon chain per molecule and has a reactive residue (for example, a carboxyl group). Sliding agent, release agent,
It is useful not only as a surface modifier for plastics, metals, woods and the like, but also as a synthetic intermediate because it can be easily derived into other fluorine-containing esters and amides.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09K 3/00 112 C09K 3/00 112D 3/18 102 3/18 102 C10M 105/54 C10M 105/54 C10N 40:36 (72 ) Inventor Nobuhiko Ritsuiri 1-1, Oike-cho, Kosai-cho, Koka-gun, Shiga Prefecture Neos Corporation (56) References JP-A-1-131137 (JP, A) JP-A-1-9958 (JP, A) 2-501311 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 69/767 C07C 69/78 C07C 69/83 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, Rf is the same or different and each is C ₆ F ₁₁ or C
It indicates perfluoroalkenyl group represented by ₉ F _17,
R is the same or different and each represents a hydrogen atom or 1 to 3 carbon atoms;
And Ar represents a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. n shows the integer of 1-8, m shows the integer of 0-7, and n + m <= 8. ) A fluorine-containing aromatic ester represented by the formula: