JPH0967334A - Fluoroalkyl alcohol and derivative therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new alcohol expressed by a specific formula and useful as e.g. a raw material for water repellents giving both water and oil repellency to base materials such as textiles, paper, wood, leathers, resins, glass and metals. SOLUTION: This new alcohol is expressed by formula I (Rf is a 1-20C fluoroalkyl or fluoroalkenyl; (m) is 1-11; (n) is 1 or 2). This alcohol, e.g. an alcohol of formula II, is obtained, pref. by reaction of a 1,3-dihalo-2-propanol (e.g. 1,3-dibromo-2-propanol) with a thiol of formula III (e.g. perfluorooctylethanethiol) in the presence of a base catalyst (e.g. an alkali metal carbonate such as NaCO3 ) in a ketone solvent such as acetone.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel fluoroalkyl alcohol and its derivative useful as a raw material and an intermediate for the fluorochemical industry, and a water repellent material for fibers, paper, wood, leather, resins, glass, metals and the like. , A water repellent agent that imparts oil repellency.

[0002]

2. Description of the Related Art Heretofore, as a water repellent comprising a polymer of acrylate or methacrylate having a perfluoroalkyl group, a homopolymer or copolymer of monomers represented by the following general formula (Formula 3) has been proposed. (Japanese Patent Laid-Open No. 61-1
No. 76560).

[0003]

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Here, Rf represents a perfluoroalkyl group having 1 to 18 carbon atoms, R represents a hydrogen atom or a methyl group, m represents an integer of 2 to 20, and n represents an integer of 2 to 20. .

[0005]

However, the above-mentioned conventional water repellents made of polymers can impart appropriate water repellency and oil repellency to porous substrates such as fibers and papers, but they are not limited to metal. There is a problem that it is not possible to impart sufficient water repellency or oil repellency to a smooth base material such as glass or glass.

The present invention solves the above-mentioned conventional problems, and a novel fluoroalkyl alcohol having a molecular chain containing two fluoroalkyl groups or fluoroalkenyl groups in the same molecule, a derivative thereof, fiber, paper, It is an object of the present invention to provide a water repellent that imparts water repellency and oil repellency to a substrate such as wood, leather, resin, glass and metal.

[0007]

In order to achieve the above object, the substance of the present invention is a fluoroalkyl alcohol represented by the general formula (Chemical formula 4) or a fluoroalkyl alcohol derivative thereof represented by the general formula (Chemical formula 5). It is a polymer containing an alkyl compound and at least one kind of the fluoroalkyl compound in repeating monomer units.

[0008]

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Here, Rf represents a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms, and m is 1 to 1
It represents an integer of 1, and n represents 1 or 2.

[0010]

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Here, Rf represents a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, m represents an integer of 1 to 11,
n represents 1 or 2.

From the viewpoint of easy handling such as solubility in a solvent, Rf is preferably a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms. From the viewpoint of the economical efficiency of the raw material for production, m is preferably an integer of 1 to 11 and n is preferably 1 or 2. However, technically, it is possible to produce carbon having a carbon number other than this range. Is.

The method for producing a fluoroalkyl alcohol represented by the general formula (formula 6) included in the substance of the present invention is 1,3-dihalo-2-propanol and a thiol represented by the general formula (formula 7). Is achieved by reacting with a base as a catalyst.

[0014]

[Chemical 6]

Here, Rf represents a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms, and m is 1 to 1
Indicates an integer of 1.

[0016]

[Chemical 7]

Here, Rf represents a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms, and m is 1 to 1
Indicates an integer of 1.

The method for producing a fluoroalkyl alcohol represented by the general formula (Chemical formula 8) included in the substance of the present invention includes 1,4-dihalo-2-butanol and a thiol represented by the general formula (Chemical formula 7). Is achieved by reacting with a base as a catalyst.

[0019]

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Here, Rf represents a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms, and m is 1 to 1
Indicates an integer of 1.

As the base catalyst in the production of the fluoroalkyl alcohol represented by the general formulas (Formula 6) and (Formula 8), alkali metal carbonates such as NaCO ₃ and KCO ₃ , Ca (CO ₃ ) ₂ and Mg ( It is possible to apply alkaline earth metal carbonates such as CO ₃ ) ₂ and alkali metal alkoxides, and as the solvent, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane are suitable. ing.

The method for producing a fluoroalkyl compound represented by the general formulas (Chemical Formula 9) and (Chemical Formula 10) included in the substance of the present invention is as follows. It is realized by reacting the fluoroalkyl alcohol represented by Chemical formula 8 with a base as a catalyst.

[0023]

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Here, Rf represents a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 11.

[0025]

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Here, Rf represents a fluoroalkyl group or a fluoroalkenyl group having 1 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 11.

As the base catalyst in the production of the fluoroalkyl compound represented by the general formulas (Chemical Formula 9) and (Chemical Formula 10), pyridine, trimethylamine and the like can be applied, and the solvent thereof can be an aliphatic or aromatic solvent. Anhydrous solvents such as hydrocarbons, halogenated hydrocarbons and ethers are suitable.

The method for producing a polymer containing at least one type of fluoroalkyl compound represented by the general formulas (Chemical Formula 9) and (Chemical Formula 10) included in the substance of the present invention in repeating monomer units is a single method. Alternatively, it is realized by reacting a mixture with another vinyl monomer using a radical initiator as a catalyst.

As the radical initiator, potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide,
Acetyl peroxide, benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azobiscyanovaleric acid, etc. Can be applied.

As the other vinyl monomer, a fluorine-containing vinyl compound is preferable, and the mixing amount thereof is 0-8.
A range of 0% by weight, preferably 0 to 60% by weight is suitable, and when the amount of the fluoroalkyl compound represented by the general formula (Formula 9) or (Formula 10) is less than 20% by weight, sufficient water repellency can be obtained. It's hard to be beaten. As the fluorine-containing vinyl compound,
Fluoroolefins, phlorogiens, fluorostyrenes, fluoroalkyl or fluorophenyl acrylates and methacrylates, fluoroalkyl or fluorophenyl vinyl esters and the like can be applied.

The polymer of the present invention can be easily produced by a method such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization as in the conventionally known vinyl polymerization.

[0032]

The fluoroalkyl alcohol and its derivative of the present invention have a molecular chain containing two fluoroalkyl groups or fluoroalkenyl groups in the same molecule, and this molecular chain contains two fluoroalkyl groups or Since the fluoroalkenyl groups are present in a spatially close state, the low surface energy property of the fluorine chain is further emphasized and expressed.
Therefore, the polymer obtained from this derivative has a side chain having strong water repellency, and when this is coated on the substrate, the side chain having this strong water repellency is arranged on the surface of the substrate.

Therefore, the water repellent of the present invention can impart sufficient water repellency and oil repellency to a substrate such as fiber, paper, wood, leather, resin, glass and metal.

[0034]

【Example】

(Embodiment 1) Hereinafter, the first embodiment of the present invention will be specifically described.

The substance of this embodiment is represented by (Chemical Formula 11).

[0036]

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Explaining the substance of (Chemical Formula 11) in comparison with the general formula of (Chemical Formula 4), Rf is a fluoroalkyl group having 8 carbon atoms, m is 2 and n is 1.

Next, a method for producing the substance represented by Chemical formula 11 will be described. The starting materials are 1,3-dibromo-2-propanol and a known perfluorooctylethanethiol represented by the chemical formula (12).

[0039]

[Chemical 12]

1,3-dibromo-2-propanol 10.9 g
(0.05 mol), perfluorooctylethanethiol 48.0 g (0.10 mol) and potassium carbonate 13.8 g
(0.10 mol) and 200 ml of methyl isobutyl ketone were sampled in a 1-liter flask equipped with a stirring blade, and the reaction was continued under reflux for 48 hours with stirring. After the reaction was completed, the solution was cooled and then stirred while stirring, and 30 ml of 4N hydrochloric acid was added.
Was gradually added, and then 300 ml of ethyl acetate was added, and this solution was repeatedly washed with distilled water until the pH reached 7, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off, and the reaction product was recrystallized as a methanol solution at 0 ° C. to obtain 34 g of a white solid having a melting point of 96 ° C. This white solid was analyzed by infrared spectroscopy (IR), gel permeation chromatography (GPC) and organic mass spectrometry (FD-).
By MS), it was found to be a fluoroalkyl alcohol represented by the formula (Formula 11) containing no starting material and by-products.

IR: Alcohol absorption peak at 3,400 cm ^-1 (Fig. 1) GPC: Starting material and by-products not detected FD-MS: Main peak at m / e 1,017 In this Example In the general formula (Formula 4), Rf is a fluoroalkyl group having 8 carbon atoms, and the production method in the case where m is 2 is explained. However, when the chain length is different from this, perfluorooctylethanethiol is used as the starting material Alternatively, for example, by using (Chemical Formula 13) or (Chemical Formula 14), (Chemical Formula 15) or (Chemical Formula 16) can be similarly produced. Also, Rf
In the case where is a fluoroalkenyl group, the starting material may be replaced with perfluorooctylethanethiol, for example (Chemical Formula 1
(Chemical Formula 18) can be similarly produced by using 7).

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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Further, in this example, the production method in the case where n in the general formula (Formula 4) was 1 was explained, but in the case where n is 2, 1,3-dibromo-2-propanol is used as the starting material. 1,4-dichloro-2-butanol and 1,4-dibromo-2-
Similarly, by using butanol, (Chemical Formula 19) can be produced.

[0049]

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(Embodiment 2) Next, a second embodiment of the present invention will be specifically described. The substance of this example is
0).

[0051]

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Explaining the substance of (Chemical Formula 20) in comparison with the general formula of (Chemical Formula 5), Rf is a fluoroalkyl group having 8 carbon atoms, R is a hydrogen atom, m is 2 and n is 1. It is a thing.

Next, a method for producing the substance represented by Chemical formula 20 will be described. 30.5 g (0.03) of the fluoroalkyl alcohol represented by the formula (Formula 11) obtained in Example 1
Mol), pyridine (4.8 g, 0.06 mol) and anhydrous diethyl ether (100 ml) were collected in a 1 liter flask equipped with a stirring blade, and acryloyl chloride (2.7 g, 0.04) was added under ice cooling.
100 ml of anhydrous diethyl ether in which (03 mol) was dissolved was added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued at room temperature for 4 hours to complete the reaction. After completion of the reaction, the reaction solution was washed with 200 ml of 5% hydrochloric acid aqueous solution to remove excess pyridine from the reaction solution. Further, the solution was repeatedly washed with distilled water until the pH reached 7, and then dried over anhydrous sodium sulfate. Next, the solvent was distilled off, and the reaction product was recrystallized as an ethanol solution at 0 ° C. to obtain 28 g of a colorless transparent liquid at room temperature. This colorless transparent liquid was found by IR, GPC and FD-MS to be a fluoroalkyl compound represented by the formula (Formula 20) containing no starting materials and byproducts.

IR; disappearance of absorption peak of alcohol at 3,400 cm ^-1 , appearance of absorption peak of ester at 1,725 cm ^-1 (Fig. 2) GPC; starting material and by-products not detected FD-MS; m / e There is a main peak at 1,071. In this example, the production method in which Rf in the general formula (Formula 5) is a fluoroalkyl group having 8 carbon atoms, m is 2 and n is 1 has been described. Also in the case where is different, by using (Chemical formula 15), (Chemical formula 16), (Chemical formula 18) or (Chemical formula 19) instead of (Chemical formula 11) as the starting material, , (Chemical formula 23) or (Chemical formula 24) can be produced.

[0055]

[Chemical 21]

[0056]

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[0057]

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[0058]

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In this example, the production method in which R in the general formula (Formula 5) is a hydrogen atom has been described. However, in the case where R is a methyl group, the starting material is replaced with acryloyl chloride and methacryloyl chloride is used. By using the same, (Chemical Formula 25) can be similarly produced.

[0060]

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(Embodiment 3) Next, a third embodiment of the present invention will be specifically described. The substance of this example is
It is a copolymer of a fluoroalkyl compound represented by formula (0) and a known perfluoroalkyl acrylate represented by (formula 26).

[0062]

[Chemical formula 26]

A 2-liter flask containing 400 parts by weight of hexafluoroxylene was purged with nitrogen and then heated to the reflux temperature, and 300 parts by weight of the fluoroalkyl compound represented by (formula 20) and (formula 26) were added thereto. A monomer solution in which 12 parts by weight of azobisisobutyronitrile (AIBN) was dissolved in 300 parts by weight of the indicated perfluoroalkyl acrylate was added dropwise in about 3 hours. Then, under reflux, AIBN
2 parts by weight was added 4 times at intervals of 1 hour, and the mixture was further refluxed for 2 hours to obtain a copolymer of (Chemical formula 20) and (Chemical formula 26).

(Examples 4 to 8) A copolymer of the fluoroalkyl compound (A) of the present invention obtained in the same manner as in Example 3 and a conventionally known fluorine-containing vinyl compound (B) and a homopolymer of A The coalescence is shown in (Table 1).

For B, (Chemical 27), (Chemical 28), (Chemical 2)
The fluorine-containing vinyl compounds represented by 9) and (Chem. 30) were used.

[0066]

[Table 1]

[0067]

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[0068]

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[0069]

[Chemical 29]

[0070]

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(Example 9) Next, the application of the water repellent of the present invention to a metal substrate will be specifically described. A smooth aluminum material having a maximum surface roughness (Rmax.) Of 3 to 4 μm was used as the base material of this example. The water repellency and oil repellency of a test piece obtained by coating the substrate with the water repellent of the present invention and a conventionally known water repellent in an amount of 10 μg per cm ² were examined.
The water repellency was examined by transferring 1 μl of distilled water from the tip of an injection needle to the surface of a horizontally placed test piece and immediately measuring the contact angle between water and the test piece. Test results show water repellency of 4
Classified into grades, 120 ° or higher is A grade, 110-119 °
Was classified as B class, 100 to 109 ° as C class, and less than 100 ° as D class. The oil repellency is examined by the method according to the standard test method of AATCC 118-1992, and the test result shows that the oil repellency is 0.0 (minimum) to 8.
It was classified into a grade of 0 (maximum). The results of these tests are shown in (Table 2). As the water repellents of Conventional Examples 1, 2 and 3 in the table, homopolymers of (Chemical formula 26), (Chemical formula 29) and (Chemical formula 31) were used, respectively.

[0072]

[Table 2]

[0073]

[Chemical 31]

It can be seen from Table 2 that all the water repellents of the present invention impart strong water repellency and oil repellency to the smooth aluminum material.

(Example 10) Next, the application of the water repellent of the present invention to a fiber base material will be specifically described.

A 100% polyester cloth was used as the base material in this example. The water repellent of the present invention was added to this base material in an amount of 0.
The water repellency and the oil repellency were examined for each of the test pieces which were applied so as to be 1% and heat-treated at 150 ° C. for 5 minutes. Water repellency is checked by the method based on JIS L1092 spray test method,
The test results were classified into water repellency with a score of 0 (minimum) to 100 (maximum). The oil repellency was examined by the method according to the standard test method of AATCC 118-1992, and the test result shows that the oil repellency is 0.0 (minimum).
Classified as ~ 8.0 (maximum). The results of these tests are shown in (Table 3). The water repellents of Conventional Examples 1, 2 and 3 in the table are (Chemical formula 26), (Chemical formula 29) and (Chemical formula 31), respectively.
Was used.

[0077]

[Table 3]

From Table 3, it can be seen that all the water repellents of the present invention impart strong water repellency and oil repellency to polyester cloth.

[0079]

As is apparent from the above description, the fluoroalkyl alcohol and its derivative of the present invention are novel organic compounds having a molecular chain containing two fluoroalkyl groups or fluoroalkenyl groups in the same molecule. These are useful as raw materials and intermediates for the fluorochemical industry. Further, the polymer obtained from the derivative of the present invention is useful as a water repellent that imparts sufficient water repellency and oil repellency to a substrate such as fiber, paper, wood, leather, resin, glass and metal.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared spectroscopic analysis result of a fluoroalkyl alcohol represented by the formula (Formula 11).

FIG. 2 is a diagram showing an infrared spectroscopic analysis result of a fluoroalkyl compound represented by the formula (Formula 20).

Claims (3)

[Claims] 1. A fluoroalkyl alcohol represented by the following general formula (Formula 1). Embedded image Here, Rf shows a C1-C20 fluoroalkyl group or a fluoroalkenyl group, m shows the integer of 1-11, and n shows 1 or 2. 2. A fluoroalkyl alcohol derivative which is a fluoroalkyl compound represented by the following general formula (Formula 2). Embedded image Here, Rf represents a C1-C20 fluoroalkyl group or a fluoroalkenyl group, R represents a hydrogen atom or a methyl group, m represents an integer of 1 to 11, and n represents 1 or 2. 3. A water repellent comprising a polymer containing at least one kind of the fluoroalkyl compound according to claim 2 in a repeating monomer unit.