JPH045260A - Fluorine-containing diester type compound and production thereof - Google Patents

Abstract

NEW MATERIAL:Fluorine-containing diester type compounds of formula I [Rf<1> is 1-20C perfluoroalkyl; X is divalent bonding group (R<3> is H or 1-20C alkyl; n is 1 or 2) represented by SO2NR<3>, CONR<3> or (CH2)n, R<1> and R<2> are 3-50C alkyl]. EXAMPLE:A compound of formula II. USE:Useful as a lubricant. By using as a mixture prepared by addition to a resin, useful also as a water repellent repelling water and a stainproofing agent preventing stains. In case of use as a lubricant for a magnetic tape for video, etc., its effect is kept for a long period only by surface coating and there is no problem in use in a cold district. A remarkable effect can be obtained even by a very thin coating. PREPARATION:For example, a fluorine-containing dihydroxy compound of formula III is reacted with an acid chloride of formula IV to obtain a compound of formula I or a compound of formula V is reacted with a compound of formula IV to obtain a compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fluorine-containing diester type compound, a method for producing the same, and a lubricant comprising the fluorine-containing diester type compound.

[Prior art and problems]

The compounds of the present invention are suitably used as lubricants and additives to resins. Conventionally, compounds such as liquid lubricants such as higher fatty acids and their esters, and solid lubricants such as molybdenum disulfide and graphite have been known as lubricants, but in recent years,
There is a growing demand for lubricants with higher performance. For example, high performance lubricants are required for magnetic tapes used in video and audio applications. These magnetic tapes have high smoothness on the surface of the magnetic layer, so the effective contact area is large, which can lead to problems with durability and runnability, such as increased adhesion and increased coefficient of friction. The use of various lubricants is being considered to improve this problem.

The main characteristics required of a lubricant used in such applications are that its effect lasts for a long time even when applied to the surface, that it can be applied extremely thinly, and that it has sufficient (3) It has excellent low-temperature properties and can be used in cold regions without any problems.

When conventional lubricants are used in these applications, there are problems in that solid lubricants are difficult to apply thinly and uniformly, and the distance between the head and the magnetic material increases. Furthermore, although liquid lubricants can obtain a lower coefficient of friction than solid lubricants, they cannot be used for magnetic tapes because they have a fatal defect in that the lubricant migrates to the head and deteriorates magnetic properties. Further, many liquid lubricants solidify and freeze at sub-zero temperatures, which poses a problem in that they cannot exhibit their full effectiveness.

On the other hand, in order to improve these problems, attempts have been made in recent years to utilize fluorine-based compounds as lubricants.

In this fluorine-based compound, both the interlayer slippage between the lubricant layer and the substance that occurs due to its small surface energy, and the intermolecular slippage that occurs due to the small intermolecular force act, which is noticeable even in extremely thin layers. It has the characteristics of being able to exhibit lubricity and durability.

As a lubricant using a fluorine-based compound, for example, a patent using a fluorine-based carboxylic acid type compound has been reported (Japanese Unexamined Patent Publication No. 58-29147). However, the above compounds still do not have sufficient lubricity, and since they are acidic compounds, ferrite and metal powder used as magnetic materials,
There are also problems in that it causes damage to the magnetic head and the like, which in turn causes deterioration of magnetic properties.

In addition, fluorinated oil (Japanese Patent Publication No. 57-49967), silicone oil with trifluoroalkyl group introduced (U,
S, P4, 369, 230) etc. are also being considered,
In addition to the fact that the above-mentioned problems have not necessarily been solved, there have been problems in using it for magnetic tapes and the like because it is expensive.

On the other hand, there are attempts to use higher fatty acid ester type compounds having perfluoroalkyl groups as lubricants (JP-A-62-161744, JP-A-62-161756).
Since this is a monoester type compound, it has a problem of insufficient lubricity. In particular, in higher fatty acid ester type compounds having perfluoroalkyl groups, some improvement has been made by changing the number of carbon atoms in the alkyl group of the ester group, but the above problem still remains unsolved. .

[Means for Solving the Problem: Structure of the Invention] The present inventors have discovered that a fluorine-containing diester compound having a long-chain alkyl group and a perfluoroalkyl group in its molecule provides high lubricity to the surface of a substance. This discovery led to the present invention.

In particular, the compound of the present invention has a branched molecular terminal and the presence of a long-chain alkyl group therein, which provides higher lubricity than conventional higher fatty acid monoester compounds.
It has characteristics that cannot be obtained.

That is, the present invention has the following features: 1. General formula (1) In the C formula, Rf1 is a perfluoroalkyl group having 1 to 20 carbon atoms, and X is SO, NR', C0NR' or (CH2)
A divalent bonding group represented by no (R3 is hydrogen or an alkyl group having 1 to 20 carbon atoms, n is 1 or 2), R1 and R2 are an alkyl group having 3 to 50 carbon atoms]. Diester type compound, 2. The fluorine-containing diester type compound represented by the above general formula (I) has the following general formula (II) (wherein Rf2 is a perfluoroalkyl group having 4 to 12 carbon atoms, or the same as above R4, R The fluorine-containing diester type compound according to claim 1, wherein ' is a long-chain alkyl group having 10 to 30 carbon atoms. (same as above) and a fluorine-containing dihydroxy compound represented by the general formula (rV)R”COCl
(IV) A method for producing a fluorine-containing diester type compound according to claim 1, which comprises reacting with a chloride represented by the formula (IV) (wherein R1 is the same as above), 4. General formula (V) (wherein Rfl, 2. The fluorine-containing diester compound according to claim 1, which comprises reacting a fluorine-containing monohydroxy monoester compound represented by (X and R2 are the same as above) and an acid chloride represented by the general formula (IV). Manufacturing method 5: A lubricant comprising the fluorine-containing diester compound according to claim 1.

The fluorine-containing diester compound of the present invention has a perfluoroalkyl group Rf1 and alkyl groups R1 and R2. The high lubricity exhibited by the compounds of the invention is due to both the perfluoroalkyl and alkyl groups.

The perfluoroalkyl group R,1 has 1 to 20 carbon atoms, and its carbon chain may have a branched chain or may contain a double bond.

Further, the alkyl groups R1 and R2 are alkyl groups having 3 to 50 carbon atoms, and the carbon chain may have a branched chain or may contain a double bond.

On the other hand, the lubricity or durability of the two ester groups present at the ends of the molecule can be adjusted by adjusting the number of carbon atoms in the alkyl group.

Further, the number of carbon atoms in each of the alkyl groups R1 and R2 may be the same or different.

Further, the fluorine-containing diester compound of the present invention has a divalent bonding group X. The bonding group X is 5o2NR3 or C0
An amide bond represented by NR3, or (CH2),
, 0 is an ether bond. Here 83 is
It is hydrogen or an alkyl group having 1 to 20 carbon atoms, and this alkyl group may have a branched chain or may contain a double bond. Further, n of the ether bond is 1 or 2.

This amide bond or ether bond connects the branched chain present at the end of the molecule with the perfluoroalkyl group, and since it has polarity, it has excellent adhesion to the base material and has the effect of increasing durability.

In this amide bond, the alkyl group bonded to the nitrogen atom has the effect of increasing its compatibility with the resin and also increasing its lubricity.

Among the fluorine-containing diester type compounds represented by formula (1) above, compounds represented by general formula (II) are preferred in practical use. Perfluoroalkyl group R,2 of the fluorine-containing diester compound represented by general formula (II)
has 4 to 12 carbon atoms, and R4 and R of the ester group
5 is a long chain alkyl group having 10 to 30 carbon atoms. R,2
, R4 and R5 each may have a branched chain and may contain a double bond. Further, the carbon numbers of R4 and R5 may be the same or different. By adjusting the number of carbon atoms, lubricity, durability, etc. can be adjusted as desired.

The fluorine-containing diester type compound represented by the general formula (-■) is the same as the compound represented by the general formula (I).

It has a divalent bonding group X. The bonding group X is exactly the same as in the fluorine-containing diester type compound represented by general formula (I).

A compound having a perfluoroalkyl group having 4 to 12 carbon atoms, which is a raw material for the compound represented by general formula (II), can be obtained industrially relatively easily and at low cost. In other words, compounds with perfluoroalkyl groups are industrially produced in large quantities as fluorine-based surfactants, water and oil repellents, etc. by electrolytic fluorination methods or telomerization methods, so it is easy to obtain raw materials. can be obtained.

Furthermore, the compound represented by general formula (II) has excellent lubricating properties.

On the other hand, when the number of carbon atoms in the perfluoroalkyl group is less than 4, although the lubricating properties are superior to those of ordinary hydrocarbon compounds, they are often still unsatisfied. Further, when the number of carbon atoms is more than 12, there is no significant change in characteristics compared to when the number of carbon atoms is less than 12.

In addition, the compound represented by the general formula (n) has 10 to 30 carbon atoms in its ester group, exhibits sufficient lubricity, and can be relatively easily converted into a hydrocarbon compound as a raw material for the ester group. Available.

Next, a method for producing the fluorine-containing diester type compounds represented by the general formulas (1) and (■) of the present invention will be explained.

The fluorine-containing diester type compound is a fluorine-containing dihydroxy compound represented by the general formula (m), or a fluorine-containing dihydroxy compound represented by the general formula (V)
A monohydroxy monoester type compound represented by
It is synthesized by reacting with an acid chloride represented by general formula (IV).

The compounds represented by general formulas (III), (V) and (IV) include R, 1. X, R", R
Contains 2nd grade.

Usually, as a method for synthesizing an ester type compound, a method is performed in which a corresponding alcohol and a carboxylic acid type compound are heated and the generated water is removed as needed. However, in the compound of the present invention, general formula (III), Or general formula (V)
The secondary hydroxyl group of the compound represented by has low reactivity, and it is difficult to completely obtain a diester type compound by heating with a carboxylic acid type compound.

The reason for the low reactivity of this secondary hydroxyl group is not clear, but it is thought to be due to steric hindrance as well as the formation of an intramolecular hydrogen bond between the hydroxyl group and the oxygen of the ether bond or the nitrogen of the amide bond in the molecule. It will be done.

Compounds represented by general formula (III) and general formula (rV)
In the reaction of the compound represented by the general formula (TV)
The compound represented by the formula (III) is used in an amount of 2 molar equivalents or more, preferably 2.0 to 2 molar equivalents, relative to the compound represented by the general formula (III).
．． It is synthesized by using 5 molar equivalents.

If the amount is less than 2 molar equivalents, the resulting compound will generally be a mixture of a diester type compound and a monoester type compound, making it difficult to selectively obtain a diester type compound.

In addition, in this case, in order to remove the hydrogen chloride that is generated,
The reaction is generally carried out in the presence of an organic base. This organic base is not particularly limited, but cyclic amines, tertiary amines, etc. are generally used, and specific examples include pyridine,
Examples include triethylamine. These bases are generally used in an amount of 2 molar equivalents or more, preferably 4 to 6 molar equivalents, based on the compound represented by the general formula (III).

Moreover, the reaction is generally carried out in a suitable solvent.

This solvent is preferably one that does not react with the compounds represented by the general formula (III) and the general formula (rV) and the coexisting base, and has high solubility for each compound. This solvent is not particularly limited, but specific examples include ether compounds such as isopropyl ether and tetrahydrofuran, halogenated hydrocarbon compounds such as dichloroethane and Freon 113, aromatic hydrocarbon compounds such as benzene and toluene,
Examples include aliphatic hydrocarbon compounds such as hexane, ketone compounds such as methyl isobutyl ketone, and the like. Isopropyl ether is usually the most commonly used.

In the reaction of the compound represented by the general formula (V) and the compound represented by the general formula (IV), the compound represented by the general formula (IV) is used in an amount of 1 molar equivalent to the compound represented by the general formula (V). The above is preferably synthesized by using 1.1 to 1.5 molar equivalents. If the amount of the compound represented by formula (IV) is 1 molar equivalent or less, it becomes difficult to selectively obtain a diester type compound.

The compound represented by the general formula (m), which is a raw material in the production of the compound of the present invention, can be synthesized by a known method, that is, by subjecting an epoxy compound having a corresponding perfluoroalkyl group to a ring-opening reaction with water ( Special request 1976
3-134569), and this epoxy compound can be easily synthesized by condensing the corresponding amide or alcohol with shrimp chlorohydrin in the presence of a base (Japanese Patent Application No. 63-17307).

On the other hand, the compound represented by the general formula (V) performs the ring-opening reaction of the above epoxy compound with the general formula R1C0□H (VI
) can be obtained by using a carboxylic acid shown in

The fluorine-containing diester type compound of the present invention is suitably used as a lubricant.

In actual use, this fluorine-containing diester type compound is added or coated during the production of coated tapes (e.g. conventional tapes made of sea ferrite as a magnetic material and fixed to a base material with urethane resin). used.

As mentioned above, the above-mentioned compounds of the present invention include those having an amide bond or an ether bond. In applications requiring wear resistance, etc., it is preferable to use a compound having an amide bond. this is.

Since this amide bond is rigid, it is based on the formation of a hard film. On the other hand, in applications requiring flexibility, etc., it is preferable to use a compound having an ether bond. This means that ether bonds are the opposite of amide bonds.
form flexible molecules.

This is based on the fact that the film also becomes flexible.

〔Effect of the invention〕

When the fluorine-containing diester type compound of the present invention is used as a lubricant for magnetic tapes for video and audio, (1) the effect lasts for a long time even when just applied to the surface;
2) It can be applied extremely thinly and provides sufficient lubricity; (3) It exhibits excellent lubrication properties such as excellent low-temperature properties and no problems when used in cold regions.

In addition, the compound of the present invention can be used not only as the above-mentioned lubricant, but also exhibits excellent effects when added to resin and used as a so-called water repellent agent that repels water and an antifouling agent that prevents stains. do.

〔Example〕

Examples of the present invention will be shown below along with applied examples and comparative examples.

Example 1 36.5 g of a fluorine-containing dihydroxy compound represented by the following formula was placed in a 5QOmU three-lens flask equipped with a mechanical stirrer, a thermometer, a reflux vessel equipped with a calcium chloride tube, and a dropping funnel.
(0.10 mol), triethylamine 40.4 g (0
, 40 mol) and 300 mQ of inpropyl ether, and add C from the dropping funnel. 45.0 g (0.22 mol) of H2□C0CD (acid chloride) was added dropwise at 30° C. over 3 hours.

After the dropwise addition was completed, the mixture was stirred at 80° C. for 5 hours, and then the reaction solution was poured into an excess dilute aqueous hydrochloric acid solution.

The organic layer was extracted with diethyl ether, neutralized, washed with water, dried over anhydrous sodium sulfate overnight, and the excess solvent was evaporated under reduced pressure to obtain a fluorine-containing diester compound 60 represented by the following formula. .3 g
I got it. The results of elemental analysis of this compound were as follows.

Calculated value (%) 54.8 7.4 2.0 Also, as a result of infrared spectroscopy (KBrBr method), 2930 cm
-12850 (hereinafter abbreviated as "cwt-"), 1740.
It showed a main absorption band between 1260 and 1130, and was confirmed to be the above compound.

Example 2 In a 1Ω three-loaf flask equipped with a mechanical stirrer, thermometer, reflux with calcium chloride tube, and addition funnel, C, H,
, CO (, R75.8 g (0.22 mol) and triethylamine 40.4 g (0.40 mol) were added through the dropping funnel.

The mQ tetrahydrofuran solution was added dropwise at 30° C. over 3 hours.

After the dropwise addition was completed, the mixture was stirred at 60° C. for 5 hours, and then the reaction solution was evaporated and concentrated under reduced pressure. Then, the reaction solution was poured into an excess dilute aqueous hydrochloric acid solution.

The formed precipitate was first washed thoroughly with water, then with acetone and hexane, and the results of elemental analysis and infrared spectroscopic analysis of this compound are shown below.

Analyzed value (%) 51.5 7.1 Calculated value (%
) 51.3 6.8 Infrared absorption band (cm-”
) 2930, 2850.1740.1400.1260-
1130 Example 3 In the same 1ρ three-loaf flask as in Example 2, add C2s Hs s
C0CQ 117.6g (0.25 mol), pyridine 3
9.5 g (0.50 mol) was put thereinto, and 500 mfl of isopropyl ether solution was added dropwise from the dropping funnel to the same Ifff flow flask as in Example 4 and Example 2 at 30° C. over 3 hours.

After the dropwise addition was completed, the mixture was stirred at 60° C. for 6 hours, and then the reaction solution was poured into an excess dilute aqueous hydrochloric acid solution.

The formed precipitate was first washed thoroughly with water, then with acetone and hexane, and the results of elemental analysis and infrared spectroscopic analysis of this compound are shown below.

), triethylamine 26.3 g (0.26 mol),
500 mQ of isopropyl ether was added, and 31.5 g (0.10 mol) of stearoyl chloride was added dropwise from the dropping funnel at 30°C over 3 hours. After the dropwise addition was completed, the mixture was stirred at 60° C. for 3 hours, and then the reaction solution was poured into an excess dilute aqueous hydrochloric acid solution, and the resulting precipitate was neutralized and washed by repeating washing with water, decantation, and crushing in a mortar.

By washing the brown solid thus obtained with a small amount of acetone, the following values were obtained: Analytical value C%) Calculated value (%) 65.9 65.2 Infrared absorption band (cll-1) 2930, 2850. 1740.1260-1130 The results of elemental analysis and infrared spectroscopic analysis of this compound are shown below.

Analysis value C%) Calculated value (%) 52.3 7.5 1.3 52.3 7.1 1.2 Infrared absorption band (am-1) 2930, 2850.1740.1400.1.260
~1130. .

Example 5 Into the same 500 mfl three-loaf flask as in Example 1.

Add 20.2 g (0.20 mol) of triethylamine, 3001I (l) of isopropyl ether, and add 11.7 g (0.11 mol) of C5H7COCΩ from the dropping funnel.
was added dropwise at 30°C for 3 hours. After the dropwise addition was completed, the mixture was stirred at 60° C. for 3 hours, and then the reaction solution was poured into an excess dilute aqueous hydrochloric acid solution, and the resulting precipitate was neutralized and washed by repeating washing with water, decantation, and crushing in a mortar.

The brown solid thus obtained was washed with a small amount of acetone, and the compound was subjected to elemental analysis and infrared spectroscopic analysis.The results are shown below.

Analyzed value (%) 61.3 9.0 Calculated value (%
) 60.0 13.7 Infrared absorption band (am-
) 2930, 2850.1740.1260~1130°Application example 1 15μm thick polyethylene terephthalate film,
Cobalt was deposited using an oblique evaporation method to create a ferromagnetic metal thin film with a thickness of 1,000 yen. 200 g of diester type compound 1, Og obtained in Example 1, was added to this metal thin film.
A sample tape was prepared by applying a solution of Freon 113 and cutting it into a 10 mm width.

The tape thus produced was measured for dynamic friction coefficient and shuttle durability under temperature conditions of 25°C and -5°C.

Application Examples 2 to 5 Regarding the diester type compounds obtained in Examples 2 to 5,
Evaluation was performed in the same manner as in Application Example 1.

Comparative Example 1 The same evaluation as in Application Example 1 was carried out using C□3H2□Co2CH2C1 (2C,F) as a fluorine-containing monoester compound without using a fluorine-containing diester compound.

Comparative Example 2 The same evaluation as in Example 1 was conducted using an untreated tape without using a lubricant. The results of Comparative Example 1.2 were applied to Application Examples 1 to 5.
The results are shown in Table 1.

Table 1 I sent it to test.

Indicates that a diester type compound was used.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, Rf^1 is a perfluoroalkyl group having 1 to 20 carbon atoms, and X is SO_2NR^3, CONR ^3 or (C
H_2)_nO divalent bonding group (R^3 is hydrogen or an alkyl group having 1 to 20 carbon atoms, n is 1 or 2
), R^1 and R^2 are alkyl groups having 3 to 50 carbon atoms]. 2. The fluorine-containing diester type compound represented by the above general formula (I) has the following general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R_f^2 is a carbon number of 4 to 12 Perfluoroalkyl group, X is the same as above, R^4, R^5 have 10 carbon atoms
2. The fluorine-containing diester compound according to claim 1, which is a compound represented by the following formula: -30 long-chain alkyl groups. 3. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R_f^1 and X are the same as above) A fluorine-containing dihydroxy compound and general formula (IV) R^1COCl ( IV) The method for producing a fluorine-containing diester type compound according to claim 1, which comprises reacting with an acid chloride represented by the formula (wherein R^1 is the same as above). 4. General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R_f^1, X and R^2 are the same as above) A fluorine-containing monohydroxy monoester type compound and the above The method for producing a fluorine-containing diester type compound according to claim 1, which comprises reacting the compound with an acid chloride represented by the general formula (IV). 5. A lubricant comprising the fluorine-containing diester compound according to claim 1.