JP2604186B2 - New ester compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel ester compound having a high fluorine content.

[Related Art] In recent years, when molding a heat-resistant thermoplastic resin whose demand is growing, a special sliding is required due to its high melting temperature, and at present, oligomers of fluorinated ethylene are widely used. ing.

[Problems to be Solved by the Invention] However, the above compounds have poor polarity and have problems in properties such as solubility. For this reason, ester compounds of fluorinated alcohols have been studied, but the expected physical properties have not been obtained due to insufficient fluorine content, molecular weight and the like.

As a result of various studies to solve the above problem, the present inventors have focused on 1,2,3,4-butanetetracarboxylic acid (hereinafter abbreviated as “BTC”) as an acid component of the ester compound. .

BTC is an organic acid with four minimal carboxyl groups. By reacting this with a fluorinated alcohol to form an ester compound, the molecular weight is sufficiently large,
And it becomes an ester having a high fluorine content.

Further, by appropriately selecting the mixing ratio of the fluorinated alcohol to the acid component, the molecular weight and the fluorine content can be set to numerical values as required, and desired characteristics can be obtained.

That is, an object of the present invention is to provide a novel fluorine-containing ester compound which is useful as a heat-resistant lubricant, a fiber treatment agent, and the like, and has not been described in any literature.

[Means for Solving the Problems] An ester compound according to the present invention is represented by the general formula (I).

(In the formula, k, l, m, and n represent an integer of 0 to 3, and may be the same or different. However, not all of them are 0. a, b, c , D is 0
Or 1 and may be the same or different, but not all of them are 0. The following esters are excluded from the ester compounds represented by the general formula (I).

The compound is prepared, for example, by the following method.
That is, (1) BTCs as an acid component and a fluorinated alcohol represented by the general formula (II) as an alcohol component are esterified according to a conventional method.

H (CH ₂ CF ₂ ) _p CH ₂ OH (II) (In the formula, p represents an integer of 1 to _3. ) Here, BTCs include BTC and the monoanhydride or dianhydride, and It is a generic term for monoesters, diesters, triesters, tetraesters and the like of lower alcohols having 1 to 4 carbon atoms exemplified by methanol, ethanol, propanol, isopropanol, butanol, isobutanol and the like.

(2) The lower alcohol ester of BTC is transesterified with the fluorinated alcohol.

The addition amount of the fluorinated alcohol is appropriately selected depending on the number of ester groups in the target ester in any method, and specifically, about 1.0 to 3.0 equivalents per carboxyl group in BTCs, preferably Is carried out using about 1.05 to 2.0 equivalents.

As the catalyst, a compound generally used as an esterification catalyst or a transesterification catalyst is sufficient, and specifically, a hydroxide of an alkali metal or an alkaline earth metal,
Mineral acids such as oxides, carbon salts, sulfuric acid, hydrochloric acid, and phosphoric acid; organic sulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid; acidic clay, sulfuric acid bands, silica alumina, and γ-
Solid acid catalysts such as alumina, phosphotungstic acid, and phosphomolybdic acid; Lewis acids such as boron trifluoride, zinc chloride and tin chloride; metal oxides such as tin oxide, titanium oxide and dibutyltin oxide; and lower alcohols thereof. And alkoxides of fatty acids such as Na, K, Ca, Mg, Zn and Pb, and alkoxides thereof with lower alcohols are effective.

The addition amount of the catalyst is about 0.001 to 50% by weight based on the BTC,
Preferably, it is about 0.01% to 10%.

The reaction temperature is generally about 30-300 ° C., preferably about 60 ° C.
~ 200 ° C.

The reaction can be allowed to proceed not only under normal pressure but also under reduced pressure or increased pressure as necessary, and is usually completed in 1 to 20 hours.

In the case of an esterification reaction, it is desirable to proceed with the reaction while distilling off and removing water produced, and in the case of a transesterification reaction, a lower alcohol. In this case, it is effective to use an entrainer such as benzene, toluene, or xylene as necessary.

After completion of the reaction, the catalyst is removed by an appropriate treatment such as neutralization, washing, or filtration, and excess alcohol is topped under reduced pressure to obtain a target product.

The ester compounds thus obtained are heat-resistant lubricants, lubricants for magnetic recording media, fiber treatment agents for various fibers such as waterproof and stain-resistant fibers, surface treatment agents for paper and leather, stain-resistant paints, car waxes, etc. It is useful as various waxes, printing ink additives, back surface treatment agents for pressure-sensitive adhesive tapes, mold release agents, fluidity improvers for plastics, boiling resistance improvers, antifogging agents and the like. In addition to the above-mentioned uses, partial esters are used for general use as an epoxy resin curing agent and a fluorine-containing surfactant, for example, as an antifoaming agent, an emulsifier, a surface treatment agent for metals or pigments, and the like.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 A fourteen-necked flask fitted with a decanter was charged with BT.
C 23.4 g (0.1 mol) and 1H, 1H, 7H-dodecafluoro-1-
160 g (0.48 mol) of ppetanol and 2 g of p-toluenesulfonic acid were added and stirred while heating. When the reaction was refluxed at a liquid temperature of 190 ° C. and the reaction was continued while removing the produced water, the liquid which was initially in a dispersed state became a uniform liquid. Further, the reaction was continued while heating until a theoretical amount of water was generated. At this time, the acid value of the solution was 2.1. To the reaction mixture was added a methanol solution of toluene and potassium hydroxide in an amount equivalent to 1.1 times the acid value, and the mixture was stirred at 60 to 70 ° C. for 30 minutes for neutralization. Hot water was added to this, washed with water three times, and then topped to obtain 142 g (95% yield) of the desired ester. The ester has a saponification value of 149.5 (theoretical value of 150.6), an acid value of 0.5,
Melting point: 86.5-88.0 ° C. The elemental analysis values of this are shown below. In addition, NMR (d ₆ -acetone) and infrared absorption spectrum (KBr method) are shown in FIGS. 1 and 2, respectively.

Actual value (%) Theoretical value (%) C 29.1 29.02 H 1.2 1.21 O 8.7 8.59 F 61.0 61.18 C ₃₆ H ₁₈ O ₈ F ₄₈ Example 2 In the same four-necked flask as in Example 1, tetramethyl ester of BTC 29.0 g (0.1 mol), 160 g (0.48 mol) of 1H, 1H, 7H-dodecafluoro-1-heptanol and 2 g of sodium methylate were added, and the mixture was stirred while heating to 100 ° C.
A transesterification reaction was carried out while distilling off the methanol to be distilled off. After the distillation of methanol was delayed, the pressure was slightly reduced to promote the removal of methanol. The reaction was followed by disappearance of the peak of the methyl group in NMR. The reaction product thus obtained was diluted with toluene, washed three times with hot water, and then topped to obtain 144 g of the desired ester (97% yield). It has a saponification value of 152 (theory 150.6) and an acid value of 0.1.
Below 1, the fluorine content was 60.9% (theoretical 61.2%).

Example 3 An ester was prepared in the same manner as in Example 2 except that 127 g (0.98 mol) of 1H, 1H, 3H-tetrafluoro-1-pentanol was used as the fluorinated alcohol, and the reaction temperature was changed to 90 ° C. The yield at this time was 62 g (90% yield). The saponification value of the obtained target product was 327 (theoretical value: 325.
2) The acid value was 0.1 or less. The elemental analysis values of this are shown below.

Actual value (%) Theoretical value (%) C 34.7 34.80 H 2.7 2.61 O 18.6 18.55 F 44.0 44.04 C ₂₀ H ₁₈ O ₈ F ₁₆ Example 4 19.8 g (0.1 mol) of BTC dianhydride and 1H, 1H, 7H- Using 66.4 g (0.2 mol) of dodecafluoro-1-heptanol as a raw material, the mixture was stirred for 30 minutes at a temperature of 160 ° C. for 30 minutes to form a half-esterified, uniformly molten dicarboxydiester compound.
Obtained in 93% yield. The saponification value of the product was 258 (theoretical value 260.3), and the neutralization value was 132 (theoretical value 130.1). The elemental analysis values of this are shown below.

Measured value (%) Theoretical value (%) C 30.7 30.65 H 1.8 1.62 O 14.9 14.85 F 52.6 52.88 C ₂₂ H ₁₄ O ₈ F ₂₄

[Brief description of the drawings]

FIG. 1 shows the NMR (d) of the ester compound obtained in Example 1.
₆ - acetone) spectra, Figure 2 shows respectively the infrared absorption spectrum of the compound (KBr method).

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C09D 11/02 PTG C09D 11/02 PTG C09K 3/00 112 C09K 3/00 112E 3/18 3 / 18 102 102 C10M 105/54 C10M 105/54 D06M 13/224 D06M 13/16 C10N 40:00 40:18

Claims (1)

(57) [Claims] 1. A novel ester compound represented by the general formula (I). (In the formula, k, l, m, and n each represent an integer of 0 to 3, and may be the same or different. However, not all of them are 0. a, b, c , D represent 0 or 1, and may be the same or different, but not all of them are 0.) The following esters are represented by the general formula (I). Excluded from ester compounds.