JP3273498B2 - Method for producing ester compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an ester compound. More specifically, the present invention relates to a method for producing an ester compound having a low content of an aliphatic alcohol or an alkyl-substituted phenol that adversely affects heat resistance and other physical properties.

[0002]

2. Description of the Related Art Ester compounds are plasticizers for various resins,
It is used as an additive such as a flame retardant or a resin modifier, or a lubricant or a stabilizer. Meanwhile, in recent years, the automotive industry,
Along with technological innovations in electronics and the like, the performance required of resins has been constantly improving. Against this background, there is a demand from the industry for ester compounds as a resin additive to significantly improve the basic performance and to develop a new method for producing an ester compound having such performance.

[0003] Ester compounds are generally produced by reacting an organic acid or an inorganic acid or a halide thereof with an alcohol or phenol (hereinafter referred to as a hydroxy compound) in the presence or absence of a catalyst. . Usually, in the above reaction, a method is employed in which a hydroxy compound is used in excess of a chemical equivalent relative to the amount of an organic acid or an inorganic acid or a halide thereof, and the remaining hydroxy compound after the reaction is removed by distillation or washing. ing.

[0004]

However, in the above-mentioned production method, the excess hydroxy compound may not be completely removed by a method such as distillation or washing. The hydroxy compound remaining in the ester compound not only lowers the product purity but also lowers the heat resistance, and when mixed with the resin, the resin has weather resistance, heat resistance, odor, insulation, and contamination resistance. It is not preferable because it has an adverse effect on sex, toxicity and the like.

Conversely, when the reaction is carried out using a hydroxy compound having a chemical equivalent less than the amount of the organic acid or inorganic acid or the halide thereof, the acid component remains and the acid value of the ester compound increases. It is not preferable because it has a bad effect on the compounded resin. In order to prevent such an increase in the acid value, a method of reducing the acid value by neutralizing with an alkali or reacting with an epoxy compound is employed. However, alkali metal salts and ether compounds produced by the above reaction are not preferable because they cause the above-mentioned adverse effects.

An object of the present invention is to provide a method for producing an ester compound having a low content of an aliphatic alcohol or an alkyl-substituted phenol which adversely affects heat resistance and other physical properties.

[0007]

Thus, according to the present invention, aliphatic or aromatic mono-, di- or tricarboxylic acids or inorganic acids or their halides (A)
With aliphatic alcohol or alkyl-substituted phenol (B) by reacting (B) with (A) in a stoichiometric amount or less (hereinafter referred to as the main reaction). (B) to obtain a mixed ester compound by reacting with an aliphatic alcohol, phenol or alkyl-substituted phenol (C) having a boiling point lower than that of (B) to obtain a mixed ester compound. .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, specific reaction steps of the present invention will be described. First, in the main reaction, an aliphatic or aromatic mono-, di- or tricarboxylic acid or an inorganic acid or a halide thereof (A) and an aliphatic alcohol or an alkyl-substituted phenol (B) are reacted with (B) as (A) ) In an amount equivalent to or less than the chemical equivalent to produce an ester compound.

(B) is 0.8 to 1.0, preferably 0.9 to 1.0, assuming that the chemical equivalent to (A) is 1. (B) is 0.8 when the chemical equivalent to (A) is 1;
If it is smaller, the acid component of (A) remains in the ester compound, and in the next complementation reaction, too much ester compound resulting from (C) remains. Is not preferable because it remains in the ester compound.

The main reaction is preferably carried out in the presence of a catalyst. Examples of the catalyst include magnesium chloride, aluminum chloride, titanium tetrachloride, sulfuric acid, hydrochloric acid, toluenesulfonic acid and the like. In the case of magnesium chloride, the amount added is 3 to 10 mmol, preferably 5 to 8 mmol, per 1 mol of (A). In the case of sulfuric acid, (A) 1
5 to 20 mmol, preferably 10 to 20 mol per mol
Millimoles. Further, the main reaction may be carried out in the presence of an organic solvent. Organic solvents include benzene, toluene,
Examples include xylene, o-dichlorobenzene, o-chlorotoluene, hexane, dimethylformamide, dioxane and the like.

The temperature condition of the main reaction is 30 to 160 ° C., preferably 100 to 160 ° C. If the temperature is lower than 30 ° C., the reaction is slow and the efficiency is low.
At higher temperatures, steam heating is difficult to perform, and coloring,
It is not preferable because problems such as decomposition are likely to occur. Also,
The pressure condition is normal pressure to 1 Torr, preferably normal pressure to 10 T
orr. Further, hydrogen halide by-produced when a halide is used in (A) can be recovered by known means. The time required for the reaction varies depending on various conditions such as temperature and pressure, but is 2 to 12 hours in order to obtain a product having good quality.

The reaction mixture obtained in the main reaction is then treated with an excess of (B) an aliphatic alcohol having a lower boiling point,
Reaction with phenol or alkyl-substituted phenol (C) gives a mixed ester compound. (C) may be an amount capable of esterifying (A) remaining in the reaction mixture in the main reaction. Specifically, (C) is 0.01 to 0.2, preferably 0.01 to 0.1, assuming that the chemical equivalent to (A) is 1.

The temperature and pressure conditions for this complementary reaction are the same as for the main reaction. Both the main reaction and the complementary reaction are esterification reactions, and after the main reaction, the complementary reaction can be continuously performed without removing the catalyst and the organic solvent in the reaction mixture. The obtained reaction mixture is discharged from the reactor, and can be commercialized through a catalyst removing step by washing with an acid or an alkali and a removing step (C) by steam distillation. In the case of steam distillation, the temperature condition is about 100 ~
160 ° C., pressure conditions are about normal pressure to 5 Torr.

(A) used in the main reaction of the present invention includes aliphatic or aromatic mono-, di- or tricarboxylic acids or inorganic acids or halides thereof, which are usually used for producing ester compounds.

The aliphatic or aromatic mono-, di- or tricarboxylic acids include formic acid, acetic acid, propionic acid,
Butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, aliphatic saturated monocarboxylic acids such as stearic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Aliphatic saturated dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid and sebacic acid; aliphatic unsaturated monocarboxylic acids such as acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, oleic acid and elaidic acid; Aliphatic unsaturated dicarboxylic acids such as acid, fumaric acid, citraconic acid and mesaconic acid; aliphatic tricarboxylic acids such as tricarballylic acid;

Aromatic monocarboxylic acids such as benzoic acid, naphthoic acid, toluic acid, hydroatropic acid, atropic acid and cinnamic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; benzenetricarboxylic acid and trimellitic acid And the like. In addition, halides of the carboxylic acids, particularly chlorides, can also be used.

Further, phosphoric acid is preferred as the inorganic acid,
Specific examples include phosphoric acid and phosphorous acid, and examples of the halide include chlorides such as phosphorus trichloride, phosphorus oxychloride, and phosphorus pentachloride.

In the above (A), aliphatic or aromatic mono-, di- or tricarboxylic acids such as acetic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, isophthalic acid and trimellitic acid, or the like. And inorganic acids such as phosphoric acid, phosphorous acid, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride or halides thereof.

The compound (B) used in the main reaction of the present invention may be a compound usually used for producing an ester compound, and specifically has 7 or more carbon atoms (preferably 7 to 18).
And an alkyl-substituted phenol having 9 or more (preferably 9 to 24) carbon atoms having one or more alkyl groups.

More specifically, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol) ), Heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, icosyl alcohol, henicosyl alcohol, docosyl alcohol, tricosyl alcohol, tetracosyl alcohol, pentacosyl alcohol, hexacosyl alcohol, heptacosyl alcohol, Aliphatic saturated alcohols such as octacosyl alcohol; aliphatic unsaturated alcohols such as oleyl alcohol (cis-9-octadecenyl alcohol);

N-propylphenol, iso-propylphenol, n-butylphenol, iso-butylphenol,
sec-butylphenol, tert-butylphenol, n-pentylphenol, iso-pentylphenol, tert-pentylphenol, neo-pentylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecylphenol, tridecyl Phenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, nonadecylphenol,
Icosylphenol;

Di-n-propylphenol, di-iso-propylphenol, di-n-butylphenol, di-iso-butylphenol, di-sec-butylphenol, di-ter
t-butylphenol, di-n-pentylphenol, di-
Examples include alkyl-substituted phenols such as iso-pentylphenol, di-tert-pentylphenol, di-neo-pentylphenol, dihexylphenol, diheptylphenol, dioctylphenol, dinonylphenol, and didecylphenol.

In the above (B), dodecyl alcohol,
Preferred are aliphatic alcohols such as tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol and oleyl alcohol; alkyl-substituted phenols such as iso-propylphenol, octylphenol, nonylphenol and dinonylphenol.

(C) used in the complementary reaction of the present invention is
It is appropriately selected from aliphatic alcohols having 1 to 6 carbon atoms having a lower boiling point than the (B) used in the main reaction, phenol, or alkyl-substituted phenols having 7 to 9 carbon atoms having one or more alkyl groups.

Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, se
aliphatic alcohols such as c-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, iso-pentyl alcohol, tert-pentyl alcohol, neo-pentyl alcohol, and hexyl alcohol; phenol; methylphenol, dimethylphenol, trimethylphenol, and ethyl Alkyl-substituted phenols such as phenol, n-propylphenol, and iso-propylphenol are exemplified.

The combination of (A) and (B) in the main reaction and the combination of (C) used in the complementary reaction may be any of the combinations of the above compounds. Is preferred.・ Nonylphenol and phosphorus oxychloride, and phenol ・ Phthalic anhydride and stearyl alcohol, and butyl alcohol ・ Adipic acid and stearyl alcohol, and butyl alcohol ・ Sebacic acid and tridecyl alcohol, and butyl alcohol ・ Phosphorous oxychloride and oleyl alcohol, and n-propyl alcohol

[0027]

The present invention will be described in detail below, but the scope of the present invention is not limited thereto.

Example 1 Synthesis of Trisnonylphenylphosphate 0.8 g (8 mmol) of magnesium chloride and 64 mg of nonylphenol were placed in a four-necked flask equipped with a Dimroth condenser connected to a stirrer, a thermometer, and a hydrochloric acid recovery unit.
3.5 g (2.925 mol), phosphorus oxychloride 151.
2 g (0.985 mol) was added and heated to 160 ° C. over 3 hours with stirring. The hydrochloric acid generated at this time was recovered in a hydrochloric acid recovery apparatus. The amount of hydrochloric acid recovered during this period is 100 g
Met. Thereafter, the inside of the flask was gradually evacuated to 16
Aging was carried out at 0 ° C. at 20 Torr for 4 hours until the reaction was completed.

After completion of the reaction, the reaction mixture was cooled to room temperature, added with 0.3 g (0.003 mol) of phenol, heated again to 160 ° C., and aged at 20 Torr for 2 hours. afterwards,
After removing the remaining catalyst components by acid washing,
Excess phenol is removed by steam distillation under the condition of 0 Torr, and trisnonylphenyl phosphate 6
77 g were obtained. Table 1 shows the physical properties of the obtained trisnonylphenyl phosphate.

(Example 2) Synthesis of distearyl phthalate In a flask equipped with a stirrer, a thermometer and a Liebig condenser, 148 g (1 mol) of phthalic anhydride, 528.5 g (1.95 mol) of stearyl alcohol and 98% sulfuric acid 1.5 g (15 mmol) and 700 g of toluene were charged, and the temperature was raised to 130 ° C. over 2 hours with stirring.
At this time, water and toluene generated by the reaction were recovered by a Liebig condenser, and the recovered toluene was returned to the reaction vessel by an additional funnel for the reaction. The water recovered at that time was 17.1 g, and the acid value of the reaction solution was 7.2 KOH.
mg / g. Thereafter, while adding 50 g of butyl alcohol, an operation of recovering toluene distilled off along with butyl alcohol and generated water was performed at the same temperature for 1 hour. Thereafter, the amount of the reaction solution was 950.3 g, and the acid value was 2.
It was 5 KOH mg / g.

To remove sulfuric acid used as a catalyst from the reaction solution prepared as described above, the mixture was neutralized with 500 g of hot water and 5 g of soda ash and then washed with hot water. The amount of the reaction solution was 958.7 g, and the amount of acid was 95%. The titer was 0.02 KOH mg / g.
Since this reaction solution contained butyl alcohol remaining in the reaction, the butyl alcohol component was then removed by steam distillation. The conditions of steam distillation at this time are 120 ° C. and 50 Torr for 1 hour, and the product yield is 63
8.5 g. Table 1 shows the physical properties of the thus obtained distearyl phthalate.

(Example 3) Synthesis of distearyl adipate In a flask equipped with a stirrer, a thermometer and a Liebig condenser, 146 g (1 mol) of adipic acid, 528.5 g (1.95 mol) of stearyl alcohol, 98% sulfuric acid 1 Then, 0.5 g (15 mmol) and 700 g of toluene were charged, and the temperature was raised to 150 ° C. over 2 hours while stirring.
The water and toluene distilled off at this time were collected by a Liebig condenser. The collected toluene was returned to the reaction vessel using an additional funnel to carry out the reaction. At this time, the recovered water was 34 g, and the acid value of the reaction solution was 6.4 KOH mg / g.
Met. Thereafter, while adding 50 g of butyl alcohol, an operation of collecting butyl alcohol and produced water was performed at the same temperature for 2 hours. Thereafter, the amount of the reaction solution was 865.
At 3 g, the acid value was 1.8 KOH mg / g.

To remove sulfuric acid used as a catalyst from the reaction solution prepared as described above, the reaction solution was neutralized with 500 g of hot water and 5 g of soda ash, and then washed with hot water. Here, the amount of the reaction solution was 866.3 g, and the acid value was 0.01 KOH mg / g.
Met. Since excess butyl alcohol used during the reaction remains in this reaction solution, butyl alcohol was removed by steam distillation. The conditions of the steam distillation at this time were 120 ° C. and 50 Torr for 1 hour, and the yield of the product was 621.5 g. Table 1 shows the physical properties of the thus obtained distearyl adipate.

Comparative Example (Comparison with Example 1) 0.8 g (8 mmol) of magnesium chloride, nonylphenol 66 were placed in a four-necked flask equipped with a Dimroth condenser connected to a stirrer, a thermometer, and a hydrochloric acid recovery unit.
9.6 g (3.044 mol), phosphorus oxychloride 151.
2 g (0.985 mol) was added and heated to 160 ° C. over 3 hours with stirring. The hydrochloric acid generated at this time was recovered in a hydrochloric acid recovery apparatus. During this period, the recovered amount of hydrochloric acid was 101.
3 g. After that, the inside of the flask was gradually evacuated to 1
Aging was performed at 60 ° C. at 20 Torr for 4 hours until the reaction was completed.

Then, after removing the remaining catalyst components by acid washing, nonylphenol was removed by steam distillation under the conditions of 140 ° C. and 20 Torr to obtain 683 g of trisnonylphenyl phosphate. Table 1 shows the physical properties of the obtained trisnonylphenyl phosphate.

[0036]

[Table 1]

In Table 1, the odor was determined by mixing 10 parts by weight of the ester compounds obtained in Examples 1 to 3 and Comparative Example with 100 parts by weight of the polyphenylene ether resin, and
A test piece having a thickness of 1/16 inch according to the test method of No. 4 was prepared, and the test piece was left standing at 120 ° C. for 48 hours, and the odor was measured. ○
Was evaluated. At this time, the surface of the test piece was visually observed.
Those that did not change from those before the test were evaluated as ○. Further, the differential heat loss was measured in an open-cell nitrogen atmosphere at a heating rate of 10 ° C.
% Loss at 300 ° C./min.

[0038]

According to the present invention, an aliphatic or aromatic mono-, di- or tricarboxylic acid or an inorganic acid or a halide thereof (A) and an aliphatic alcohol or an alkyl-substituted phenol (B) are used as a component (B). Is reacted with a chemical equivalent or less relative to (A) and then the resulting reaction mixture is reacted with an excess of an aliphatic alcohol, phenol or alkyl-substituted phenol (C) having a lower boiling point than (B). To obtain a mixed ester compound. Therefore, especially when a high molecular weight aliphatic alcohol or a high molecular weight alkyl-substituted phenol is used as (B), an ester compound having a low content of the aliphatic alcohol or the alkyl-substituted phenol that adversely affects heat resistance and other physical properties is used. Obtainable. Further, according to the present invention, since a post-processing step such as a purification step can be simplified, a reduction in manufacturing time and a reduction in cost can be realized.

Claims (8)

(57) [Claims] 1. An aliphatic or aromatic mono-, di- or tricarboxylic acid or inorganic acid or a halide thereof (A), an aliphatic alcohol or an alkyl-substituted phenol (B), , And then reacting the resulting reaction mixture with an excess of an aliphatic alcohol, phenol or alkyl-substituted phenol (C) having a lower boiling point than (B) to obtain a mixed ester compound. A method for producing an ester compound, characterized by obtaining 2. The method according to claim 1, wherein (B) has a chemical equivalent of 1 to (A).
2. The method according to claim 1, wherein the value is 0.8 to 1.0. 3. The method according to claim 1, wherein the inorganic acid is phosphoric acid.
The method described in. 4. The method according to claim 1, wherein (A) is an aliphatic or aromatic mono-, di- or tricarboxylic acid such as acetic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, isophthalic acid or trimellitic acid, or a salt thereof. The method according to any one of claims 1 to 3, wherein the halide is an inorganic acid such as phosphoric acid, phosphorous acid, phosphorus trichloride, phosphorus oxychloride or phosphorus pentachloride, or a halide thereof. 5. A method according to claim 1, wherein (B) is an aliphatic alcohol having 7 to 18 carbon atoms or 9 to 9 carbon atoms having at least one alkyl group.
The method according to any one of claims 1 to 4, wherein the alkyl-substituted phenol is 24. 6. (B) is an aliphatic alcohol such as dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol or oleyl alcohol; an alkyl substitution such as iso-propylphenol, octylphenol, nonylphenol or dinonylphenol. The method according to any one of claims 1 to 5, which is phenol. 7. The method according to claim 1, wherein (C) is an aliphatic alcohol having 1 to 6 carbon atoms, phenol, or an alkyl-substituted phenol having 7 to 9 carbon atoms having at least one alkyl group.
7. The method according to any one of claims 1 to 6. 8. (C) is methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, se
aliphatic alcohols such as c-butyl alcohol or tert-butyl alcohol; phenol; methylphenol;
An alkyl-substituted phenol such as dimethylphenol, trimethylphenol, ethylphenol, n-propylphenol or iso-propylphenol.
The method according to any one of claims 1 to 7.