JPH07145105A - Production of 2-hydroxycyclohexyl (meth)acrylate - Google Patents

Abstract

PURPOSE:To provide a production process of 2-hydroxycyclohexyl (meth)acrylate in high yield while side reactions are inhibited. CONSTITUTION:In the production of 2-hydroxycyclohexyl (meth)acrylate from acrylic or methacrylic acid and cyclohexene oxide, a compound of an element in groups 2a to 4a, groups 1b to 7b or an element in group 8 in the Periodic Table, particularly at least one selected from compounds of chromium, iron, copper, zinc, titanium or aluminum is used as a catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 2-hydroxycyclohexyl (meth) acrylate used in the fields of paints, adhesives, coating agents and the like.

[0002]

2. Description of the Related Art As a method for producing 2-hydroxycyclohexyl (meth) acrylate from acrylic acid or methacrylic acid and cyclohexene oxide as raw materials, a method using trimethylphenylammonium iodide as a catalyst (West Politics et al. Polymer Chemistry, 25th
Vol., No. 284, p. 850, 1968), a method using triethylamine (Ivkina, AV et al., Z.
h. Prikl. Khim. (Leningrad),
47 (9), 2135 (1974); Chemical Abstract 81 (25): 169068m), a method using potassium methacrylate (Ivkina, AV et al., D.
Positioned Doc. , VINITI 2065
-74, 12 pp. (1974); Chemical Abstract 86 (16): 107063a) is known.
However, in these methods, the desired product cannot be obtained in a sufficient yield due to side reactions such as cyclohexene oxide oligomer formation which is presumed to be due to the catalytic action of the (meth) acrylic acid proton.

The cause of this is that the carbon to which the oxygen atom of the epoxy group of the cyclohexene oxide is bonded is a secondary carbon, so that ethylene where any of the carbon to which the oxygen atom is bonded is a primary carbon. It is considered that, unlike oxide and propylene oxide, the reaction rate of cyclohexene oxide with acrylic acid or methacrylic acid, which is the main reaction, is considerably slowed, and as a result, side reactions are more likely to occur.

[0004]

Therefore, a method for producing 2-hydroxycyclohexyl (meth) acrylate from acrylic acid or methacrylic acid and cyclohexene oxide as a raw material in high yield by preventing the above-mentioned side reaction is desired. Was there.

[0005]

The present inventors have found that the above problems can be solved by using a specific catalyst, and have completed the present invention. That is, the present invention uses 2a to 4a as a catalyst when 2-hydroxycyclohexyl (meth) acrylate is produced using acrylic acid or methacrylic acid and cyclohexene oxide as raw materials.
At least one compound selected from compounds of Group 1b-7b and Group 8 elements is used.
The present invention relates to a method for producing hydroxycyclohexyl (meth) acrylate, preferably using at least one compound selected from metal compounds of chromium, iron, copper, zinc, titanium or aluminum as a catalyst. Hydroxycyclohexyl (meth)
The present invention relates to a method for producing an acrylate.

Groups 2a to 4a and 1b used as catalysts
~ Chromium as a compound of group 7b or group 8 element,
Examples include simple substances such as iron, copper, zinc, titanium, aluminum, tin, vanadium, manganese, cobalt, nickel, molybdenum, and tungsten, halides, hydroxides, organic carboxylates, inorganic acid salts, and oxides. Of these, chromium, iron, copper, zinc, titanium, aluminum simple substances, halides, hydroxides, organic carboxylates, inorganic acid salts, oxides, etc., such as chromium acetate, chromium chloride, chromium oxide, and chloride chloride. It is preferable to use diiron, iron hydroxide, iron nitrate, zinc chloride, aluminum chloride or the like, and it is particularly preferable to use an organic carboxylate of chromium such as chromium acetate.

These catalysts may be used either individually or in combination of two or more, and may be used in combination with other promoters if necessary. The amount of the catalyst used is not particularly limited, but is 0.01 to 15.0 with respect to acrylic acid or methacrylic acid.
Weight% is preferable, and 0.1-10.0 is more preferable.
If the concentration is lower than 0.01% by weight, the effect of the catalyst is not sufficient and by-products increase, and if the concentration is higher than 15.0% by weight, the amount of the catalyst used becomes large, which is not economical.

The amount ratio of cyclohexene oxide to acrylic acid or methacrylic acid is not particularly limited, but the molar ratio is preferably 0.1 to 10.0, more preferably 0.5 to 1.5, and 0.8 to 1.2. Is more preferable, and when the molar ratio is larger than 10, cyclohexene oxide and 2-
When the side reaction by hydroxycyclohexyl (meth) acrylate is smaller than 0.1, the side reaction by acrylic acid or methacrylic acid and 2-hydroxycyclohexyl (meth) acrylate becomes remarkable, respectively, and the yield is lowered, which is not preferable.

In the present invention, the reaction temperature is 20 to 200.
C. is preferable, and 40 to 150.degree. C. is more preferable. When the reaction temperature is higher than 200 ° C., the starting material is acrylic acid, methacrylic acid, or the desired product, 2-hydroxycyclohexyl (meth) acrylate, and a by-product having a vinyl group, dicyclohexene glycol mono (meth) acrylate, cyclohexene glycol diester. The polymerization reaction due to (meth) acrylate or the like becomes remarkable, and the yield is lowered, which is not preferable.

The reaction pressure can be carried out under normal pressure or under pressure and is not particularly limited, but since all the raw materials are liquid, it is carried out under normal pressure or slightly increased pressure unless particularly required. The reaction method can be a continuous reaction, a batch reaction, a semi-batch reaction by sequentially adding cyclohexene oxide, etc., but is not particularly limited, but the batch reaction and the semi-batch reaction method are more preferably used because of high polymerizability of the reaction product. .

In the present invention, it is desirable to use a polymerization inhibitor in order to prevent the polymerization reaction of the reaction product during the reaction or during the purification after the reaction. Specifically, phenolic hydroxyl group-containing compounds such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, catechol, naphthol and nitrosophenol, p-phenylenediamine, N,
N'-diphenyl-p-phenylenediamine, N, N '
-Di-2-naphthyl-p-phenylenediamine, N,
Aromatic diamine compounds such as N′-diphenyl-naphthylenediamine, paraquinone dioxime, phenothiazine,
Copper dialkyldithiocarbamate, sulfur, nitrite,
Examples thereof include tannic acid, and particularly preferably aromatic diamine compounds such as N, N'-di-2-naphthyl-p-phenylenediamine. Further, the amount of these polymerization inhibitors used is usually 0.1 with respect to acrylic acid or methacrylic acid.
It is used in the range of 01 to 10% by weight.

The desired product, 2-hydroxycyclohexyl (meth) acrylate, is usually separated and purified from the reaction product by means such as atmospheric distillation or reduced pressure distillation after the reaction is completed. In order to prevent polymerization of the reaction solution, Distillation temperature 20 under reduced pressure
It is preferable to carry out distillation at 0 ° C. or lower, preferably 150 ° C. or lower. Further, in order to prevent the polymerization reaction during distillation, it is desirable to further add the above polymerization inhibitor to the reaction solution in advance, or to carry out the distillation in the presence of molecular oxygen by blowing air or the like. Since the distillate at the time of distillation does not contain a polymerization inhibitor, it is easy to polymerize, and it is desirable to prevent the polymerization reaction by means such as rapid cooling, addition of a polymerization inhibitor in advance or promptly.

[0013]

EXAMPLES Next, the present invention will be described in more detail by way of examples.

[0014]

Example 1 A flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel was charged with 72.4 g of methacrylic acid, non-flex F (N, N'-di-2-naphthyl-p-phenylenediamine, 3.67 g (manufactured by Seiko Chemical Co., Ltd.) and 1.55 g of chromium (II) acetate were charged, and the mixture was heated with stirring at 70 ° C. 78.6 g of cyclohexene oxide on the dropping funnel
After charging, the mixture was gradually added dropwise to the flask over 1 hour. Furthermore, the mixture was heated and stirred at 70 ° C. for 1 hour. According to gas chromatography analysis of the reaction solution, the conversion of cyclohexene oxide was 88% and the selectivity to 2-hydroxycyclohexyl methacrylate was 91%.

[0015]

Comparative Example 1 The reaction was carried out in exactly the same manner as in Example 1 except that 1.26 g of triethylamine was used instead of chromic acetate and 0.063 g of hydroquinone monomethyl ether was used instead of Nonflex F. As a result, the conversion rate of cyclohexene oxide 1 hour after the end of dropping was 5
3%, the selectivity to 2-hydroxycyclohexyl methacrylate was 62%, the conversion of cyclohexene oxide 5 hours after the dropping was 92%, and the selectivity to 2-hydroxycyclohexyl methacrylate was 57%.

[0016]

Examples 2 to 6 The reaction was carried out in exactly the same manner as in Example 1 except that the metal compounds shown in the table were used as catalysts instead of chromic acetate. The reaction results are shown in Table 1.

[0017]

[Table 1]

[0018]

INDUSTRIAL APPLICABILITY According to the present invention, 2-hydroxycyclohexyl (meth) acrylate can be produced from acrylic acid or methacrylic acid and cyclohexene oxide as raw materials in a high yield while preventing side reactions. The industrial value is extremely high.

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Claims (2)

[Claims] 1. When a 2-hydroxycyclohexyl (meth) acrylate is produced from acrylic acid or methacrylic acid and cyclohexene oxide as a raw material, the catalyst is selected from compounds of the 2a-4a group, 1b-7b group and 8 group elements. 2-Hydroxycyclohexyl (meth), characterized by using at least one compound
Acrylate manufacturing method. 2. The method for producing 2-hydroxycyclohexyl (meth) acrylate according to claim 1, wherein at least one compound selected from the metal compounds of chromium, iron, copper, zinc, titanium or aluminum is used as a catalyst.