JPS5828856B2 - Method for producing tricyclo(5.2.1.0↑2'↑6)-3-decene-8 (or 9)ol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides purified tricyclo(5.2.1.02°6
)-3-Decene-8(or 9)ol.

Tricyclo(5・2・l・02°6)-3-decene-8
(or 9)ol (hereinafter referred to as hydroxylated dicyclopentadiene).

) is useful as a raw material for unsaturated polyester resins as well as various other resins, perfumes, resin stabilizers, and plasticizers.

This hydroxylated dicyclopentadiene is produced by a water conservancy reaction of dicyclopentadiene using an acidic catalyst such as a mineral acid or a cation exchange resin.

The hydroxylated dicyclopentadiene obtained in this way is colored yellow to yellowish brown, and even if air is removed during distillation purification, the thermal history is shortened, and distillation is carried out carefully, the color remains yellow or yellowish brown. It is colored in.

Therefore, its use was extremely limited.

According to Japanese Patent Publication No. 47-39106, the cause of the coloring is a trace amount of impurity (methyldicyclopentadiene) in the raw material dicyclopentadiene, and the following method is proposed as a method for decolorizing the product hydroxylated synclopentadiene. It had been.

That is, the colored hydroxylated dicyclopentadiene is treated with a compound that acts as a genophile during the Diels-Alder reaction, such as maleic anhydride or p-
This is a method in which benzoquinone is added and mixed and then distilled.

As described in the comparative examples of the present invention, although this method is certainly effective in decolorizing products, it is not an economical method.

That is, in the case of maleic anhydride, by adding 2% by weight to the hydroxylated dicyclope and ntadiene and distilling it after heating and stirring, a product with a Hazen hue of 10 to 20 can be obtained, but the residue after distillation is 13%. Product loss is significant due to the large amount produced.

This is thought to be because maleic anhydride is not only used for decolorization, but also undergoes an esterification reaction with hydroxylated dicyclopentacyenka and maleic anhydride.

Furthermore, decolorization is also possible when p-benzoquinone, which does not cause an esterification reaction, is used, and the amount of distillation residue is smaller than when maleic anhydride is used.

However, p-benzoquinone is an expensive reagent, is not commonly used, and is difficult to use industrially.

The present invention solves these problems and provides a novel method different from the conventional method.

That is, the present invention is characterized in that crude hydroxylated dicyclopentadiene obtained by hydration reaction of synchlopentadiene in the presence of an acidic catalyst is heat-treated in the presence of an alkali metal hydroxide and then distilled. The present invention relates to a method for producing purified hydroxylated synchlopentadiene.

The crude hydroxylated dicyclopentadiene obtained by hydrating the above dicyclopentadiene in the presence of an acidic catalyst is the oil layer separated from the water layer after the hydration reaction, or the oil layer obtained by distilling this oil layer. This is a hydroxylated dicyclopentadiene fraction, which is colored yellow or tan as described above.

Alternatively, even if it is colorless and transparent after distillation, it will turn yellow or yellowish brown during storage.

The crude hydroxylated dicyclopentadiene is usually obtained by subjecting dicyclopentadiene to a hydration reaction in the presence of an acidic catalyst such as sulfuric acid or an ion exchange resin at a temperature of 80 to 1.20°C.

This crude hydroxylated synchlopentadiene can be directly used as an alkali metal hydroxide such as sodium or potassium hydroxide, or can be mixed with methyl alcohol,
0.1 of crude hydroxylated dicyclopentadiene dissolved in alcohol such as ethyl alcohol.
Add ~5% by weight.

If the amount added at this time is less than 0.1% by weight, the contact time with crude hydroxylated dicyclopentadiene becomes longer, and if it exceeds 5% by weight, the amount of distillation residue increases. The range of the amount of hydroxide added is 0.
1 to 5% by weight is suitable.

Regarding the temperature, 50 to 200°C, preferably 70°C.
~150°C is suitable.

If the temperature is less than 50°C, a colorless and transparent product cannot be obtained unless the contact time is long, and if it exceeds 200°C, there will be a significant amount of distillation residue, so the temperature should be between 50°C and 20°C.
00°C, preferably in the range of 70 to 150°C.

Next, the contact time is determined by the above two conditions.

In other words, when the heating temperature is high and the amount of alkali metal hydroxide is large, the contact time is shortened to suppress the increase in the amount of residue, and when the temperature is low and the amount of alkali is small, the contact time is lengthened to facilitate decolorization. However, it is usually 05 to 10 hours.

Thereafter, by distilling this treated solution, substantially colorless and transparent hydroxylated dicyclopentadienka with a Gardner hue of 1 or less was obtained, and the amount of distillation residue at this time was 2 to 6.
Weight%.

Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 Synchropentadiene was converted into an ion exchange resin having a sulfone group [manufactured by Rohm & Co., Ltd., Amberly] IR-
After hydration reaction in the presence of 200C), the hydroxylated dicyclopentadiene fraction was collected by distillation. Crude hydroxylated dicyclopentadiene [colored yellowish brown (Gardner hue 8)]1. 000S' and sodium hydroxide Fl (0.5% by weight) were placed in four flasks equipped with reflux condensers and heated to 120°C in an oil bath.
Heat to and stir for 1 hour.

The reaction solution turned dark brown. This treatment solution was poured into a flask equipped with a Claisen-type connecting tube at 4 to 57 ILrILHg (
Distillation was carried out under reduced pressure at an oil bath temperature of 125° C.), and the distillate was collected. The liquid was a colorless and transparent viscous liquid (hydroxylated dicyclopentadiene) with a concentration of 9331.

The degree of coloring of this product was 1 or less for Gardner hue and 60 for Hazen hue.

Further, the amount of residue after distillation was 6,231.

Therefore, the residue ratio (residue amount/charged amount) was 6.2% by weight.

Examples 2 to 5 Examples 2 to 5 were carried out using the sample and apparatus of Example 1, but varying the temperature and the type and amount of alkali.

Table 1 shows the processing conditions and results. Comparative Example 1 Table 1 shows the results of simple distillation of the sample used in Example 1 in a Claisen flask without heating or treatment with an alkali metal hydroxide.

Comparative Example 2 Sample 1oooy used in Example 1 was placed in the same fourth flask, heated and stirred, and after 30 minutes at 200°C, 20'? (2% by weight) of maleic anhydride was added, and the mixture was heated and stirred at 200° C. for an additional 30 minutes.

When this was subjected to simple distillation in a Claisen flask, the amount of residue was 13.2% by weight.

Note that the Gardner hue 1 corresponds to the Zen hue of 120, and if the hue is 100 or less, the material is substantially colorless and transparent.

Further, the purified hydroxylated dicyclopentadiene obtained in Examples 1 to 5 above did not become colored even after long-term storage.

As is clear from the above, the present invention heat-treats purified hydroxylated dicyclopentadiene in the presence of an alkali and then distills it to obtain substantially colorless and transparent hydroxylated dicyclopentadiene, which has a long No coloration even after storage for a period of time.

Claims (1)

[Claims] 1 Crude tricyclo(5・2・1・02°
6) -Purified tricyclo(5.2.1-02'') characterized by heat-treating 3-decene-8 (or 9)ol in the presence of an alkali metal hydroxide and then distilling it.
A method for producing 3-decen-8 (or 9)ol.