JPS5817173B2 - 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(5,2,1,02j6
)-3-Decene-8 (or 9)ol.

Tricyclo(5,2,1,02j6) -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 hydration 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 due to a trace amount of impurity (methyldicyclopencdiene) in the raw material dicyclopencdiene, and the following method is used to decolorize the product hydroxylated dicyclopentadiene. It had been proposed.

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

Although this method is certainly effective for decolorizing products, it is not an economical method.

That is, in the case of maleic anhydride, a product with a Hazen hue of 10 to 20 can be obtained by adding double hydrogen to hydroxylated dicyclopentadiene, heating and stirring, and then distilling it, but the distillation residue is about 13%. Because large quantities are produced, product loss is significant.

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

Further, 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, in the present invention, crude hydroxylated dicyclopentadiene obtained by subjecting dicyclopentadiene to a water conservation reaction in the presence of an acidic catalyst is brought into contact with oxygen or an oxygen-containing gas at a temperature of 130 to 220°C, and then distilled. The present invention relates to a method for producing purified hydroxylated dicyclopentadiene, which is characterized by the following.

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. There 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 above-mentioned 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 120°C.

Conventionally, this crude hydroxylated dicyclopentadiene is purified by removing air and distilling it in a vacuum, but in the present invention, the crude hydroxylated dicyclopentadiene is purified by simply distilling it after contacting it with oxygen or an oxygen-containing gas. However, during distillation, it may be brought into contact with oxygen or an oxygen-containing gas.

That is, 13 crude hydroxylated dicyclopentadiene
The mixture is heated and stirred at 0 to 220°C, and oxygen or an oxygen-containing gas is blown into the mixture.

The amount of oxygen or oxygen-containing gas at this time is the amount of oxygen in sample 1.
0.021/- or more, preferably 0.1 to 1
The contact time varies depending on the above two conditions, but is usually 0.5 to 10 hours.

By simple distillation of the sample treated with heated air in this way, hydroxylated dicyclopentadiene is obtained which is substantially colorless and transparent and has a Gardner hue of 1 and does not become colored during storage.

The amount of distillation residue at this time is 3 to 4 weight factors.

The reason for setting the above temperature, oxygen amount, and treatment time ranges is as follows.
It is as follows.

Regarding the temperature, if it is less than 100°C, a colorless and transparent product cannot be obtained unless the contact time is long, and if it exceeds 250°C, there will be a significant amount of distillation residue, so the temperature should be between 100°C and above. 250°C, preferably 130°
It is in the range of C to 220C.

Next, regarding the amount of oxygen, as in the case of temperature, when the amount of air is less than 0.021/*'n with respect to the sample 11, the contact time becomes longer.

On the other hand, if it is too large, the amount of distillation residue will increase.

The preferred range of oxygen amount is 0.1 to 11 per liter of sample.
/-.

The contact time is determined by the above temperature and oxygen amount.

In other words, when the heating temperature is high and the amount of oxygen is high, the contact time is shortened to suppress the increase in the amount of residue, and when the temperature is low and the amount of oxygen is low, the contact time is increased to proceed with decolorization, but normally is 0.5 to 10 hours.

Hereinafter, it will be described in more detail with reference to Examples and Comparative Examples.

Example 1 Ion exchange resin containing dicyclopentadiene and sulfone group [manufactured by Rohm & Birth, Amberlite IR-2]
After a hydration reaction in the presence of 0003, the mixture was immediately distilled under reduced pressure to collect a human'oxylated dicyclopentadiene fraction.

The crude hydroxylated dicyclopentadiene obtained had a tan color (Gardner hue 6).

Crude hydroxylated dicyclopentadiene 300CC (320i) colored yellowish brown is placed in a four-way flask equipped with a reflux condenser and heated in an oil bath while stirring.

When the temperature of the sample reaches 200°C, dry air is blown into the sample through a silica gel cylinder at a rate of 60 (Iff/111t), and heating and stirring are continued for 2 hours.

The reaction solution turned dark red. This sample was distilled under reduced pressure at 4 to 5 MHg (the oil path temperature at this time was 125°C) in a flask equipped with a Claisen-type connecting tube. When the distillate was collected, the liquid was a colorless and transparent viscous liquid (hydroxylated dicyclopentadiene), the yield was 316.2. It was F.

The coloring degree of this product was 1 in Gardner hue and 30 in Hazen hue.

Moreover, the residue from the distillation was 12.9 g.

Therefore, the residue ratio (residue amount/charged amount) was 4.0%.

The purified hydroxylated dicyclopentadiene obtained was virtually colorless and did not become colored even after long-term storage.

Examples 2 to 3 and Comparative Examples 1 to 2 Experiments were carried out in the same manner as in Example 1, using the sample (crude hydroxylated cyclopentadiene) and apparatus, and varying the temperature and amount of air.

The treatment conditions and results are shown in the table.

Comparative Example 3 The sample used in Example 1 was subjected to simple distillation in a Claisen-type flask without heating or contact with air, and the results are shown in the table.

Comparative Example 4 The sample used in Example 1 was heated at 150°C for 2 hours,
The results are shown in which the same amount of nitrogen as in Example 1 was blown in instead of air during this time.

As is clear from the above, there is almost no decolorization in simple distillation or heated nitrogen treatment, but substantially colorless and transparent hydroxylated dicyclopentadiene can be obtained by contacting it with oxygen, and the amount of distillation residue at this time is It can be kept to a small amount.

By the method according to the present invention, it has become possible to produce colorless and transparent hydroxylated dicyclopentadiene at low cost.

Claims (1)

[Claims] 1 Crude tricyclo(5,2,1°()2
,6) 3-decene-8 (or 9)ol at 130
Production of purified tricyclo(5,2,1,02j6)-3-decen-8(or)ol, characterized by distillation after contact with oxygen or an oxygen-containing gas at a temperature of ~220°C Law.