JPH02253851A - Catalyst for hydrogen reaction of dicyclopentadiene - Google Patents

Abstract

PURPOSE:To enhance the yield of a product per unit weight of a catalyst, to eliminate a harmful effect on a reactor and to make post-treatment unnecessary by incorporating sulfonated polysiloxane having specific sulfonic acid groups into the catalyst. CONSTITUTION:A catalyst contg. sulfonated polysiloxane represented by the general formula 3 and having sulfonic acid groups represented by a formula -Ph-SO3H (where Ph is 6-8C arom. hydrocarbon) is obtd. Dicyclopentadiene is brought into a hydration reaction in the presence of the catalyst to produce tricyclo(5,2,1,0<2.6>)-3-decane-8-ol or tricyclo(5,2,1,0<2.6>)-3-decane-9-ol. The activity of the sulfonic acid groups to the hydration reaction is increased, the yield of the product per unit weight of the catalyst is enhanced, a reactor is not adversely affected and post-treatment is not required.

Description

Detailed Description of the Invention [Industrial Field] The present invention relates to a catalyst for dicyclopentadiene hydration reaction and tricyclo(5,2,1°02.6)-3 using the catalyst.
-decene-8(or 9)-ol (DCPD-OH
). More specifically, the present invention relates to a hydration catalyst containing a sulfonated polysiloxane.

[Prior Art] Sulfuric acid has long been well known as a catalyst used in the hydration reaction of dicyclopentadiene (hereinafter referred to as DCPD) (Journal of American Chemical
Society Vol. 67, p. 723, 1945). This method uses a stoichiometric amount of sulfuric acid to DCFD,
It performs a hydration reaction of DCPD. Specifically, D
By heating CFD with 20-40% sulfuric acid and maintaining it at reflux temperature for several hours, a hydration reaction of DCPD is carried out to obtain DCPD-OH.

Other methods include a hydration method using a heteropolyacid as a catalyst (Japanese Patent Publication No. 19205/1983) and a method using a strongly acidic ion exchange resin as a catalyst (U.S. Pat.
．． 345.419). The former is a hydration method in which DCPD-OH is produced using a water-soluble heteropolyacid such as tungstosilicic acid or phosphomolybdic acid instead of sulfuric acid as a catalyst.

Specifically, a heteropolyacid aqueous solution having a concentration of 0.0510% is heated together with DCPD to perform a hydration reaction of DCPD.

The latter is a hydration method that uses a strongly acidic ion exchange resin as a solid acid catalyst.

[Problems to be Solved by the Invention] However, in the method of using sulfuric acid as a catalyst, the amount of sulfuric acid used is stoichiometric and large relative to the substrate DCPD, and therefore (1) corrosion of the reaction vessel occurs. Intense (2
) There are disadvantages such as the necessity of neutralizing the reaction solution with an alkali after the completion of the reaction, and (3) the necessity of processing a large amount of waste sulfuric acid. On the other hand, methods using heteropolyacids also have the disadvantage of (4) heteropolyacids decomposing during the reaction depending on the material of the reactor. 5) The yield of DCPD-OH per equivalent of acid sites in the catalyst is low.In order to improve these drawbacks, there has been a desire to develop catalysts with higher activity and efficiency.

Therefore, the purpose of the present invention is to have a high yield per unit amount of catalyst,
It is an object of the present invention to provide a catalyst for the DCPD Eiwa reaction that does not have an adverse effect on a reaction vessel and does not require post-treatment.

A further object of the present invention is to provide a method for producing DCPD-OH using an excellent DCPD permanent reaction catalyst.

[Means for Solving the Problems] The present invention provides Ph5O3H (where Ph is a carbon number of 6 to 8
aromatic hydrocarbons. ) A catalyst for dicyclopentadiene hydration reaction containing a sulfonated polysiloxane having a sulfonic acid group.

Furthermore, the present invention provides tricyclo(5,2,
1,0'・6)-3-decen-8-ol and/or tricyclo(5,2,1°02″8)-3-decene-9-
This invention relates to a method for manufacturing oars.

The present invention will be explained below.

The sulfonated polysiloxane that is the catalyst of the present invention has a siloxane bond consisting of silicon atoms and oxygen atoms as a skeleton structure, similar to so-called silicone resins, and a part of the skeleton structure contains -Ph5OiH (Ph is carbon number 6 ~8 aromatic hydrocarbons). As a result, the catalyst functions as a solid acid.

In addition, Ph is phenylene or substituted phenylene,
Examples of the substituent include methylene and ethylene groups.

Conventionally, sulfonated polysiloxanes have been studied for use as ion-exchange packing materials for liquid chromatography. On the other hand, the applications of sulfonated polysiloxane as a solid acid as tlK include (1) dehydration reaction of 2-propanol in the gas phase flow method, (2) alkylation of benzene with methanol. reaction, (3) dil-o conversion reaction of aromatic hydrocarbons and (4) esterification of acetic acid with 2-methylpropanol in the liquid phase, (5) formation of ε-caprolactam from cyclohexanone oxime. Only the synthesis has been attempted, and there have been no reports on the use of the hydration reaction of unsaturated hydrocarbons discovered by the present inventors. In addition, regarding the catalytic properties in the previously reported reaction examples, when compared with the catalytic activity of strongly acidic ion exchange resins that are similar in that they have sulfonic acid groups, the sulfonation used in these reaction examples is The catalytic activity of polysiloxanes does not exceed that of ion exchange resins in most cases. However, as described later, in our research on hydration reactions, the present inventors selected a polysiloxane structure as the skeleton structure into which sulfonic acid groups are introduced. The present inventors have discovered that the activity of the sulfonic acid group can be improved, and have completed the present invention. In other words, by using this catalyst for the hydration reaction of DCPD, the reaction rate is 2 to 2 times faster than when using an ion exchange resin for the same acid.
It will be tripled. Taking advantage of this characteristic of sulfonated polysiloxane, the present inventors have solved various problems of conventional methods.

The sulfonated polysiloxane used as a catalyst in this patent is a siloxane skeleton having a three-dimensional network structure with a hydrocarbon side chain interposed, and a sulfonic acid group (-Ph-3O
, H) are combined. Sulfonated polysiloxane has a sulfonic acid group and thus functions as a solid acid catalyst.

Sulfonated polysiloxanes can be produced by a two-step process. That is, there are a step of forming a siloxane skeleton and a step of introducing a sulfonic acid group.

First, in order to form a siloxane skeleton, a monoalkyltrialkoxysilane and a tetraalkoxysilane are used as raw materials, and by mixing these and subjecting them to hydrolysis and polycondensation, a siloxane skeleton having a network structure can be obtained. Specifically, monophenyltriethoxysilane and tetraethoxysilane can be used.

Here, tetraethoxysilane is necessary for forming a crosslinked structure. That is, when only monophenyltriethoxysilane is subjected to hydrolytic condensation polymerization, a ladder-like polymer as shown in Formula 1 is formed, and a network structure cannot be obtained. Therefore, the heat resistance of the obtained siloxane skeleton becomes poor. Therefore, by hydrolyzing and condensing tetraethoxysilane together, a siloxane skeleton having a crosslinked structure as shown in Formula 2 can be formed, and as a result, heat resistance can be easily improved. For example, a polymer with the structure of formula 1 softens at 60-80°C, but a polymer with the structure of formula 2
By introducing a crosslinked structure as shown in the figure, it becomes possible to use the reaction at 150°C. Therefore, when the purpose is to improve heat resistance, it is effective to use a larger amount of tetraethoxysilane. However, if too much tetraethoxysilane is used, the amount of phenyl groups (Ph) in the siloxane skeleton will be reduced. As a result, this results in a decrease in the amount of sulfonic acid groups in the resulting sulfonated polysiloxane Ph , which lowers its activity as an acid catalyst. Therefore, the mixing ratio (molar ratio) of the two is preferably about 1 to 2.3 parts of monophenyltriethoxysilane to 1 to 2.3 parts of tetraethoxysilane. Therefore, in order to prepare a sulfonated polysiloxane, first, monophenyltriethoxysilane and tetraethoxysilane are thoroughly mixed at a mixing ratio of 1 to 2.3. Add alcohol and dilute hydrochloric acid to this. However, since alcohol is a common solvent for silanes and dilute hydrochloric acid and will be distilled off later, it is preferable to use an alcohol with a low boiling point, such as methanol or ethanol-impropanol.

Furthermore, dilute hydrochloric acid is said to have the effect of giving priority to hydrolysis over condensation polymerization. The reason why hydrolysis is selectively promoted is that when hydrolysis and polycondensation occur in concert, polysiloxane with a large amount of unreacted alkoxy groups, that is, ethoxy groups in this example, remains, that is, a crosslinked structure. This is because polysiloxane with a low concentration of is obtained. Condensation polymerization can be completed by making the reaction solution basic after completion of hydrolysis.

For example, ammonia water can be used. The above co-hydrolyzed condensation product of monophenyltriethoxysilane and tetraethoxysilane is a white fine powder of about 42 to 100 meshes.

Chlorosulfuric acid is used as a sulfonating agent to introduce a sulfonic acid group into the siloxane skeleton. Sulfonic acid groups can be introduced simply by mixing polysiloxane and chlorosulfuric acid and heating.

Here, it is preferable to use chlorosulfuric acid in an amount equal to or more than the phenyl group (Ph 2 ). However, since chlorosulfuric acid is a strong acid, if more than 10 times the equivalent amount is used for the phenyl group, the phenyl group itself will be oxidized, resulting in a decrease in the number of acid sites in the catalyst, which is not preferable. In the end, it is appropriate that the amount of chlorosulfuric acid be 2 to 10 times the equivalent amount to the phenyl group. The acid content of the sulfonated polysiloxane thus obtained is 0.5 to 2.5+++e per gram.
It is q. In this way, the sulfonated phenyl group (-P
A polysiloxane (23) having h-3O,H) is obtained.

The above sulfonated polysiloxane catalyst is used for the hydration reaction of DCPD. Preferred conditions for the reaction (amount of catalyst, amount of water added, temperature, pressure) are listed below.

The amount of catalyst used primarily affects the reaction time. That is, by using a large amount of catalyst, the reaction time can be shortened. The acidity of commonly used catalysts is 0.
It is sufficient to add 1 to 4% by weight of 5 to 2.5 meq/g to the substrate.

Therefore, the sulfonic acid group necessary for the hydration reaction of one molecule of substrate DCPD is sufficient in an extremely small amount of 2 to 22 milliequivalents.
Sulfonic acid groups having catalytic activity can be utilized with extremely high efficiency.

The molar ratio of water to DCPD (H20/DCPD) is 2
~30, preferably 5~IO.

If there is too little water, the polymerization of DCPD will occur with priority over the hydration reaction, while if there is too much water, the reaction volume will increase and the efficiency will decrease.

When carrying out a hydration reaction, it is possible to proceed with the reaction under various combinations of temperature and pressure, but the pressure only needs to be equal to or higher than the vapor pressure of the reaction liquid, particularly water. Regarding temperature, reactions at low temperatures require significantly longer reaction times, while overheating also promotes the formation of polymers.
The reaction temperature is 120-180°C, preferably 140-160°C
It is better to set the temperature to 0°C.

The reaction solution obtained by the reaction described above can be easily separated from the catalyst by filtration. The reaction solution is separated into an aqueous phase and an oil phase. The product DCPD-OH can be obtained by distilling this oil phase in a very conventional manner. That is, the distillation method may be either a batch method or a continuous method, and the distillation is performed under normal pressure or reduced pressure.

As described above, in the present invention, DCPD can be converted to DCFD-OH in high yield using a very small amount of catalyst containing 2 to 22 meq of acidic groups that act as a catalyst for the hydration reaction of the substrate.
It becomes possible to hydrate to.

[Effects of the Invention] (1) The catalyst of the present invention can utilize extremely small amounts of acidic groups with high efficiency.That is, focusing on the amount of acid in the catalyst, the same amount of sulfuric acid, heteropolyacid, or ion exchange resin can be used. Even when compared to the case where the sulfonated polysiloxane of the present invention is used, the product can be obtained in high yield.

(2) As a result of (1), in the production method of the present invention,
It becomes possible to use a small amount of catalyst, 1 to 4% by weight based on the substrate.

[Example] Next, in order to concretely demonstrate the present invention, an example will be given and explained.

Example 1 143 g of tetraethoxysilane and 72 g of phenyltriethoxysilane were mixed in a molar ratio of 7:3 with 1 part of ethanol.
Mix in 25 ml and add 35 ml of 0.0 IN hydrochloric acid.
was added and heated at about 80°C until the liquid volume was reduced to one-third of the original volume. Then, after cooling the reaction solution to room temperature, diluting the reaction solution with 60 ml of ethanol and 9 Qn+1 of cyclohexane, 50 ml of 25% aqueous ammonia and 27 ml of distilled water.
Qml was added.

In this way, white powder polyphenylsiloxane 79,
2 g was obtained.

Example 2 20 g of the polyphenylsiloxane prepared in Example 1 was treated with chlorosulfonic acid 24 as a sulfonating agent in carbon tetrachloride.
Sulfonation treatment was carried out using m1 by heating and refluxing at 77° C. for 3 hours.

After sulfonation, the acidity of sulfonated polyphenylsiloxane is about 1.8 mi! J hit! /g.

Example 3 The sulfonated polyphenylsiloxane obtained in Example 2 was used to carry out a hydration reaction of DCPD.

0.51 induction stirring autoclave (Material: Hastelloy)
132 g of DCPD and 90 g of pure water were charged together with sulfonated polyphenylsiloxane (9 ml) and pressurized to 20 kg/cl]l with nitrogen.The temperature of the reaction solution was 1.
The reaction was carried out at 50°C for 4 hours. After reaction, DCPD-OH
The yield was determined (Table 1).

Example 4 Under the reaction conditions of Example 3, the liquid temperature during the reaction was 140°C.
The hydration reaction was carried out under the same conditions as in Example 3, except for the following changes. After the reaction, the yield of DCPD-○H was determined (Table 1)
.

Example 5 A hydration reaction was carried out under the same conditions as in Example 3, except that the H,0/DCPD molar ratio was changed to 1O. After the reaction, the yield of DCPD-OH was determined (Table 1).

Example 6 20 g of the polyphenylsiloxane prepared in Example 1 was mixed with chlorosulfonic acid 10 g as a sulfonating agent in carbon tetrachloride.
Sulfonation treatment was carried out using m1 by heating and refluxing at 77° C. for 3 hours.

After sulfonation, the acidity of the sulfonated polyphenylsiloxane was approximately 0.5 IJ equivalents/g.

Example 7 123 g of tetraethoxysilane and 96 g of phenyltriethoxysilane were mixed in a molar ratio of 6:4 with 1 part of ethanol.
Mix in 25 ml, and add 35 ml of 0.01N hydrochloric acid.
was added and heated at about 80°C until the liquid volume was reduced to one-third of the original volume. After that, the reaction solution was cooled to room temperature, diluted with 6 Qml of ethanol and 9 Qml of cyclohexane, and then mixed with 5 Qml of 25% aqueous ammonia and 2 Qml of distilled water.
7 Qml was added.

In this way, white powder polyphenylsiloxane 85,
3 g was obtained.

Example 8 15 g of the polyphenylsiloxane prepared in Example 7 was treated with chlorosulfonic acid 45 g as a sulfonating agent in carbon tetrachloride.
Sulfonation treatment was carried out using m1 by heating and refluxing at 77° C. for 3 hours.

After sulfonation, the acidity of the sulfonated polyphenylsiloxane was approximately 2.4 m') equivalents/g.

Example 9 The sulfonated polyphenylsiloxane obtained in Example 8 was used to carry out a hydration reaction of DCPD. DCP in 0.51 induction stirring autoclave (Material: Hastelloy)
132g of D and 90g of pure water were charged together with sulfonated polyphenylsiloxane (12 milliequivalents), and heated to 20k with nitrogen.
The pressure was increased to g/crl.

The reaction was carried out for 4 hours at a reaction solution temperature of 120°C. After the reaction, the yield of DCPD-OH was determined (Table 1).

Comparative Example 1 Under the same conditions as Example 3, only the catalyst was replaced with sulfuric acid (9 meq.)
I reacted by changing this. After the reaction, the yield of DCPD-OH was determined (Table 1).

Comparative Example 2 Under the same conditions as Example 3, only the catalyst was mixed with Amberlyst 15.
(9 milliequivalents) and the reaction was carried out.

Claims (2)

[Claims] (1) -Ph-SO_3H (However, Ph has 6 to 8 carbon atoms
aromatic hydrocarbons. ) A catalyst for dicyclopentadiene hydration reaction containing a sulfonated polysiloxane having a sulfonic acid group. (2) Tricyclo(5,2,
1,0^2^,^6)-3-decen-8-ol and/
Or tricyclo(5,2,1,0^2^,^6)-3-
Method for producing decen-9-ol.