KR19990017713A - Method for preparing 5-vinyl-2-norbornene using heterogeneous catalyst - Google Patents

Abstract

The present invention relates to a method for producing 5-vinyl-2-norbornene using a heterogeneous catalyst, and more particularly, to an alkali metal of Group 1, an alkaline earth metal of Group 2, or a mixture thereof. 1 mole of cyclopentadiene and 1 to 4 moles of 1,3-butadiene are 160 ° C to 250 ° C in the presence of a catalyst and a solvent prepared by supporting a heterogeneous solid carrier substrate selected from the group consisting of silica, silica-alumina, activated carbon and zeolite. The present invention relates to a method for producing 5-vinyl-2-norbornene with high conversion and high yield by reaction under pressure of 160 to 500 psig for 10 minutes to 2 hours.

Description

Method for preparing 5-vinyl-2-norbornene using heterogeneous catalyst

The present invention relates to a method for preparing 5-vinyl-2-norbornene using a heterogeneous catalyst, and more particularly, to an element periodic alkali group 1 and / or group 2 alkali In the presence of a catalyst prepared by supporting an earth metal on a commercially available carrier, cyclopentadiene (hereinafter referred to as CPD) and 1,3-butadiene (hereinafter referred to as BD) are reacted to give high yield and 5-vinyl-2- A method for producing norbornene (hereinafter referred to as VNB).

VNB, a raw material of 5-ethylidine-2-norbornene (hereinafter referred to as ENB), a heavy substance used as the third molecule of ethylene-propylene-diene terpolymer (EPDM) rubber, is a Diels-Alder of CPD and BD. Diels-Alder) can be prepared through the reaction.

For example, Japanese Patent Application Laid-Open No. 48-92353 discloses a method for producing VNB in the presence of a catalyst in which metal chlorides are supported on activated alumina, and the reaction yield described in the above patent is rather good, but a long reaction time (3 hours) is required. By using an active carrier having a small particle size, there is a disadvantage in that the efficiency of the catalyst is sharply reduced when applied to a general commercial process (continuous process). In addition, since the patent is not registered in the patent, the progress of the technology is questionable, and the technology was verified by the method of the embodiment, and as a result, the VNB yield shown in the embodiment could not be obtained at all.

Another method is to prepare a reactant CPD and BD in a continuous process. Japanese Patent Application Laid-Open No. 61-2000930 (see Comparative Example 1 below) is a method used as a commercial process for mass production, but since the reaction is carried out without a catalyst, the conversion rate of the reactants is very low at about 25% and many by-products are generated. In particular, 3a, 4,7,7a-tetrahydrointen (hereinafter referred to as THI), produced by BD acting as a diene instead of CPD, causes difficulties in VNB separation as isomers of VNB.

Accordingly, the present inventors have conducted extensive research to solve the problem of applying the mass production process, and as a result, the conversion and yield are improved compared to the method of preparing VNB under a catalyst, and the formation of reaction byproduct THI is suppressed, Compared to the method using the alumina carrier catalyst, the reaction conditions, in particular, the conditions for easy application to a commercial process by shortening the reaction time were established, and the present invention was completed based on this.

It is therefore an object of the present invention to provide a process for producing 5-vinyl-2-norbornene with high conversion and yield using heterogeneous catalysts.

The production method of the present invention for achieving the above object is composed of alumina, silica, silica-alumina, activated carbon and zeolite of an alkali metal of the Group 1 elemental group, an alkaline earth metal of the Group 2, a mixture thereof, or an alloy thereof. In the presence of a catalyst and a solvent prepared by supporting a heterogeneous solid carrier substrate selected from the group, 1 to 4 moles of cyclopentadiene and 1 to 4 moles of 1,3-butadiene are subjected to a temperature of 160 ° C to 250 ° C and 160 to 500 psig for 10 minutes to 2 minutes. It is made to react over time.

Hereinafter, the method of the present invention will be described in more detail.

CPD used in the present invention can be prepared by the pyrolysis-distillation method of dcclopentadiene (hereinafter referred to as DCPD), which is generally well known. Purity can be measured using gas chromatography, and there is no particular restriction on the purity, and it is possible if it is 91% or more commercially available. BD may be 97% or more of purity obtained through pyrolysis of naphtha followed by a fractional distillation-extraction process.

The reaction is preferably to use a solvent, the solvent should be inert so as not to affect the reaction itself, the solubility of the reactants should be good, the more the difference in boiling point and VNB for the ease of separation is preferred. Preferable solvents include hydrocarbon solvents and aromatic hydrocarbon solvents, toluene and benzene are preferred among various hydrocarbon solvents, and toluene is particularly preferred.

On the other hand, to suppress the amount of oligomers and polymers formed from byproducts during the reaction, a polymerization inhibitor is used at the beginning of the reaction, and hydroquinone, N, N'-diethylhydroxyamine (hereinafter referred to as DEHA) is suitable. .

The reaction ratio of BD to 1 mole of CPD is preferably about 1 to 4 molar equivalents, and preferably 1.5 to 2 molar equivalents. The reaction temperature is 160 ° C. to 250 ° C., preferably 190 ° C. to 210 ° C., and the reactivity is lower at temperatures lower than the above temperature, and at higher temperatures, isomerization of VNB to THI occurs very rapidly and the amount of oligomers is rapidly increased.

The reaction time may vary depending on reaction conditions such as reaction temperature, catalyst, reaction ratio of reactants, etc., but usually 10 minutes to 2 hours, preferably 10 to 60 minutes, and particularly 10 to 30 minutes is preferable. As the reaction time increases, the conversion is slightly increased, but the selectivity to the VNB is lowered as a whole, resulting in an overall decrease in yield.

According to the present invention, the reaction pressure is maintained at 160 to 500 psig, preferably 200 to 450 psig, particularly preferably 300 to 450 psig using an inert gas (nitrogen, argon, neon). When the reaction is carried out in this pressure range, a good result is obtained that the yield is much improved compared to the normal pressure. In the present invention, the reason for applying the pressure at the beginning of the reaction by using an inert gas is to form the reactants CPD and BD in a uniform liquid phase as the temperature increases in the reaction conditions, causing an increase in the reactivity to the conversion rate of CPD, VNB This provides an increase in selectivity and yield. For example, as a result of the simulation of this phase form, the reaction solution mixture was confirmed to be 100% liquid phase under the reaction conditions of 200 ° C. and 400 psi of the present invention. About 33.6% by volume, the rest being weather).

Examples of the material used as a carrier in the preparation of the catalyst include alumina, silica, silica-alumina, activated carbon, zeolite, and the like. Alumina, zeolite and the like are preferable. The zeolite used as the carrier is not limited, but mordenite, X-type zeolite, Y-type zeolite, zeolite beta (β), ZSM-5, L-type zeolite and the like are preferable, and more preferably mordenite. The carrier comprises alkali metals (Na, K, Cs, Rb, mixtures thereof, or alloys thereof) and / or alkali rare earth metals (Mg, Ca, Sr, Ba, mixtures thereof, or alloys thereof). The compound is added in the form of an aqueous solution, so as to impregnate about 4 to 10% by weight with respect to the carrier, and then dried and calcined to use as a catalyst. At this time, if the content is less than 4% by weight, the conversion and selectivity are lowered. If the content is more than 10% by weight, there is a disadvantage of increasing the by-products and raising the catalyst manufacturing cost.

The metal component useful in the present invention is one or more metals from the group consisting of Group 1 alkali metals and Group 2 alkaline earth metals, and the compounds used as precursors of the metal catalyst components are as follows.

Examples of the sodium compound include sodium nitrate, sodium sulfate, sodium chloride, sodium acetate, sodium carbonate or sodium hydroxide, and sodium nitrate, sodium carbonate or sodium acetate, and the like, and more preferably sodium acetate.

Examples of the potassium compound include potassium nitrate, potassium sulfate, potassium chloride, potassium acetate, potassium carbonate or potassium hydroxide, and potassium nitrate, potassium carbonate or potassium acetate, and the like, and more preferably potassium acetate.

Examples of the cesium compound include cesium nitrate, cesium sulfate, cesium chloride, cesium acetate, cesium carbonate or cesium hydroxide, and the like. Cesium nitrate, cesium carbonate or cesium acetate is preferred, and more preferably cesium acetate.

Examples of the rubidium compound include rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium acetate or rubidium carbonate. Rubidium nitrate, rubidium carbonate and the like are preferable, and rubidium acetate is particularly preferable.

Examples of the magnesium compound include magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium acetate, magnesium carbonate, magnesium hydroxide, and the like, and magnesium nitrate, magnesium carbonate or magnesium acetate is preferable, and magnesium acetate is particularly preferable.

Examples of the calcium compound include calcium nitrate, calcium sulfate, calcium carbonate, calcium acetate or calcium hydroxide, and calcium nitrate, calcium carbonate or calcium acetate, and the like, and calcium acetate is particularly preferable.

When impregnating an alkali metal and / or an alkali rare earth metal to a support body, after impregnating by adding the compound containing an alkali metal and / or alkali rare earth metal in aqueous solution, it is dried at 100-120 degreeC for 3 to 10 hours, and 400- to It is calcined in an oxygen atmosphere flowing at 600 ° C. and used as a catalyst. Thus prepared catalyst is used 5 to 50% by weight, preferably 20 to 30% by weight based on the CPD reaction.

As described above, when the improved production method of the present invention is used, the yield is improved, the formation of by-product THI is suppressed, and the reaction time is significantly shortened, so that it can be easily applied to a commercial process.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Catalyst Production Example

Catalyst A

A solution of 7.3 g of cesium acetate dissolved in 1,000 ml of distilled water was added to 100 g of mordenite (Na-MordeniteSiO ₂ / Al ₂ O ₃ = 13: Na ₂ O = 6wt%) and evaporated at 120 ° C. for 3 to 4 hours. Cesium is evenly distributed on the surface of the carrier and dried. The dried catalyst precursor is calcined at 500 ° C. for at least 3 hours in an oxygen atmosphere. Induced Coupled Plasma-Atomic Emission Chromatography (ICP) analysis showed that the Cs component was 5.0% by weight.

Catalyst B

Except that 8.5g of rubidium acetate was used, and the same method as for the preparation of Catalyst A was performed.

Catalyst C

Except for using 12.6 g of potassium acetate, the same method as for the preparation of Catalyst A, and the K component of the ICP analysis was 5.0 wt%.

Catalyst D

Except for carrying 12.6 g of potassium acetate using ZSM-5 (SiO ₂ / Al ₂ O ₃ = 36) as a carrier, it was the same as the preparation method of Catalyst A. The K component was 5.1 wt% as a result of ICP analysis.

Catalyst E

Except for carrying 12.6 g of potassium acetate using Y-type zeolite (SiO ₂ / Al ₂ O ₃ = 5.2) as a carrier, it was the same as the preparation method of Catalyst A. The K component was 5.1 wt% as a result of ICP analysis.

Catalyst F

Except for carrying 12.6 g of potassium acetate using X-type zeolite as a carrier, it was the same as the preparation method of catalyst A. The K component was 5.1 wt% as a result of ICP analysis.

Catalyst G

Except for carrying 25.2 g of potassium acetate using ZSM-5 (SiO ₂ / Al ₂ O ₃ = 36) as a carrier, it was the same as the preparation method of Catalyst A. The K component was 10.1% by weight as a result of ICP analysis.

Catalyst H

Except for carrying 25.2 g of potassium acetate using Y-type zeolite (SiO ₂ / Al ₂ O ₃ = 5.2) as a carrier, it was the same as the preparation method of Catalyst A. The K component was 10.1% by weight as a result of ICP analysis.

Catalyst I

Except for carrying 25.2 g of potassium acetate using X-type zeolite as a carrier, it was the same as the preparation method of catalyst A, and K component was 10.0 wt% as a result of ICP analysis.

Catalyst J

Except for supporting 25.2 g of potassium acetate using mordenite (Na-MordeniteSiO ₂ / Al ₂ O ₃ = 13: Na ₂ O = 6wt%) as a carrier, the same method as in the preparation of Catalyst A was performed. As a result, K component was 10.0 weight%.

Catalyst K

Except for supporting 17.0 g of rubidium acetate using mordenite (Na-MordeniteSiO ₂ / Al ₂ O ₃ = 13: Na ₂ O = 6wt%) as a carrier, the same method as in the preparation of Catalyst A was performed. As a result, the Rb component was 10.0 wt%.

Catalyst L

Mordenite (Na-MordeniteSiO ₂ / Al ₂ O ₃ = 13: Na ₂ O = 6wt%), which is a carrier, is used as a reaction catalyst without supporting other components.

Comparative Example 1 and Reference Example 1

Pressure effect on the reaction under no catalyst

In a 100 ml autoclave, 60 ml of solvent benzene, 3.3 g CPD and 5.2 g BD are added under a nitrogen atmosphere. The results were compared for the case where no additional pressure was applied (Comparative Example 1) and the inert gas was injected at a pressure of 400 psig at the reaction temperature (Reference Example 1). The temperature was raised while stirring the reactor and the reaction was performed at 200 ° C. for 10 minutes. After the reaction was completed, the temperature was lowered to room temperature, the reaction product was taken, and the product was analyzed using gas chromatography. The analysis results are shown in Table 1 below.

Reaction pressure Comparative Example 1 (150 psi) Reference Example 1 (400 psi) % CPD conversion 56.8 88.8 Selectivity (%) VNB 10.1 37.5 THI 4.3 9.6 DCPD 71.9 47.5 Oligomer 13.7 5.4

In Table 1, the calculation method of the conversion rate and the selectivity of CPD is shown in Equations 1 and 2, respectively.

Comparative Example 2

No catalyst, reaction time effect at 400 psig

As in Reference Example 1, the reactants were added to the high pressure reactor, the inert gas was injected to give an additional pressure, and the effects on the reaction time at 200 ° C. were compared. After the reaction was completed, the temperature was lowered to room temperature, the reaction product was taken, and the product was analyzed using gas chromatography. The analysis results are shown in Table 2 below.

Response time (minutes) 10 30 60 % CPD conversion 88.8 90.2 95.4 Selectivity (%) VNB 37.6 43.1 30.3 THI 9.6 16.2 39.9 DCPD 47.5 33.4 11.2 Oligomer 5.4 7.3 18.6

Example 1

Reaction according to modified catalyst

1 g of various types of heterogeneous catalysts modified in the catalyst preparation example were put in the same conditions as in Reference Example 1, and the reaction pressure was fixed at 400 psig and the reaction time was 10 minutes using an inert gas. After the reaction was completed, the temperature was lowered to room temperature, and the reaction product was taken. After the solid catalyst was removed from the reaction, the reaction solution was analyzed using gas chromatography. The results are shown in Table 3 below.

catalyst CPD conversion rate (%) Selectivity (wt%) VNB THI DCPD Oligomer Catalyst L 94.0 36.7 18.5 10.0 34.8 Catalyst C 95.4 54.8 19.9 17.3 8.0 Catalyst J 91.1 54.4 19.8 17.9 7.9 Catalyst D 93.1 54.2 20.6 16.1 9.1 Catalyst G 91.1 53.5 22.5 14.3 9.7 Catalyst E 92.2 52.7 22.8 15.6 8.9 Catalyst H 92.0 53.5 22.4 15.1 9.0 Catalyst F 93.7 48.6 21.5 14.4 15.5 Catalyst I 94.0 53.6 23.0 12.6 10.8

Comparative Example 3

Reaction result according to the metal supported on the catalyst at normal pressure

In Example 1, various alkali metal salts were supported on mordenite and used as a catalyst, and reacted at 200 ° C. for 10 minutes without additional pressure. The results are shown in Table 4 below.

Reaction catalyst Catalyst C Catalyst A Catalyst B Catalyst K % CPD conversion 89.5 69.2 82.9 81.3 Selectivity (%) VNB 33.8 20.2 32.3 24.3 THI 13.9 7.9 14.5 11.0 DCPD 40.2 66.7 46.9 57.5 Oligomer 7.1 5.2 6.3 7.2

Comparative Example 4

Response to temperature change

In Example 1, 1g of the catalyst C and the reactant were injected into the reactor, and the reaction was carried out for 10 minutes by raising the temperature to 160 ° C to 220 ° C without additional pressure. Results according to each temperature are shown in Table 5 below.

Reaction temperature (℃) 160 180 200 220 % CPD conversion 64.4 64.2 85.9 46.8 Selectivity (%) VNB 9.9 11.6 33.8 8.5 THI 2.4 2.1 13.9 10.9 DCPD 87.7 85.7 40.1 71.0 Oligomer 0 0.6 7.1 9.8

Example 2

Reaction result according to metal salt supported on catalyst at reaction pressure of 400 psig

1 g of a catalyst having Na, K, Cs, and Rb supported on mordenite at 5 wt% was reacted for 10 minutes at 400 psig at a reaction pressure of 200 ° C as in Example 1. The results are shown in Table 6 below.

Reaction catalyst Catalyst L Catalyst C Catalyst B Catalyst A % CPD conversion 90.2 89.6 90.8 90.9 Selectivity (%) VNB 48.7 48.2 49.4 49.2 THI 16.5 17.6 19.0 20.4 DCPD 27.1 26.7 24.3 21.9 Oligomer 7.7 7.5 7.3 8.5

Example 3

Mordenite catalyst carrying reaction-metal salts with time variation at 400 psig

In Example 1, the reaction was carried out at 400 ° C. under a reaction pressure of 200 ° C. using a catalyst described in Table 7 below. The results are shown in Table 7 below.

catalyst Catalyst B Catalyst A Reaction temperature (℃) 10 minutes 30 minutes 60 minutes 10 minutes 30 minutes 60 minutes % CPD conversion 90.8 93.0 96.4 90.9 91.4 81 Selectivity (wt%) VNB 49.4 42.3 27.8 49.2 48.2 43.6 THI 19.0 37.0 50.4 20.4 18.8 34.6 DCPD 24.3 9.2 2.6 21.9 24.9 8.8 Oligomer 7.3 11.5 19.2 8.5 8.1 13.0

Example 4

Reaction with temperature change at reaction pressure of 400 psig

The reaction was carried out as in Example 1 by raising the temperature to the desired temperature while stirring the reactor at a reaction pressure of 400 psig. The reaction time was fixed at 10 minutes. The results are shown in Table 8 below.

Reaction temperature (℃) 160 180 200 220 % CPD conversion 85.9 84.6 90.8 90.8 Selectivity (wt%) VNB 33.8 31.6 49.4 24.5 THI 13.9 7.9 19 53.9 DCPD 40.2 56.0 24.3 6.8 Oligomer 7.1 4.5 7.3 14.8

As can be seen from the above examples, when comparing the pressure effect in the reaction in the presence of the catalyst according to the present invention, as the pressure is increased to 400 psi, not only the conversion of CPD increases but also the selectivity to VNB is about 20%. It showed an increase. This is believed to be due to facilitating contact between the reactants under the catalyst as the reaction mixture is in the liquid phase under the above conditions. In addition, when comparing Example 1 with Comparative Example 1 and Reference Example 1, the reaction in the presence of a catalyst has the effect of increasing the selectivity to VNB by 15% or more. In addition, when the catalyst according to the present invention is compared with the activated alumina carrier catalyst reported in Japanese Patent Application Laid-Open No. 48-92353, the performance of the reaction appears to be slightly lower, but considering the particle size, durability and reaction time, etc. It can be seen that it is much more advantageous for the application of the continuous process.

Claims (11)

Catalysts and solvents prepared by loading an alkali metal of Group 1, alkaline earth metals of Group 2, or a mixture thereof on a heterogeneous solid carrier substrate selected from the group consisting of alumina, silica, silica-alumina, activated carbon and zeolite 5-vinyl-2-norbornene characterized by reacting 1 mole of cyclopentadiene and 1 to 4 moles of 1,3-butadiene for 10 minutes to 2 hours at 160 ° C to 250 ° C and 160 to 500 psig. Manufacturing method. The method of claim 1, wherein the catalyst is used in an amount of 5 to 50% by weight based on cyclopentadiene. The method of claim 1, wherein the alkali metal is Na, K, Cs, Rb, a mixture thereof, or a mixture thereof. The method for preparing 5-vinyl-2-norbornene according to claim 1, wherein the alkaline earth metal is Mg, Ca, Sr, Ba, a mixture thereof, or an alloy thereof. The process for producing 5-vinyl-2-norbornene according to claim 1, wherein the catalyst is supported at 4 to 10% by weight based on the carrier. The method of claim 1, wherein the zeolite is mordenite, X-type zeolite, Y-type zeolite, ZSM-5, zeolite beta or L-type zeolite. The method of claim 1, wherein the reaction molar ratio of 1,3-butadiene is 1.5 to 2 moles with respect to 1 mole of cyclopentadiene. The method of claim 1, wherein the reaction pressure is 300 to 450 psig. The method according to claim 1, wherein the reaction temperature is 190 to 210 ° C. The method of claim 1, wherein the reaction time is 10 to 30 minutes. The method of claim 1, wherein the solvent is a hydrocarbon solvent or an aromatic hydrocarbon solvent.