KR101616071B1 - Method for producing norbornadiene dimer using hetorogneous catalyst - Google Patents

Method for producing norbornadiene dimer using hetorogneous catalyst Download PDF

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KR101616071B1
KR101616071B1 KR1020150146886A KR20150146886A KR101616071B1 KR 101616071 B1 KR101616071 B1 KR 101616071B1 KR 1020150146886 A KR1020150146886 A KR 1020150146886A KR 20150146886 A KR20150146886 A KR 20150146886A KR 101616071 B1 KR101616071 B1 KR 101616071B1
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norbornadiene
catalyst
zeolite
dimer
reaction
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정병훈
한정식
전종기
박은서
정관형
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국방과학연구소
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C07C13/64—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings with a bridged ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
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Abstract

The present invention relates to a preparation method of a norbornadiene dimer using a dimerization reaction of norbornadiene (bicyclo(2.2.1) heptadiene-2,5, NBD). More particularly, the preparation method of the present invention prepares a norbornadiene dimer by promoting a dimerization reaction of norbornadiene using a heterogeneous catalyst including a microporous zeolite catalyst and a mesoporous aluminosilicate catalyst.

Description

TECHNICAL FIELD The present invention relates to a method for producing a norbornadiene dimer using a heterogeneous catalyst,

The present invention relates to a dimerization reaction of norbornadiene (hereinafter also referred to as 'NBD'), and more particularly to a heterogeneous catalyst, which comprises a microporous zeolite and a medium- The present invention relates to an invention for producing a norbornadiene dimer (NBDD) by promoting a dimerization reaction of norbornadiene using alumino silicate of meso pore .

High energy density fuels are attracting much attention as fuel for aircraft with limited volume of fuel tanks such as missiles and rockets due to their high volumetric energy content and excellent stability. The norbornadiene dimer (NBDD) is a candidate for ideal high energy density fuel because the ratio of carbon / hydrogen in the molecule is as large as 91.25 / 8.75 and the number of rings is high and dense structure increases density and causes additional strain energy. Hydrogenated norbornadiene dimers (H-NBDD), a hydrogenated norbornadiene dimer, have a high density (1.08 g / ml) and a calorific value (161,000 Btu / gal).

Norbornadiene dimer (NBDD) was synthesized through dimerization using norbornadiene (NBD) as a raw material by the production of norbornadiene (NBD) through the reaction of cyclopentadiene and acetylene. ), And such a norbornadiene dimer can be prepared from a pentacyclic exo-t-exo NBD dimer (Pxtx), a hexacyclic exo-endo NBD dimer (Hxn), a hexacyclic endo-endo NBD dimer (Hnn), and the like (U.S. Patent No. 4,207,080).

US Pat. No. 3,282,663 discloses a method for preparing norbornadiene dimer by using Ni (PPh 3 ) 4 or ferric acethylacetonate or triethylalumimum as a catalyst, (pentacyclic dimer) and hexacyclic dimer were synthesized. However, since the homogeneous catalyst having the same phase of the reactant and the catalyst was used, catalyst recovery and reuse were impossible.

In U.S. Patent No. 3,326,993, Mm [Co (CO) 4 ], in which carbonyl (tetracarbonylcobaltate) anions including cobalt and metal cations such as zinc (Zn) and cadmium (Cd) n-type main catalyst and Lewis acid (BF 3 , AlBr 3, etc.) are used as cocatalysts, there is a problem that separate catalyst production is difficult and manufacturing cost is increased.

In addition, U.S. Patent No. 3,377,398 reported that norbornadiene dimer was synthesized at a temperature of 140 ° C or higher using ferric acetylacetonate or triethylalumimum catalyst. However, a homogeneous catalyst which can not be recovered and reused Were used.

In addition, U.S. Patent No. 4,031,150 and U.S. Patent No. 4,208,355 disclose that tris (triphenyl-phosphine) rhodium chloride, RhCl (PPh 3 ) 3 ), diethyl Catalysts such as aluminum chloride (diethylaluminum chloride, AlEt 2 Cl) or cobalt acethylacetonate, diethylaluminum chloride (AlEt 2 Cl) and triphenylphosphine triphenylphosphine (PPh 3 ) , Reported that a heptacyclic Binor-S type norbornadiene dimer was prepared. However, since the catalyst was sensitive to moisture, it was difficult to handle and the expensive homogeneous catalyst was used.

In addition, U.S. Patent No. 4,094,916 discloses a method of preparing a catalyst for the production of a catalyst by using a three-way catalyst system such as ferric acetylacetonate, diethylaluminum chloride (AlEt 2 Cl), triphenylphosphine triphenylphosphine (PPh 3 ) It has been reported that the hexacyclic endo-endo NBDD isomer and the exo-exo NBDD isomer are obtained with a high yield in the case of the NBDD isomer. However, there is a problem in using a homogeneous catalyst which can not be recovered and reused.

In U.S. Patent No. 4,207,080, cobalt acethylacetonate-bis (1,2-diphenylphosphino) ethane or diethylaluminum chloride (AlEt 2 Cl), including cobalt, , And US Pat. No. 5,608,131 reported that a norbornadiene dimer was produced using a ruthenium complex, but they were separately prepared from expensive catalysts and used do.

In order to facilitate the recovery of the catalyst after the norbornadiene dimerization reaction in the literature, it has been reported that the norbornadiene dimer is prepared by using an ionic liquid catalyst and the catalyst is separated and reused. However, There is a problem that the conversion rate and the yield are drastically lowered as the number of times of reuse is repeated (J. Catalysis, 2008, 2588, 5-13).

The above-mentioned conventional norbornadiene dimer manufacturing techniques have a problem of using homogeneous catalysts which are excellent in reactivity but are mostly moisture-sensitive, difficult to handle, impossible to be recovered and reused, and expensive.

United States Patent No. 3,282,663 United States Patent No. 3,326,993 United States Patent No. 3,377,398 U.S. Patent No. 4,031,150 United States Patent No. 4,208,355 U.S. Patent No. 4,094,916 United States Patent No. 4,207,080 U.S. Patent No. 5,608,131

Mai Dao Nguyen et al., J. Catalysis, 2008, 258, 5-13.

Accordingly, the present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a zeolite having a micro pore structure and a medium size zeolite as a heterogeneous catalyst which is easy to recover and reusable in a liquid reactant for the production of norbornadiene dimer, The object of the present invention is to provide a method for efficiently producing a norbornadiene dimer by promoting the dimerization reaction of norbornadiene using alumino silicate of meso pore.

In order to accomplish the above object, the present invention provides a process for preparing a norbornadiene dimer, which comprises introducing norbornadiene as a reactant into a solvent, adding norbornadiene as a heterogeneous catalyst to a norbornadiene dimer using a zeolite or an aluminosilicate, Diene, and when the aluminosilicate is used, it can be reused as a catalyst after the dimerization reaction step of the norbornathione.

Specifically, the catalyst regeneration can be reused by regenerating the alumino silicate washed with toluene as a solvent after calcination at 300 to 550 ° C. for 4 hours to regenerate the alumino silicate after the dimerization reaction, more preferably 400 If the temperature is less than 300 ° C, the polymer substances deposited on the surface of the catalyst are not burned, which is difficult to regenerate. If the temperature exceeds 550 ° C, the catalyst is damaged.

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

Meanwhile, in the present invention, the size of the pores of the aluminosilicate used as the heterogeneous catalyst is larger than the pore size of the zeolite. Specifically, the pores of the zeolite and meso pore As defined in International Union of Pure and Applied Chemistry (IUPAC), the term 'micro pore' means that the pore diameter is less than 2 nm, and 'medium pore meso pore 'means that the pore diameter is 2 to 50 nm.

The microporous zeolite is a solid acid catalyst rich in acid sites and has a Brnsted acid site (Lewis acid site) and a Lewis acid site (Lewis acid site). The catalyst can be recovered and reused easily in the reaction in which the reaction product and the reaction product are in the vapor phase or the liquid phase because the heterogeneous catalyst can facilitate the polymerization and the isomerization reaction.

As the microporous zeolite, any one selected from HY zeolite, H beta zeolite and HZSM-5 may be preferably used as the zeolite ion-exchanged with hydrogen.

The mesoporous aluminosilicate is composed of a Y zeolite unit structure, a beta (zeolite) unit structure, or a ZSM-5 unit structure, and thus has a rich acid site like the microporous zeolite. And because of the heterogeneous catalyst, it is easy to recover and reuse the catalyst in the reaction in which the reaction product and the reaction product are in vapor or liquid phase. In the present invention, MMZ-beta can be preferably used as the mesoporous aluminosilicate.

The mesoporous aluminosilicate pore size is 2 to 10 nm and the surface area is preferably 425 m 2 / g to 720 m 2 / g, so that the norbornadiene molecule or the norbornadiene dimer molecule is in contact with the catalyst porosity And it is easy to reach the surface active sites in the catalyst pores.

The zeolite of the heterogeneous catalyst and the aluminosilicate catalyst of the mesopore can be applied to the dimerization reaction using norbornadiene as a reactant under the following reaction conditions.

In the present invention, the reaction for preparing the norbornadiene dimer by promoting the dimerization reaction of the norbornadiene using the zeolite of the heterogeneous catalyst and the mesoporous aluminosilicate is carried out at a reaction temperature of 200 to 300 ° C And the reaction is preferably carried out at a reaction temperature of 230 to 270 ° C. If the reaction temperature is lower than 200 ° C., the activity of the dimerization reaction is lowered. If the reaction temperature is higher than 300 ° C., the reaction product norbornadiene is decomposed It can be damaged.

The amount of the heterogeneous catalyst is 1 to 10 wt%, preferably 3 to 7 wt%, based on the weight of the norbornadiene as a reactant. If the amount of the catalyst is less than 1 wt% of the reactant, the activity is low. If the amount of the catalyst is more than 10 wt%, the viscosity of the slurry composed of the reactant and the catalyst mixture is too high.

The amount of toluene in the reaction conditions is 10 to 90 wt%, preferably 20 to 40 wt%, based on the weight of the norbornadiene as the reactant, %. When the amount of the toluene is less than 10 wt%, the slurry composed of the mixture of the dimer of the norbornadiene and the catalyst, which is the reaction product, is too viscous to operate the reactor. When the amount of the toluene exceeds 90 wt% The concentration of dienes is too low and the efficiency of the dimerization reaction may be lowered.

In the present invention, the reaction for preparing the norbornadiene dimer by promoting the norbornadiene dimerization reaction using the microporous zeolite as the heterogeneous catalyst and the mesoporous aluminosilicate is carried out in the batch reactor for 3 to 30 hours, Preferably 8 to 20 hours. If the reaction time is less than 3 hours, the reaction activity is low, and if the reaction time is more than 30 hours, a large amount of polymer having a large molecular weight is produced, resulting in a solid product having a high viscosity.

According to the present invention, when zeolite having a micro pore structure and aluminosilicate catalyst having a medium pore size are used as heterogeneous catalysts in comparison with a conventional homogeneous liquid phase catalyst, the norbornadiene dimerization reaction is promoted to produce a norbornadiene dimer Can be effectively performed.

In addition, the method for producing a norbornadiene dimer according to the present invention is capable of recovering and regenerating catalysts, in particular, when using an aluminosilicate catalyst, and the regenerated aluminosilicate catalyst exhibits excellent performance before the regeneration efficiency , And the fact that the catalyst can be regenerated and reused can be advantageously used industrially in the field of high energy density fuel production.

Figure 1 shows the possible isomers of the previously disclosed norbornadiene dimer.
Figure 2 shows the results of gas chromatography analysis of reaction products according to one embodiment of the present invention.
FIG. 3 shows the ammonia temperature desorption analysis results of the heterogeneous catalysts of the present invention.

The process for preparing a norbornadiene dimer according to the present invention is characterized by using a microporous zeolite and a mesoporous aluminosilicate as a heterogeneous catalyst for the dimerization reaction of norbornadiene and reusing it if necessary .

Hereinafter, the present invention will be described in more detail by way of Comparative Examples and Examples, but the scope of the present invention is not limited thereto.

In Comparative Example 1, 90 g of norbornadiene and 28 g of toluene were fed into a 160 ml high-temperature high-pressure batch reactor, and the dimerization reaction was carried out with stirring. At this time, the dimerization reaction is carried out for 12 hours at a temperature of 250 ° C., a reaction pressure of 10 atm and a stirring speed of 300 rpm to prepare a norbornadiene dimer.

In Example 1, 3.7 g of HY zeolite (Zeolyst Co.), Y-zeolite ion-exchanged with hydrogen as a heterogeneous catalyst, was charged in a 160 ml high-temperature high-pressure batch reactor, and 90 g of the reaction product norbornadiene and 28 g of toluene were charged , And the dimerization reaction is carried out while stirring. At this time, a dimonization reaction of norbornadiene is carried out at a temperature of 250 ° C., a reaction pressure of 10 atm and a stirring speed of 300 rpm for 12 hours to prepare a norbornadiene dimer.

Example 2 is the same as Example 1 except that Hβ zeolite (Zeolyst Co.), which is a beta zeolite ion-exchanged with hydrogen as a heterogeneous catalyst, is used and a dimerization reaction is carried out to prepare a norbornadiene dimer.

Example 3 was carried out in the same manner as in Example 1 except that HZSM-5 zeolite (Zeolyst Co.), which was a ZSM-5 zeolite ion-exchanged with hydrogen as a heterogeneous catalyst, was used and a norbornadiene dimer .

Example 4 is to carry out the dimerization reaction using aluminosilicate of mesopore as a heterogeneous catalyst.

The mesoporous aluminosilicate prepared above is used as the mesoporous aluminosilicate. The mesoporous aluminosilicate is prepared by using a zeolite and a basic aqueous solution to prepare a mesoporous material having a zeolite skeleton.

First, 22.5 g of sodium hydroxide (NaOH) was dissolved in 76.5 g of distilled water to prepare an aqueous solution of sodium hydroxide. 33.75 g of hydrogen-ion-exchanged Hβ zeolite (ratio of silicon to aluminum = 25) It is used as a precursor solution for the synthesis of mesoporous materials. A surfactant solution was prepared by dissolving 69 g of cationic surfactant cetyltrimethylammonium bromide (CTAB) (1050 g) in distilled water, and the surfactant solution was added dropwise to the solution containing Hβ zeolite Stir for 24 hours. After hydrothermal synthesis in an oven at 100 ° C for 12 hours without stirring, cool the reaction solution at room temperature, add 50% by weight of acetic acid dropwise while stirring, and adjust the pH to 10. The hydrothermal synthesis reaction and the pH adjustment process described above are repeated three more times. The precipitate thus obtained was collected by vacuum filtration, washed thoroughly with distilled water several times, dried in an oven at 100 ° C. for 24 hours, washed with ethanol to remove the surfactant, and filtered and dried in an oven at 100 ° C. for 24 hours . Then, if the calcination is carried out in an electric firing furnace at a temperature of 550 ° C. for 4 hours in an air atmosphere, it is possible to obtain mesoporous aluminosilicate (MMZ-beta) having mesopores.

In the present invention, the mesoporous iridium silicate was molded into a pellet having a diameter of 2 mm and a height of 4 mm using a biaxial extruder.

In Example 4, 3.7 g of the mesoporous aluminosilicate (MMZ-beta) pellet prepared as described above was charged in a catalyst basket equipped with a heterogeneous catalyst in a 160 ml capacity high-temperature high-pressure batch reactor, , The dimerization reaction was carried out in the same manner as in Example 1 to prepare a norbornadiene dimer.

In Example 5, after performing the dimerization reaction in Example 4, the alumino silicate (MMZ-beta) pellet of the medium pore mounted on the catalyst basket was recovered, washed with toluene, (MMZ-beta), which is a catalyst for medium-sized pores, is regenerated by heating at 550 ° C for 3 hours in an air atmosphere. The mesoporous aluminosilicate (MMZ-beta) thus regenerated was subjected to a dimerization reaction in the same manner as in Example 4 to prepare a norbornadiene dimer.

In Comparative Example 1 and Examples 1 to 5, the yield of norbornadiene dimer was analyzed by gas chromatography using a reaction product after 12 hours from the start of the dimerization reaction.

An example of the analysis result of the gas chromatography of the reaction product of the present invention according to the analysis conditions of gas chromatography as shown in the following Table 1 is as shown in Fig. As shown, the yields of norbornadiene dimers can be analyzed from the peaks near the residence time of 12 minutes.

Injector
(Injector) Injector temperature
(Injector temperature) 250 ℃ Carrier gas
(Carrier gas) Helium (He) Flow rate of carrier gas
(Flow rate of carrier gas) 2.0 ml / min Split ratio 20 column
(Column) column CP-Sli5 (Capillary, 30 m × 0.32 μm × 0.25 μm) Oven temperature
(Oven temperature) 50 캜, 2 minutes
50 ° C to 70 ° C, 10 ° C / min (70 ° C, 1 minute)
70 to 140 占 폚, 20 占 폚 / min (140 占 폚, 0.5 min)
140 DEG C to 150 DEG C, 20 DEG C / min (150 DEG C, 1 minute)
150 to 250 占 폚, 25 占 폚 / min (250 占 폚, 20 minutes) Detector
(Detector) Detector temperature
(Detector temperature) 250 ℃ Flow rate of hydrogen gas
(Flow rate of hydrogen) 30 ml / min Air flow rate
(Flow rate of Air) 300 ml / min

Table 2 below shows the molar ratio of SiO 2 / Al 2 O 3 and the BET (Brunauer Emmett Teller) surface area to the heterogeneous catalysts described above.

Surface area and pore size distribution in the present invention, the nitrogen adsorption on the catalyst sample of used in the embodiment of the present invention after obtaining the desorption isotherms (N 2 adsorption-desorption isotherm) , the surface area is measured by the method (Brunauer Emmett Teller) BET And the pore size distribution is calculated by the BJH (Barrett-Joyner-Halenda) method.

catalyst SiO 2 / Al 2 O 3 mole ratio BET surface area (m 2 / g) HY zeolite 60 720 Hb zeolite 25 680 HZSM-5 Zeolite 23 425 MMZ-beta 291 518

As a result, the specific surface area of HY zeolite, H beta zeolite, HZSM-5 zeolite and aluminosilicate (MMZ-beta) catalysts was found to be 425 m 2 / g or more, preferably 425 m 2 / m 2 / g, and thus has a structure capable of retaining a large amount of dimerization active sites on the catalyst surface.

FIG. 3 shows the results of ammonia desorption desorption analysis performed to investigate acid characteristics of the heterogeneous catalysts of the present invention. Generally, the acid strength can be compared through the energy required to desorb the adsorbed base, and the amount of the desorbed salt can be measured while the temperature is raised at an appropriate rate after adsorbing the base. In the present invention, the acid characteristic is analyzed from the TCD signal through the peak temperature by the thermal conductivity detector (TCD) according to the heating rate.

As shown in FIG. 3, HY zeolite, H beta zeolite and HZSM-5 zeolite catalyst have both weak acid sites and strong acid sites, and especially aluminosilicate (MMZ-beta) Able to know. Such acid sites can serve to enhance the yield of the norbornadiene dimerization reaction of the present invention since they can promote the dimerization reaction.

Table 3 below shows the results of Comparative Example 1, which is a dimerization reaction of norbornadiene without catalyst, and Examples 1 to 5, which is a dimerization reaction of norbornadiene by the method of the present invention, Shows the yield of norbornadiene dimer according to reaction conditions such as reactants, solvent, type of catalyst, size of catalyst pores, reaction temperature, reaction time and the like.

division catalyst pore
size
(nm) Reactant menstruum Reaction temperature
(° C) Reaction time
(city) Norbornadiene dimer yield
(wt%) Comparative Example 1 - - NBD toluene 250 12 0.0 Example 1 HY zeolite 0.7 NBD toluene 250 12 41.5 Example 2 Hb zeolite 0.6 to 0.7 NBD toluene 250 12 37.8 Example 3 HZSM-5 Zeolite 0.5 to 0.6 NBD toluene 250 12 33.4 Example 4 MMZ-beta 3.7 NBD toluene 250 12 34.2 Example 5 MMZ-beta
(Regenerated catalyst) 3.7 NBD toluene 250 12 33.4

In Table 3, the yield of norbornadiene dimer is represented by the weight percentage of norbornadiene (NBD) as a reactant, based on the total amount of norbornadiene dimer produced by the dimerization reaction.

As shown in the above Table 3, HY zeolite, H beta zeolite, and H beta zeolite as heterogeneous catalysts in Examples 1 to 4 according to the present invention, compared with Comparative Example 1, which is a catalyst-free reaction in the dimerization reaction of norbornadiene, In the case of using HZSM-5 zeolite and mesoporous alumino silicate (MMZ-beta), the yield of the norbornadiene dimer was improved, and in particular, the alumino silicate Even when the recycled catalyst recycled by the calcination process of the silicate (MMZ-beta) was reused, the yield of the norbornadiene dimer was 33.4 wt%, and the use of the mesoporous aluminosilicate (MMZ-beta) The dimer yield was maintained similar to the yield of 34.2 wt% of the norbornadiene dimer in Example 4, so that the catalyst could be recovered and reused .

Therefore, it is expected that the present invention will be very useful in the field of high energy fuel production through the norbornadiene dimerization reaction using a heterogeneous catalyst in order to highly efficiently promote the norbornadiene dimerization reaction.

It should be noted that the above-described embodiment is a preferred embodiment for allowing a person skilled in the art who is skilled in the art to easily carry out the present invention, and is not limited to the above- The scope of rights is not limited. It will be apparent to those skilled in the art that various substitutions, modifications and variations are possible within the scope of the present invention, and it is obvious that those parts easily changeable by those skilled in the art are included in the scope of the present invention .

Claims (8)

In the batch reactor, norbornadiene as a reactant and 10 to 90 wt% of toluene relative to the weight of the norbornadiene were charged. As the heterogeneous catalyst, MMZ-beta was prepared with HY zeolite or mesoporous aluminosilicate as microporous zeolite, And a dimerization reaction step of adding a norbornadiene dimer to produce a norbornadiene dimer by stirring at a stirring rate of 300 rpm for 12 hours at a reaction temperature of 250 ° C,
In the case of the above-mentioned mesoporous aluminosilicate, the aluminosilicate washed with toluene is recovered after the dimerization reaction step of the norbornadiene and is reusable by firing at 550 DEG C under an air atmosphere using an electric firing furnace,
Wherein the microporous zeolite or mesoporous aluminosilicate is a heterogeneous catalyst for increasing the yield of norbornadiene dimer and has a surface area of 450 to 720 m 2 / g. delete delete delete delete The method according to claim 1,
Wherein the microporous zeolite is H? Zeolite or HZSM-5.
delete delete
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Cited By (2)

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KR101976075B1 (en) * 2018-03-30 2019-08-28 국방과학연구소 Composition for manufacturing high-energy density power source, high-energy density power source composition and method for manufacturing high-energy density power source composition
RU2765442C1 (en) * 2020-12-16 2022-01-31 Общество с ограниченной ответственностью "Оргнефтехим-Холдинг" (ООО "ОНХ-ХОЛДИНГ") Method for producing pentacyclic dimers of bicyclo[2.2.1]hepta-2,5-diene (norbornadiene)

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