KR101014625B1 - Method for preparing composition comprising norbornadiene dimers and method for controling production ratio of norbornadiene dimers - Google Patents

Abstract

The present invention relates to hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene by dimerization of norbonadiene. , Hexacyclo [7.2.1.0 ^2,8 . 1 ^3,7 .1 ^5,13 . 1 ^4,6 ] tetrades-10-ene and pentacyclo [8.2.1.0 ^{2,9 3,8} .1 ^4,7 ] tetradeca-5,11-diene in weight ratio 52-94%, 2 A method for producing a composition containing in an amount of ˜25% and 1 to 21% and a method for regulating the production ratio of norbornadiene dimer. In the present invention, since a composition containing three adult species in the same ratio can be produced by one reaction, it is very efficient and economical.

Norbornadiene, Norbornadiene Dimer, Endo-Endo Hexagonal Ring Norbornenadiene Dimer, Endo-Exo Hexagonal Ring Norbornadiene Dimer, Exo-Trans-Exo Pentacyclic Ring Norborneadiene Dimer

Description

METHOD FOR PREPARING COMPOSITION COMPRISING NORBORNADIENE DIMERS AND METHOD FOR CONTROLING PRODUCTION RATIO OF NORBORNADIENE DIMERS}

The present invention relates to a method for producing a dimer composition of norbornadiene and a method for controlling the production ratio of norbornadiene dimer.

When dimerizing one of the compounds derived from petrochemicals, norbornadiene (bicyclo [2.2.1] hepta-2,5-diene, hereinafter referred to as "NBD"), the dicyclic polymer Is generated. These dimers are known to release energy upon decomposition due to their high strain energy due to their molecular structure. Many studies have been conducted on these compounds in the past, and it has been reported that dimerization of NBD yields 14 dimers, theoretically shown below (US Pat. No. 4,207,080).

Among the dimers, hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene (hexacyclo [7.2) is an endo-endo isomer. ^{.1.0 2,8} .1 ^3,7 .1 ^5,13 .0 ^4,6 ] tetradec-10-ene, hereinafter referred to as "HNN"), ^{exocyclo hexacyclo} [7.2. 1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene (hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ] tetradec-10-ene (hereinafter referred to as "HXN") and the exo-trans-exo isomer pentacyclo [8.2.1.0 ^{2,9 3,8} .1 ^4,7 ] tetra Deca-5,11-diene (pentacyclo [8.2.1.0 ^2,9 .0 ^3,8 .1 ^4,7 ] tetradeca-5,11-diene, hereinafter referred to as "Pxtx") is useful as a high performance fuel. And methods of making each are also known.

US Pat. No. 4,094,916 discloses iron acetylacetonate (FeAA ₃ ), triphenylphosphine (TPP) and diethylaluminum chloride as main catalyst, stabilizing catalyst and reducing catalyst, respectively, as shown in Scheme 1 below. When dimerizing NBD using DEAC), it was reported that HNN can be obtained with a yield of 80%.

US Pat. No. 4,275,254, on the other hand, dimerizes NBD using rhodium acetylacetonate (RhAA ₃ ) and diethylaluminum chloride (DEAC) as main catalysts and reduction catalysts, respectively, as shown in Scheme 2 below. In the case of HXN, 76% yield was reported, but HNN and trimer (trimer) were reported to be produced by 13% and 9%, respectively. However, this process is uneconomical because the price of the main catalyst RhAA ₃ is high.

In addition, U.S. Patent No. 3,258,502 reports that when a nickel compound is used as the main catalyst, a pentacyclic isomeric mixture comprising Pxtx is prepared, as shown in Scheme 3 below.

As well as each pure NBD dimer prepared as described above, the composition is adjusted by adjusting the ratio between them is also used as fuel for special purposes. Among them, three substances of HNN, HXN and Pxtx are mixed at a weight ratio of 55 to 75%, 16 to 22% and 9 to 20%, respectively, and are known under the product name Shelldyne-H. This material is an optimized fuel composition with optimum properties suitable for use as a high performance fuel, ie, moderate density, high calorific value and low viscosity properties. Shelldyne-H is prepared by mixing three dimers, each of which has been produced. A number of new fuel compositions using this material have been published (US Pat. Nos. 4,087,257, 4,099,931, 4,165,969, 4,410,749, 4,367,351). See et al.).

However, the method of separately preparing and mixing HNN, HXN, and Pxtx separately requires the use of expensive catalysts such as RhAA ₃ , three separate reactors and processes, and a mixing process. Improvement is urgent.

U.S. Patent No. 4,207,080 reports an example of a mixture of these three dimers obtained by one dimerization reaction. According to this document, iron acetylacetonate (FeAA ₃ ), bis (1,2-diphenylphosphino) ethane [bis (1,2-diphenylphosphino) as main catalysts, stabilization catalysts and reduction catalysts for the production of HXX, respectively. ethane] and triethylaluminum (TEA) were reported to produce a mixture of HNN, HXN and Pxtx, but yields were very low at 14%, 13% and 17%, respectively. Could not be.

Therefore, in order to economically and efficiently prepare a composition containing HNN, HXN and Pxtx by one reaction as shown in Scheme 4 below, by selecting an appropriate catalyst, the overall yield of the dimer is increased, and further, HNN , It is necessary to adjust the production ratio between HXN and Pxtx.

It is an object of the present invention to provide hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene by one dimerization of norbornadiene (NBD). (HNN), hexacyclo [7.2.1.0 ^2,8 . 1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene (HXN) and pentacyclo [8.2.1.0 ^{2,9 3,8} .1 ^4,7 ] tetradeca-5, It is to provide a method for economically and efficiently producing a composition in which the production rate of 11-diene (Pxtx) is adjusted to 52 to 94%, 2 to 25% and 1 to 21% by weight, respectively.

It is also an object of the present invention to control the method of adjusting the production ratio of HNN, HXN and Pxtx in the dimerization reaction product of norbornadiene (NBD) to 52 to 94%, 2 to 25% and 1 to 21% by weight, respectively. To provide.

The object of the present invention is to use a dialkylaluminum hydride as a reduction catalyst in the dimerization reaction of NBD, and to add a catalytic activity enhancer as necessary, whereby the production ratio of HNN, HXN and Pxtx is 52 to 94% by weight. , 2 to 25% and 1 to 21% in the range.

Accordingly, the present invention comprises the dimerization reaction of NBD using dialkylaluminum hydride as the reduction catalyst, wherein HNN, HXN and Pxtx are 52 to 94%, 2 to 25% and 1 to 21% by weight, respectively. It relates to a method for producing a composition containing in the range.

In addition, the present invention uses dialkylaluminum hydride as the reduction catalyst, and the ratio of HNN, HXN and Pxtx in the dimerization reaction product of NBD is in the range of 52 to 94%, 2 to 25% and 1 to 21% by weight, respectively. It is about how to adjust.

Method for producing a composition containing HNN, HXN and Pxtx in the range of 52 to 94%, 2 to 25% and 1 to 21% by weight, by one reaction for dimerizing NBD according to the present invention and NBD A method of adjusting the ratio of HNN, HXN and Pxtx in the dimerization reaction product in the range of 52 to 94%, 2 to 25% and 1 to 21% by weight, respectively.

In the present invention, instead of preparing and mixing HNN, HXN, and Pxtx, respectively, the optimized composition having the same composition as that of the three dimers prepared and mixed can be prepared in one reaction. The method for preparing the composition of HNN, HXN and Pxtx and the method for controlling the production ratio of NBD dimer are very efficient and economical.

The method for preparing the composition of HNN, HXN, and Pxtx and the method for controlling the production ratio of NBD dimer according to the present invention uses a dialkylaluminum hydride as a reduction catalyst for the dimerization reaction of NBD, It is characterized by further using.

Iron acetylacetonate (FeAA ₃ ) is used as a main catalyst for dimerization of NBD, and triphenylphosphine (TPP) is used as a product stabilizer, respectively.

The most preferred example of the dialkylaluminum hydride is diisobutylaluminum hydride (DIBAL), and the catalytic activity enhancer is preferably aluminum halide, most preferably aluminum chloride (AlCl ₃ ).

In the dimerization reaction of NBD, the reactants and catalyst are NBD 50 to 500, main catalyst FeAA ₃ 0.5 to 2, product stabilizer triphenylphosphine 1 to 10, reduction catalyst DIBAL 1 to 20, catalyst activity enhancer AlCl ₃ It is preferable to use it in the molar ratio of 0-5. It is preferable that reaction temperature is 60-100 degreeC, and reaction time is 1 to 3 hours, and toluene, tetrahydrofuran (THF), or a mixture thereof can be used as a reaction solvent.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the embodiments are only examples of the present invention, and the scope of the present invention is not limited thereto.

Table 1 below shows the reaction conditions such as the molar ratio of the reactant and the catalyst in the dimerization reaction of NBD (Comparative Examples 1 to 5) by the method of the prior art, the type of the solvent, the reaction temperature and the reaction time, and the In the dimerization reaction of NBD by the method (Examples 1 to 3), the reaction conditions such as the molar ratio of the reactant and the catalyst, the kind of the solvent, the reaction temperature and the reaction time are shown.

The dimer composition of NBD was prepared by performing a dimerization reaction of NBD according to the procedure described below under the reaction conditions shown in Table 1 above.

First, a catalyst (main catalyst, product stabilizer, reduction catalyst and / or catalytic activity enhancer) and solvent are placed in a 250 mL two-necked flask equipped with a reflux condenser under a nitrogen stream that is not in contact with air, and then a syringe or metering pump NBD was slowly injected using.

After NBD injection, the reaction vessel was heated in an oil bath under a nitrogen stream to allow the dimerization reaction of NBD to occur. When the reaction was complete, the product was washed with 1N NaHCO ₃ aqueous solution to neutralize and passed through a silica gel packed column to remove impurities.

The obtained final product was analyzed by gas chromatography (model name: Agilent 6890N, detector: FID, column: HP-5 (30m ㅧ 0.32mm ㅧ 0.25μm), oven temperature: 240 ° C), and the nucleus of the compound corresponding to the obtained peak. Magnetic resonance analysis confirmed HNN, HXN and Pxtx compounds, and calculated the composition ratio of the product by converting each peak area in weight percentage.

Comparative Examples 1 to 3 relate to a process for preparing dimer HNN, using FeAA ₃ as the main catalyst, TPP as the product stabilizer, DEAC as the reducing catalyst, and AlCl ₃ as the catalytic activity enhancer. FeAA ₃ , TPP and DEAC were used in amounts of 1 mol, 8 mol and 20 mol, respectively, and AlCl ₃ was used in the range of 0 to 2.5 mol.

Comparative Example 4 relates to a method for preparing dimer HXN, using RhAA ₃ as the main catalyst and DEAC as the reducing catalyst, using RhAA ₃ and DEAC in an amount of 1 mol and 10 mol, respectively, relative to 500 mol of NBD. Was,

Comparative Example 5 relates to a method for preparing the dimer Pxtx, using NiBr ₂ / Zn in a molar ratio of 2/15 as the main catalyst to 40 moles of NBD, and no product stabilizer, reduction catalyst or catalyst activity enhancer. .

Examples 1 to 3 relate to a method for producing a composition in which three types of NBD dimers, HNN, HXN and Pxtx, are mixed at a constant ratio, wherein FeAA ₃ is used as the main catalyst, TPP is used as the product stabilizer, and DIBAL is the reduction catalyst. Was used, with or without additional AlCl ₃ . The reactants and catalysts were used in amounts of 1 mole, 8 moles and 10 moles of FeAA ₃ , TPP, DIBAL, respectively, and 250 moles of NBD, and AlCl ₃ in the range of 0 to 2.5 moles relative to 250 moles of NBD.

Table 2 below shows the composition of the NBD dimer composition calculated from the analysis results of the product obtained by dimerizing the NBD according to the reaction conditions shown in Table 1.

As shown in Table 2, in Comparative Examples 1 to 3 using DEAC, which is a conventional reducing catalyst, the conversion rate of NBD was low as much as 90%, and the content of HNN, HXN, and Pxtx in the product according to the change in the amount of AlCl ₃ was used as a weight ratio. Respectively 73 to 75%, 6 to 9% and 9 to 10%. Therefore, this mixture has a high viscosity and low performance as lead and is not suitable for use as a high performance fuel composition. Therefore, it was confirmed that it is impossible to adjust the production | generation ratio of NBD dimer to a desired value on the reaction conditions of Comparative Examples 1-3.

In Comparative Example 4, only HNN and HXN were obtained by weight ratio of 9% and 62%, respectively, and in Comparative Example 5, only Pxtx was obtained by weight ratio of 61%. Therefore, it can be seen that it is impossible to produce a composition containing HNN, HXN and Pxtx in a desired ratio by the methods of Comparative Examples 4 and 5.

In contrast, in Examples 1 to 3 according to the present invention, the conversion of NBD was increased to 97% or more by using DIBAL instead of DEAC, and HNN, HXN, and Pxtx were respectively 52 by weight as the molar ratio of AlCl ₃ was changed. It turns out that it was produced in the range of -94%, 2-25%, and 1-21%.

Figure 1 shows the comparison of the results of Examples 1 to 3 and Comparative Examples 1 to 3. As shown in Fig. 1, in Examples 1 to 3, when the molar ratio of AlCl ₃ / DIBAL was changed to 0/10, 1/10, and 2.5 / 10, the ratios of HNN, HXN, and Pxtx in the dimer product were represented by weight ratio, respectively. 52 to 94%, 2 to 25% and 1 to 21%.

On the other hand, in Comparative Examples 1 to 3, even when the molar ratio of AlCl ₃ / DEAC was changed to 0/10, 1/10 and 2.5 / 10, the weight ratio of HNN, HXN and Pxtx in the dimer product was 73 to 75% and 6, respectively. As 9% and 9%-10, the production | generation ratio of dimer was hardly controlled.

Therefore, according to the present invention, by using FeAA ₃ as the main catalyst, TPP as the product stabilizer, DIBAL as the reduction catalyst, and the amount of AlCl ₃ used as the catalyst activity enhancer, the dimerization reaction products of NBD, HNN, HXN and It was confirmed that the generation ratio of Pxtx can be adjusted in the range of 52 to 94%, 2 to 25%, and 1 to 21%, respectively.

1 shows hexacyclo [7.2.1.0 ^2,8 .1 ^{3, which} is an NBD dimerization product according to the molar ratio of AlCl ₃ / DIBAL (Examples 1 to 3) or the molar ratio of AlCl ₃ / DEAC (Comparative Examples 1 to 3). ⁷ .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene (HNN), hexacyclo [7.2.1.0 ^2,8 . 1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene (HXN) and pentacyclo [8.2.1.0 ^{2,9 3,8} .1 ^4,7 ] tetradeca-5, The change in production rate of 11-diene (Pxtx) is expressed as weight percentage.

Claims (18)

Hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ], comprising dimerizing norbornadiene using diisobutylaluminum hydride as the reduction catalyst. Tetrades-10-ene, hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene and pentacyclo [8.2.1.0 ^2,9 .0 ^3,8 .4 ^4,7 ] The method for producing a composition containing tetradeca-5,11-diene in an amount of 52 to 94%, 2 to 25% and 1 to 21% by weight, respectively. delete The method of claim 1, further comprising using a catalytic activity enhancer. The method of claim 3, wherein the catalytic activity enhancer is aluminum halide. The method of claim 4, wherein the aluminum halide is aluminum chloride. The production method according to claim 3, wherein the molar ratio of norbornadiene to catalytic activity enhancer is 50 to 500: 0 to 5. The production method according to claim 1 or 3, wherein iron acetylacetonate is used as a main catalyst and triphenylphosphine is used as a product stabilizer. The production process according to claim 7, wherein the main catalyst: product stabilizer: reduction catalyst is set at a molar ratio of 0.5 to 2: 1 to 10: 1 to 20. The process according to claim 1, wherein toluene, tetrahydrofuran or a mixture thereof is used as the reaction solvent. The method according to claim 1, wherein the reaction temperature is adjusted to 60 to 100 DEG C and reacted for 1 to 2 hours. Hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4, ] is a dimer of norbornadiene using diisobutylaluminum hydride as a reduction catalyst for the dimerization reaction of norbornadiene ^{. 6} ] tetrades-10-ene, hexacyclo [7.2.1.0 ^2,8 .1 ^3,7 .1 ^5,13 .1 ^4,6 ] ^tetrades -10-ene and pentacyclo [8.2.1.0 ^2,9 .0 ^3,8 .1 ^4,7 ] The method of adjusting the production ratio of tetradeca-5,11-diene in the range of 52 to 94%, 2 to 25% and 1 to 21% by weight. delete The method of claim 11, further comprising using a catalytic activity enhancer. The method of claim 13, wherein the catalytic activity enhancer is aluminum halide. The method of claim 14, wherein the aluminum halide is aluminum chloride. The method according to claim 13, wherein the molar ratio of norbornadiene to catalytic activity enhancer is 50 to 500: 0 to 5. The process according to claim 11 or 13, wherein iron acetylacetonate is used as the main catalyst and triphenylphosphine is used as the product stabilizer. 18. The process according to claim 17, wherein the main catalyst: product stabilizer: reduction catalyst is in a molar ratio of 0.5 to 2: 1 to 10: 1 to 20.

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