JPH0825920B2 - Method for deactivating cyclododecatriene-1,5,9 catalyst - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a catalyst used in the production of cyclododecatriene-1,5,9 (hereinafter referred to as cyclododecatriene) from 1,3-butadiene. It relates to a method of deactivating a catalyst without losing dodecatriene. Cyclododecatriene-1,5,9 is a raw material widely used as a useful intermediate raw material in the chemical industry and petrochemical industry such as resin, plasticizer, adhesive or polyester. In addition, this cyclododecatriene is useful as an intermediate raw material of nylon-12 produced by hydrogenation to produce cyclododecan, mainly via lauryllactam, and is also a flame retardant, polyamide, polyurethane, synthetic fragrance. It is useful as a raw material.

[0002]

2. Description of the Related Art Trimerization of 1,3-butadiene as a raw material with a mixed catalyst of titanium halogenide and alkylaluminum halogenide (commonly called Ziegler-Natta catalyst),
To produce cyclododecatriene-1,5,9,
It is known (German Patent No. 1050333). It is difficult to distill off cyclododecatriene-1,5,9 from the reaction solution obtained by this production industrially immediately. This is because it is not industrially possible to separate and purify in this state because organometallic aluminum, which is an extremely highly active catalyst, is highly concentrated, and there is a risk of ignition and explosion. Therefore, it is necessary to deactivate the active catalyst before distillation / separation.

In this deactivation method, it is generally known that the catalyst is decomposed by adding water or alcohol, which is a compound containing an active hydrogen atom. However, when the reaction liquid containing the Ziegler-Natta catalyst and the produced cyclododecatriene-1,5,9 is decomposed with water,
At the same time as deactivation of the catalyst, cyclododecatriene-1,5,9
However, there is a problem that the yield decreases if the catalyst used is decomposed and deactivated with water. Further, in the case of deactivating with alcohol or the like, there is a problem that the equipment for industrially recovering and reusing alcohol becomes complicated and the equipment cost becomes expensive.

Japanese Patent Publication No. 38-6468 describes that, as a pretreatment, a small amount of an organic substance having an electron pair, such as ketone, ether, ammonia or ester, is added and then deactivated with water or alcohol. The addition of the substance in two steps to deactivate the reaction solution, and then the addition of water will form a heterogeneous phase, which not only complicates the deactivation operation, but also increases the amount of organic matter added. There is a problem that a material recovery process is required, the apparatus becomes complicated, and the equipment cost becomes high.

Further, in Japanese Patent Publication No. 52-4541, the catalyst is deactivated with aqueous concentrated ammonia. However, in the case of a liquid containing a relatively large amount of polybutadiene as a reaction by-product, addition of aqueous concentrated ammonia causes precipitation of fine particles. However, there are drawbacks such as formation of a liquid phase and poor interfacial separation, and the state of precipitation formation is not reproducible, which is a problem for industrial operation.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to cyclododecatriene-1,5, which is obtained by trimerizing 1,3-butadiene.
In a method for deactivating a catalyst from a mixed solution containing 9,
It is intended to provide a treatment method for deactivating a reproducible catalyst without losing cyclododecatriene-1,5,9.

[0007]

Means for Solving the Problems The present inventor has diligently studied the above problems, and has earnestly studied an operation method for deactivating in a short time without loss of cyclododecatriene as a target product. , It was found that a compound which is well miscible with water and which forms an adduct with organometallic aluminum may be added and treated with water, and a reaction containing cyclododecatriene-1,5,9 after completion of the reaction It has been found that the catalyst can be deactivated without loss of cyclododecatriene-1,5,9 by contacting with a mixture of water containing a compound forming an adduct with organometallic aluminum in the mixed solution. Was completed.

The present invention is a reaction for producing cyclododecatriene-1,5,9 by trimerization of 1,3-butadiene in an inert solvent using a Ziegler-Natta catalyst in a mixture after completion of the reaction. A method for deactivating a cyclododecatriene-1,5,9-producing catalyst, which comprises deactivating the catalyst by adding a mixed solution containing water to the organometallic aluminum-containing compound which forms an adduct. .

The Ziegler-Natta catalyst used in the present invention is a mixed catalyst of a halide of a transition metal such as titanium, nickel, iron and chromium or a salt of an organic compound and an alkylaluminum halide. Specific examples of metal salt compounds include titanium tetrachloride, titanium trichloride, nickel chloride, iron trichloride, nickel acetate, nickel acetylacetonate, and tetraethoxy titanium. On the other hand, examples of the alkyl aluminum halide include diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride and the like.

As the inert solvent used in the trimerization of butadiene, a Ziegler-Natta catalyst and a saturated aliphatic hydrocarbon having 5 to 12 carbon atoms and an aromatic solvent which does not react with butadiene or the product cyclododecatriene are used. Use hydrocarbons. Specific solvents include benzene,
Toluene, pentane, hexane, heptane, octane,
Nonane, decane, undecane, dodecane, etc. are mentioned.

Further, the compound which is well miscible with water and forms an adduct with organometallic aluminum is a compound containing a phosphorus compound such as phosphine or sulfur in addition to a compound having an ether or a cyano group, and is easily mixed with water. Any compound that is mixed with

Specific compounds include cyclic ethers such as tetrahydrofuran and 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol,
Aliphatic ethers such as dimethyl ether, diethylene glycol, diethyl ether, trimethylamine, triethylamine, tris-hydroxypropylamine,
Ammonia compounds such as diethylenetriamine, N,
Examples thereof include acid amides such as N-dimethylformamide, aromatic nitrogen-containing compounds such as pyridine, piperidine and piperazine.

Examples of the compound having a cyano group include aliphatic nitriles such as acetonitrile, propionitrile and adiponitrile, and aromatic nitriles such as benzonitrile. Further, phosphorus compounds such as triphenylphosphine and triethylphosphine, and sulfur compounds such as diethyl thioether, dimethyl sulfoxide and diethyl sulfoxide can be mentioned. The amount of these compounds may be 0.1 times or more the molar amount of the Ziegler-Natter catalyst used, but preferably 0.2 to 1.0 times the molar amount is desirable. If it is lower than this value, cyclododecatriene is polymerized and converted into a by-product, which deteriorates the yield. In addition, if the addition amount is large, it is economically disadvantageous including the recovery step.

The amount of water contained at the same time must be 3.0 times or more the mole of the catalyst, and preferably 3.3.
It is preferably -10.0 times by mole. If it is lower than this value, the decomposition of the catalyst becomes insufficient and a part of the catalyst remains in the organic phase, which is not preferable. Further, when it is high, not only cyclododecatriene is lost but also it may be separated into two phases, which is not preferable.

As the reaction conditions for deactivating the catalyst used in the reaction mixture, the reaction temperature is optimally room temperature to 90 ° C., preferably 50 to 70 ° C., and when the temperature is low, there is no reproducibility and at high temperature. Is not preferable because the solvent volatilizes.
As the reaction pressure, conditions from atmospheric pressure to pressurization are selected.
The reaction time varies depending on the temperature, pressure, and amount of solvent, but 0.1 to 1 hour is preferable if mixing is performed with sufficient stirring.

The method according to the present invention can be carried out batchwise or continuously, and the deactivated catalyst can be removed from the system after the usual filtration / separation operation. Further, the produced cyclododecatriene can be separated and purified by a known distillation unit operation.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples.
The present invention is not limited to this. Next, examples and comparative examples of the present invention will be shown. Examples 1 to 12 A magnetic rotor was placed in a 100 ml two-necked eggplant-shaped flask equipped with an argon gas blowing tube, and dehydrated toluene 10 was added at room temperature under atmospheric pressure while sufficiently purging with argon.
Add ml. Next, commercially available cyclododecatriene-
1,5,9 10cc (8.85g; 54.6mmo
l) In addition, 2 cc of a toluene solution (0.5 mmol / ml) containing diethylaluminum sesquichloride and a toluene solution (0.05 mmol) containing titanium tetrachloride.
/ Ml) 1 cc was added and stirred.

A solution 0.2 consisting of 0.7 mmol of tetrahydrofuran (abbreviated as THF) and 8 mmol of water is added to this system.
After adding 20 ml and stirring at 200 rpm for 20 minutes, a part of the sample was sampled and analyzed by gel permeation chromatography (GPC). As a result, there was no loss with respect to the initial charge of cyclododecatriene, and the recovery rate was 100%. Of cyclododecatriene-1,5,9. Hereinafter, various compounds for deactivating were added and the same operation was performed. The results are shown in Table 1.

[0019]

[Table 1]

Comparative Examples 1 to 6 Comparative Example 1 was carried out under the same reaction conditions as in Example 1 except that the solvent, catalyst and cyclododecatriene-1,5,9 were charged. Add 0.2 cc of water to this system and apply 200 r for 20 minutes.
When stirring at pm, heat generation and foaming occurred, and white turbidity occurred. When I sampled a part and analyzed GPC,
The recovery rate of cyclododecatriene-1,5,9 is 81%.
It was found that a part of the polymer was polymerized. Further, Comparative Examples 2 and 3 are examples in which the amount of the added organic compound for deactivating was decreased. Comparative Examples 4 and 5 show examples in which the amount of added water for deactivating is increased, and Comparative Example 6 shows an example in which the additive for deactivating is added only to water to the actual reaction liquid. It was The recovery rate of all the comparative examples deteriorated. The results are shown in Table 2.

[0021]

[Table 2]

Examples 13 to 15 0.74 g (3.5 mmol) of ethylaluminum sesquichloride and 47.4 mg (0.25 mmol) of titanium tetrachloride were added to 200 rp in 100 ml of dehydrated toluene.
It is dissolved with stirring at m, the temperature is raised to 60 ° C., and butadiene is mixed at 15 to 16 l / hr while maintaining the temperature at 60 ° C. After 2 hours, stirring was stopped, and after cooling, a part of sampling was conducted by GPC analysis and gas chromatography analysis to find that the reaction of cyclododecatriene yield 91%, polymer compound 8%, dimer and other mixture 1% A liquid was obtained.

THF was added to this reaction solution under the same conditions as in Example 1.
0.53 solution consisting of 2.4 mmol and 28 mmol of water
After adding ml and stirring, the same analysis as above was performed, but there was no loss of cyclododecatriene. Then, various compounds for deactivating were added and the same operation was performed. The results are shown in Tables 1 and 2.

Claims (1)

[Claims] 1. In a reaction for producing cyclododecatriene-1,5,9 by trimerization of 1,3-butadiene in an inert solvent using a Ziegler-Natta catalyst, organic matter in the mixture after the reaction is completed. A method for deactivating a cyclododecatriene-1,5,9-producing catalyst, which comprises deactivating the catalyst by adding a mixed liquid containing water to a compound forming an adduct with metallic aluminum.