JPS6228129B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for purifying a 1,3-diene oligomer reaction product liquid.

BACKGROUND OF THE INVENTION Catalytic oligomerization of 1,3-dienes is usually carried out in solution in the presence of a Ziegler-type catalyst (a catalyst system consisting of a combination of a transition metal compound and a reducing metal compound); There are halogens and fine solids caused by the catalyst, and their separation and removal and recovery of the oligomer solution are problems.

As a prior art, for example, a method of adding anhydrous ammonia and (1) subsequently distilling it (Japanese Patent Publication No. 44)
-15773), (2) A method of treatment with a purifying agent such as nitrogen or phosphorus compounds while blowing oxygen (Special Publication No. 15773).
8265) and (3) monoethanolamine (preferably pure, but may contain small amounts of di- or tri-ethanolamine or ammonia or water) in a non-oxidizing atmosphere. There is a method of treating and then washing with water (Japanese Patent Publication No. 52-6962). In (1), the remaining polymer after distillation is contaminated with halogen, which causes problems such as the use of the remaining polymer and corrosion of the equipment, and in (2), fine solids are precipitated due to reaction with the purifying agent. However, since this remains in the oligomer solution even after distillation, it affects the final product. It also remains in the pot residue polymer, posing a problem in its utilization. (3) has a significantly reduced halogen content compared to the former two and does not produce fine solids, but because the molecular weight and degree of association of the reaction product between monoethanolamine and catalyst are small, it will be dispersed in the reaction product liquid. , washing with water is essential. In addition, the boundary between the aqueous layer containing catalyst residue and the oligomer solution layer after washing with water is not clear, and the intermediate layer (a cloudy layer formed by mixing the oligomer solution layer and the aqueous layer containing catalyst residue)
exists to a large extent. Since this intermediate layer also contains some catalyst residue, if the intermediate layer is not completely removed, it will cause contamination of the subsequent heat distillation column, etc. Therefore, the recovery rate of the oligomer solution was 83 to 87%, which could hardly be said to be satisfactory (see Comparative Example 1 below).

SUMMARY OF THE INVENTION The present inventors have solved the various problems mentioned above, obtained an oligomer solution with extremely low halogen content at an extremely high recovery rate, and also made it possible to effectively utilize the residue in the pot, thereby reducing the corrosion of equipment, etc. We have established a method for purifying 1,3-diene oligomers free of 1,3-diene oligomers.

That is, in the present invention, a halogen-containing 1,3-diene oligomer reaction product solution based on catalyst residue is mixed with triethanolamine alone 0.1 to 50 times the weight of the catalyst, or a triethanolamine or diethanolamine 0.1 to 50 times the weight of the catalyst. b A mixture consisting of one or more of an acyclic aliphatic hydroxy compound, monoethanolamine, or water, 0.1 to 5 times the weight of the catalyst [However, component a is always used in a larger amount than component b] a' Monoethanolamine 0.1 times the weight of the catalyst A mixture consisting of ~50 times the weight of the catalyst and b' glycerin 0.1 to 5 times the weight of the catalyst [However, the a' component is always used more than the b' component]. The present invention provides a method for purifying 1,3-diene oligomers, which is characterized by reducing the halogen content in the 1,3-diene oligomer to 6 ppm or less.

Detailed Description of the Invention 1 1,3-Diene Oligomer Reaction Product Liquid This is the liquid to be purified of the present invention, and contains the following components.

B 1,3-diene oligomer All 1,3-diene oligomers that can be oligomerized are targeted, but 1,3-diene oligomers are applicable.
-butadiene or homo- or cooligomers of lower alkyl (especially methyl) substituted 1,3-butadiene (eg isoprene, 1,3-pentadiene, etc.) are particularly suitable. The degree of polymerization is usually about 2 to 10, particularly 2 to 3, and the oligomer may be chain or cyclic.

Specifically, for example, 1,3,7-octatriene is used as a chain dimer of 1,3-butadiene, 4-vinylcyclohexene-1 is used as a cyclic dimer, and cyclododecatriene-1,5 is used as a cyclic trimer. ,9, cyclododecatriene-1,6,9 is converted into 2,6-dimethylocta-1,3,7- as a chain dimer of isoprene.
Triene, 2,4-dimethyl-4-vinylcyclohexene-1 as a cyclic dimer, 1,6,9-trimethylcyclododecatriene-1,5,9,1,5,9-trimethylcyclo as a cyclic trimer Dodecatriene-1,5,9
However, as a cyclic cotrimer of butadiene and isoprene or piperylene, 1-methylcyclododecatriene-1,5,9,1,5
-dimethylcyclododecatriene-1,5,
9 are listed.

(b) Oligomerization catalyst residue The catalyst according to the present invention generally belongs to the category of Ziegler-type catalysts, and contains a transition metal compound component (a) and a reducing metal compound (b) as shown below. Electron-donating compounds depending on
It consists of a combination with (c). It is thought that the reaction product liquid contains residues of these two components and their complex combinations or decompositions.

a Transition metal compound component represented by the general formula MXnYn' or MOlXl'.

M = titanium, zirconium, nickel,
Iron, cobalt or chromium, etc. X = halogen Y = alkoxy group, chloroalkoxy group,
Acetylacetonate group, organic acid group, etc. n, n' = integer of 0 to 4 l, l' = integer of 1 to 2 b Reducing metal compound component Those represented by the general formula AlR'mX _3-n .

R′ = alkyl group or aryl group These are usually aromatic hydrocarbons such as benzene, toluene, and xylene, or aliphatic hydrocarbons such as hexane and heptane.

2 Purification Agent The purification agent of the present invention can take the above embodiments.

It is believed that diethanolamine or triethanolamine reacts with the transition metal compound and the reducing metal compound to form a characteristic complex, thereby deactivating the excess catalyst and causing it to precipitate.

The amount of diethanolamine or triethanolamine used is 0.1 to 0.1 of the amount of the catalyst system (transition metal compound component + reducing metal compound component) used.
50 times the weight, preferably 0.5 to 5 times the weight.

Acyclic aliphatic hydroxy compounds are monohydroxy, dihydroxy or trihydroxy compounds having 1 to 12 carbon atoms in which the carbon chain may have an oxygen link therebetween, such as methanol, ethanol, butanol, octanol, decanol,
ethylene glycol, diethylene glycol,
These include propylene glycol, dipropylene glycol, 1,5-pentanediol, 1,3-hexanediol, glycerin, 1,2,6-hexanetriol, trimethylolpropane, and pentaerythritol.

These hydroxy compounds and monoethanolamine not only oxidatively decompose the catalyst, but also increase the specific gravity and fluidity of the catalyst decomposition residue layer. Monoethanolamine alone suppresses the formation of fine powder in the oligomer solution layer. It is difficult.

The amount of component b and component b' used is about 0.1 to 5 times, preferably about 0.5 to 5 times, the amount of the catalyst system used in the oligomerization reaction.

3. Treatment A purifying agent is added to the 1,3-diene oligomer reaction product liquid to be purified, and the mixture is stirred at a predetermined temperature for a predetermined time. Temperature is 0~200℃, preferably 10~100℃
°C, stirring time is 0.5~10 hours, preferably 0.5~
It is 3 hours. The pressure may be normal pressure to pressurized. However, in the case of normal pressure treatment, the treatment temperature is
If the boiling point is higher than that of the solvent or purification material, it may be necessary to use a device equipped with a reflux condenser.

The treatment may be carried out in either an oxidizing or non-oxidizing atmosphere, but in order to shorten the treatment time, an oxidizing atmosphere such as air bubbling is preferred.

4 Separation and recovery of oligomer solution By allowing the solution obtained by the above treatment to stand still, the boundary between the upper layer of transparent oligomer solution layer and the lower layer of highly fluid catalyst residue layer is clearly separated, and the middle layer is separated. Virtually non-existent.

Thereafter, the bottom is extracted, the catalyst residue layer is separated by decantation, etc., and the oligomer solution is recovered.

The separated oligomer solution is subjected to an oligomer and solvent recovery process such as distillation.

Effects of the Invention Diethanolamine and triethanolamine, which are the purifying agents of the present invention, have a large molecular weight and are polyfunctional, so they have high reactivity with catalyst residues. It is therefore considered that the molecular weight of the formed complexes also increased, making them easier to settle.

Furthermore, by adding component b, it helps diethanolamine and triethanolamine, completes the catalyst decomposition, and improves the dissolution and dispersibility of diethanolamine and triethanolamine in the reaction product solution, so that decomposition and purification can be carried out smoothly and in a short time. It will be held in In addition, since the b and b' components contract the volume of the formed complex, the (b, b') components bond with the complex through their OH groups or hydrogen bonds due to the OH groups, and furthermore through intermolecular bonds. It is thought that this phenomenon occurs and the morphology of the molecules becomes denser. ) There is no loss due to impregnation of the oligomer solution into the decomposition residue, and the fluidity of the decomposition residue is improved. As a result, it is thought that the interface between the oligomer solution and the catalyst residue layer became clear, no intermediate layer was formed, and separation became easier. Needless to say, there is no need for a washing process.

Experimental Examples Example 1 A 0.5 reactor equipped with a stirrer, a reflux device, and a heating device was prepared.

Next, as a catalyst system, a reaction product solution obtained by trimerizing butadiene (toluene = 70 gr, cyclododecatriene = 26g, others = 4g) 100g was put into the above reactor.

Next, add 1 ml of triethanolamine and 0.5 ml of propylene glycol, and heat at approximately 100°C for 30 minutes for 200 min.
The treatment was carried out under the conditions of revolutions/minute.

When stirring was stopped and the mixture was allowed to stand for 3 hours, the upper, colorless and transparent oligomer solution layer and the lower, viscous catalyst residue layer were clearly separated. Decantation yielded 97 g of oligomer solution (97% recovery). The chlorine content of the obtained oligomer solution was 6 ppm. Since the content before purification was 1300 ppm, it can be said that the catalyst was almost completely removed.

Example 2 In the same reactor as in Example 1, isoprene was dimerized using a catalyst system of diethylaluminum chloride, ethylenediamine, and titanium tetrachloride prepared in a molar ratio of 5:1:1, respectively. reaction product solution (toluene = 70
g, 2,6-dimethyloctatriene-1,3,
6 = 15g, 1,4-dimethyl-4-vinylcyclohexene-1 = 11g, and others = 4g).

Next, 2 ml of triethanolamine and 0.5 ml of water were added, and the mixture was stirred at room temperature for 1 hour at 200 rpm, and then air was bubbled while stirring for 3 hours.

As a result, the colorless and transparent oligomer solution layer and the catalyst residue layer were clearly separated, and the chlorine content of the oligomer solution obtained by decantation was 4 ppm, and the amount recovered was 96 g (recovery rate 96%).

Example 3 In the same reactor as in Example 1, diethylaluminum chloride, triphenylphosphine and titanium tetrachloride were added as catalyst systems in a ratio of 5:1:1, respectively.
A reaction product solution obtained by trimerizing a mixed monomer of butadiene and pentadiene (molar ratio 1:0.6) using a solution prepared with a molar ratio of (toluene = 70g, methylcyclododecatriene = 26g,
Other 4g) 100g was added.

Next, 2 ml of triethanolamine and 0.5 ml of monoethanolamine were added, and the treatment was carried out under the same conditions as in Example 1.

As a result, the colorless and transparent oligomer solution and the catalyst residue layer were clearly separated, and upon decantation,
The chlorine content of the obtained oligomer solution was 3 ppm,
The amount recovered was 98 g (recovery rate 98%).

Example 4 In the same reactor as in Example 1, butadiene was produced using a catalyst system of triethylaluminum, nickel acetylacetonate and tetraphenyldipropylene glycol diphosphite prepared in a molar ratio of 3:1:1. 100 g of the reaction product solution obtained by dimerization (toluene = 70 g, cyclooctadiene = 24 g, vinylcyclohexene = 2 g, others = 4 g) was added.

Next, 2 ml of diethanolamine and 1,5-
Add 0.5ml of pentanediol and heat at 50℃ for 2 hours.
The treatment was carried out at 200 revolutions/minute, and the mixture was further stirred with air bubbling for 1 hour, and then left to stand for 1 hour.

As a result, a colorless and transparent oligomer solution layer and a catalyst residue layer were clearly separated. The amount of recovered oligomer solution obtained by decantation was 97 g (recovery rate 97%), and the chlorine content was 3 ppm.

Example 5 In the same reactor as in Example 1, a catalyst system containing zirconium tetraoctate, allyl iodide, triphenylphosphine, and diethylaluminium chloride in a molar ratio of 1:1:2:15 was used. , 124 g of a reaction product solution obtained by dimerizing isoprene (toluene = 70 g, dimethyl octatriene = 43 g, and others 11 g) were added.

Next, 3 ml of monoethanolamine and 1 g of glycerin were added, and the mixture was treated at 70° C. for 3 hours at 200 revolutions/minute, and then allowed to stand for 1 hour.

As a result, the colorless and transparent oligomer solution layer and the catalyst residue layer were clearly separated. The halogen content of the oligomer solution obtained by decantation is
The amount recovered was 118 g (95% recovery rate).

Example 6 In the same reactor as in Example 1, a catalyst system containing trisacetylacetonatochrome (), tin tetrachloride, phenothiazine and triethylaluminum prepared in a molar ratio of 1:1:1:10 was used. 135 g of a reaction product solution obtained by cyclic trimerization of isoprene (70 g of toluene, 53 g of trimethylcyclododecatriene, and 12 g of others) was added.

Next, add 5 ml of triethanolamine and leave at room temperature (25°C) for 3 hours while bubbling air.
The process was carried out at 200 revolutions/min and then left overnight.

As a result, the colorless and transparent oligomer solution layer and the catalyst residue layer were clearly separated, and 131 g (recovery rate: 97%) of the oligomer solution was obtained by decantation. The chlorine content was also as low as 5ppm.

Comparative example [Unexamined Japanese Patent Publication No. 47-42605
Example 1] Using the same reactor and the same reaction product liquid as in Example 1, 0.37 g of monoethanolamine and 0.37 g of sodium hydroxide were added as purifying agents, and the process was carried out at 97°C for 2 hours at 1000 revolutions/min. I went to

Then add 37ml of water to this solution and heat at 87℃ for 30 minutes.
The solution was washed with water at 1000 revolutions/min.

Although the stirring was stopped and the mixture was allowed to stand for 5 hours, a cloudy white layer was present between the oligomer solution layer and the catalyst residue layer, which was a mixture of both layers. By decantation, 86 g of oligomer solution (recovery rate: 86%) was obtained.

Claims (1)

[Claims] 1. 1,3 containing halogen based on catalyst residue
- Diene oligomer reaction product liquid, triethanolamine alone 0.1 to 50 times the weight of the catalyst, or a) triethanolamine or diethanolamine 0.1 to 50 times the weight of the catalyst, and b acyclic aliphatic hydroxy compound, monoethanolamine, or water. A mixture consisting of one or more 0.1 to 5 times the weight of the catalyst [However, component a is always used more than component B] a' monoethanolamine 0.1 to 50 times the weight of the catalyst and b' glycerin 0.1 to 5 times the weight of the catalyst [However, the a' component is always used in a larger amount than the b' component.] The halogen content in the 1,3-diene oligomer is reduced to 6 p.pm or less by treatment with a purifying agent selected from the above. A method for purifying 1,3-diene oligomer.