JPS581972B2 - Laxane methyl - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid aluminum chloride catalyst solutions, and more particularly to liquid aluminum chloride catalyst solutions that exhibit excellent controllability, uniformity and reproducibility, and are stable and pumpable liquids over long periods of time. It concerns an aluminum catalyst solution.

As is well known to those skilled in the art, aluminum halides, particularly aluminum chloride and aluminum bromide, have been proposed as Lewis acids to catalyze many reactions including polymerization, alkylation and isomerization.

Aluminum chloride and aluminum bromide are solids;
On the other hand, since the reactants are liquids, it has been difficult to control the reaction and obtain reproducible results.

For example, polymerization of olefins is carried out in several ways.

Those methods have disadvantages. (a) Adding all the olefin to the catalyst results in an uncontrollable, exothermic reaction.

(b) Adding the olefin gradually to the catalyst causes the catalyst concentration to change during operation.

This has a negative impact on reproducibility.

(c) Metering the catalyst and olefin in appropriate proportions into the reactor.

However, the problem of metering solid materials makes it difficult to maintain the desired proportions of catalyst and olefin.

Another drawback generally associated with all such methods is the difficulty in uniformly contacting the solid catalyst and the liquid olefin.

On the other hand, if both catalyst and reactants are liquids, uniform contact is obtained and accurate metering is easily achieved.

Thus, the difficulties encountered in using solid aluminum chloride or bromide can be substantially eliminated if the aluminum chloride or bromide is obtained in a catalytically active liquid form.

Aluminum chloride is mixed with various solvents such as alcohols,
Kokichi has been proposed to dissolve (or complex) in ethers and methyl acetate.

However, in those cases less than 1 mole of aluminum chloride is dissolved per mole of solvent.

Solutions with such molar ratios are not catalytically active.

FR 1,433,373 discloses that catalyst solutions containing one or more moles of aluminum halide dissolved in certain esters can be used in the polymerization of olefins and that such solutions are It is disclosed that it can be recycled to the next run.

It has also been proposed to isomerize n-penkune by using AlCl3 dissolved in ethyl acetate to quench the reaction product and reuse the catalyst solution in the next run (Ind. & Eng. Chem. .42 ,3
42 (1950)).

In both the polymerization recycle operation and the isomerization recycle operation described above, the solvent is ethyl acetate;
It was only carried out for less than 4 hours.

As a result of the pilot plant implementation, the AICI3-ethyl acetate catalyst solution was heated to 20-25°C due to the evolution of HCl.
It was found that it decomposes into a hard solid at a temperature of .

Therefore, the catalyst solution could not be recycled for extended periods of days or months.

Solutions of aluminum halides in ethyl propionate are described in French Patent No. 1,433,373.

However, although solutions of more than 1 molar aluminum halide in ethyl propionate remain liquid and stable over long periods of time, they have the disadvantage of rapidly increasing viscosity over time.

For example, the viscosity of a solution doubles in less than two days at 38°C.

When using such solutions, the increased viscosity makes accurate metering difficult and, more importantly, requires greater pumping power (pumpability is reduced).

) Of course, such factors reduce the efficiency of processes using such catalyst solutions.

The present inventor has discovered that n-monobutyric acid, n-valeric acid, n-hexanoic acid,
i Monovaleric acid, trimethylacetic acid, 2-methylvaleric acid, 2-
It has been discovered that methyl esters of ethylbutyric acid and 2-ethylhexanoic acid can be used to form aluminum halide catalyst solutions that do not suffer from the disadvantages of viscosity changes and processing difficulties.

In general, the present invention comprises n-monobutyric acid, n-monobutyric acid, n-monobutyric acid, n-monobutyric acid, dissolved in an amount of at least 1 mole of aluminum chloride per mole of methyl ester.
- a stable liquid aluminum chloride catalyst solution characterized in that it consists of a methyl ester of valeric acid, n-hexanoic acid, ivaleric acid, trimethylacetic acid, 2-methylvaleric acid, 2-ethylbutyric acid, or 2-ethylhexanoic acid; It provides:

The diagram shows the kinematic viscosity at 100°F and 1.3 moles of A dissolved in the ethyl probionate, methyl n-butyrate, methyl n-monovalerate, and methyl n-hexanoate products.
1 is a curve on a semi-logarithmic scale showing the relationship between ICl3 and the number of days of storage of a solution.

The solution of the invention is a solution or complex of aluminum chloride in the methyl ester described above.

The solution contains at least 1 mole of aluminum chloride per mole of ester.

Preferably, the amount of aluminum chloride dissolved in one mole of ester is about 1.1 to 1.4 moles.

A 1 molar solution is not useful as it has little or no catalytic activity as a Lewis acid.

The 1 molar excess of aluminum chloride in the solution is believed to be the component that imparts catalytic activity to the solution.

The amount of solution used to catalyze the reaction in this way is governed solely by the need to provide a sufficient excess (1 mole or more) of aluminum chloride, which is usually catalyzed by solid aluminum halide. 1. to exert a catalytic effect on the desired reaction similar to 1. A solution of aluminum chloride in ester is easily formed.

This solution or complex is easily formed at room temperature.

Additional aluminum chloride can be dissolved in this solution at a temperature of 30-50°C.

In order to avoid hydrolysis due to moisture, it is preferred to make the catalyst solution in a dry inert atmosphere, such as nitrogen or dry air.

The solvent esters used in this invention are methyl esters of certain alkanoic acids.

The esters used are the methyl esters of n-butyric acid, n-valeric acid, n-hexanoic acid, i-valeric acid, trimethylacetic acid, 2-methylvaleric acid, 2-ethylbutyric acid, and 2-ethylhexanoic acid.

As noted above, the solutions of the present invention can be used to catalyze any reaction normally catalyzed by solid aluminum chloride.

Such reaction and operating conditions are well known in the art.

Included are alkylation of aromatic compounds with olefins or aliphatic halides, hydration of olefins and isomerization of paraffins.

The invention is particularly preferably used for the alkylation of isoparaffins and the polymerization of olefins.

Of particular interest is the use of the solutions of the present invention in the recycling of the solutions as catalysts to continuously polymerize olefins into liquid polymers useful as synthetic lubricants.

The use of the solution of the present invention will be explained with respect to polymerization.

A wide variety of olefins can be polymerized by the stable catalyst solutions of this invention.

Generally, olefins have about 2 to 25 carbon atoms per molecule, and may be straight or branched, with or without aromatic ring substituents.

The preferred olefin is 1-olefin, but olefins with internal double bonds are used.

The olefin reactant can be a single olefin or a mixture of olefins.

The following substances are examples.

Ethylene, butene-1, isobutene, hexene, octene-2,2-ethyl\xene-1, decene-2, decene-1, undecene-1, dodecene-1, hexadecene-1, occudecene-1, occudecene-9, eicosene , trichosene-1, tetracosene-1, and triacontene-1.

Polymerization is carried out at a temperature of about 0 to io o C for about 1 to 3 hours.

Polymerizations are usually carried out at substantially atmospheric pressure, although superatmospheric pressures sufficient to maintain a liquid phase may be advantageously used, particularly in the case of low density olefins.

Generally, the amount of catalyst used is about 1 to 5 parts by weight of olefin based on excess aluminum chloride.

In some cases, inert solvents can be used in the polymerization to reduce the viscosity of the polymer product and make it more easily processed.

Suitable solvents include kerosene and paraffins, e.g.
Included are heptane, octane, isooctane, decene, and the like.

Since the catalyst solution of the present invention is a heavy liquid, the effluent from the reactor is left undisturbed and the main amount of catalyst solution is separated as a heavy lower layer.

Alternatively, centrifugal force can be used to speed up the separation.

Recirculate the above layer with fresh aluminum chloride if necessary.

The remaining polymer product can then be washed free of residual catalyst solution, dried, and distilled free of solvent and monomer.

The present invention will be further illustrated by the following examples and reference examples.

Reference Example 1 A series of solutions were prepared by dissolving AlCl3 in various esters at a molar ratio of 1.32 mole AICl3 per mole ester, using temperatures slightly above room temperature if necessary. Had made.

The physical state of each solution (or mixture), i.e. AIC
The state at 1 hour and 24 hours after addition of l3, i.e. liquid (L), solid (S), liquid + solid (L + S
) was observed at room temperature.

In the case of a single effective solvent, ie ethyl probionate, observations were also made after one month.

Table 1 below shows the data obtained.

As is clear from Table 1, when AICl3 was dissolved in various ester solvents other than the methyl ester solvent used in the present invention, ethyl zolopionate had the best solution stability.

However, solutions of aluminum chloride in ethyl propionate rapidly increase in viscosity over time (e.g.
It has the disadvantage that it doubles in less than two days at 8°C.

Example 1 A series of solutions were made by dissolving AICl3 in various esdels at a molar ratio of 13 moles AICl3 per mole ester, using temperatures slightly above room temperature when necessary. .

The initial physical appearance of each solution was observed at room temperature.

What was liquid was observed periodically.

The times listed in Table 2 indicate the length of time each solution was observed and the physical state at that time, and do not indicate that the solution became unstable at that point.

As is clear from the results in Table 2, ester solvents other than methyl ester either do not dissolve AICl3 or the stability of the resulting solution is poor (ethyl propionate has poor stability as described in Reference Example 1). Although there are no particular difficulties, the disadvantage is that the viscosity of the solution changes significantly over time).

In addition, even if it is a methyl ester, methyl propionate (
It can be seen that those outside the scope of the present invention) cannot form a solution.

Change in Viscosity on Storage As mentioned above, the change in viscosity during storage of solutions of aluminum chloride in methyl n-butyrate and methyl n-monovalerate is relatively small over long periods of time.

On the other hand, the viscosity of solutions in ethyl propionate changes quite significantly within a relatively short time.

This is shown below. Examples 2-5 Four AICl3 solutions were made, each in a different n-fatty acid ester.

Each solution contains 1.3 moles of AICl3 per mole of ester.

The esters used are shown in Table 3.

Each solution was stored at 100°F for several days and the kinematic viscosity at 100°F was measured periodically (ASTM D445).

The results obtained are shown in Table 3.

Based on the data listed in Table 3, a curve showing the change in kinematic viscosity over time is plotted.

1.3 moles of AICl3 per mole of ethyl propionate
(curve A), a solution of 1.3 mol of AIC13 per mol of methyl n-monobutyrate (curve B), methyl n-valerate 1
A solution of 1.3 mole AICI3 per mole (curve B) and 1.3 mole AI per mole of methyl n-hexanoate.
Kinematic viscosity (IO
A curve plotted on a semi-logarithmic scale showing the relationship between time (in days) and time (in days) is shown in the figure.

By looking at these curves, the viscosity of the solution in ethyl propionate increases rapidly, whereas the viscosity of the solution in methyl ester changes relatively little.

For example, the viscosity of an ethyl propionate solution is approximately 8
．． It increased from 5 cs to about 585 cs.

On the other hand, the viscosity of the n-methyl butyrate solution is approximately 1 after 5 days.
The thickness increases only slightly from 0cs to about 11cs.

Therefore, the pumpability becomes even worse in order to move the solution into a recirculation operation.

Aluminum halide solutions in ethyl propionate cannot be used for extended periods without increasing pumping power.

On the other hand, methyl n-monobutyrate, methyl n-valerate, and n-
The solution in methyl hexanoate is pumpable.

This makes process operation more efficient.

Prior to the present invention, applications similar to the present invention indicate that the acid portion of the ester solvent must be a normal acid.

However, as noted above, it was generally believed that branched chain acids were not effective, but certain branched acid esters have been shown to be effective and stable pumpable solvents. Understood.

This will be clear from the examples below.

Examples 6-10 Five AICls, each in a different branched fatty acid ester
Three solutions were made.

Each solution contained 1.3 moles of AICl3 per mole of ester.

The esters used are shown in Table 4.

Store each solution at 100°F for the number of days listed in Table 4;
The kinematic viscosity (KV) at 100°F was measured periodically (ASTM D445) and the results obtained are shown in Table 4.

It is clear from the data listed in Table 4 that the solutions of aluminum halide in esters listed in Table 4 are stable and pumpable over long periods of time.

It can also be seen that the curves plotting the peaks in Table 4 are of the same magnitude as curves D, C, and D in the drawings.

Uses of the Solution of the Invention One of the important uses of the solution of the invention is its use as a catalyst solution for the ethylation or alkylation of isobutane.

Such ethylation resulted in the formation of significant amounts of diisopropyl-2,3-dimethylbutane, which had a high formulation octane number.

It is clear that the above components with high formulation octane numbers without the use of lead are valuable components in lead-free gasoline.

Therefore, it contributes to reducing the pollution caused by leaded gasoline.

Cisopropyl is a product produced by the acid-catalyzed ethylation of isobutane.

However, if the reaction conditions are not controlled, secondary reactions will occur and higher paraffins will be formed by C8.

Also, ethylene is then added to the moiety and decomposes, forming molecules with an odd number of carbons.

Such secondary reactions dominate the octaneity of the total output.

The catalyst used in the ethylation process described herein is a solution of aluminum chloride at a concentration of 1.1 to 1.4 moles per mole of said methyl ester.

Esters that can be used are the compounds listed in Tables 3-4.

Menal n-monobutyrate and methyl n-valerate are preferred.

Although not required, halogenated alkyl cocatalysts such as ethyl chloride, hydrogen chloride, and t-butyl chloride can be used.

The amount of cocatalyst used is about 0 to 0.85 moles per mole of active aluminum chloride catalyst.

The term activated aluminum chloride refers to the amount of aluminum chloride in excess of one molar equivalent of ester present in the ester solution.

Although the ethylation reaction can be carried out batchwise, it is more easily and economically carried out continuously.

The continuous operation method will be explained below.

Catalyst concentration is approximately 1.0 based on the isobutane charged.
~5%.

The alkylation temperature is about 70-200°F.

The residence time is about 60 minutes or less under stirring.

The molar ratio of isobutane to ethylene is about 5-10.

The continuous ethylation of isobutane described in the above reference example is 3
The experiments were carried out in a 00ml steel autoclave.

Further advantageously, the reaction can also be carried out in any type of reactor that provides intimate mixing, for example in a thin film reactor.

In all runs, the initial ethylene (C2) pressure and reactor temperature were established.

The ethylene flow rate was adjusted to maintain the initial ethylene pressure.

Then isobutane and catalyst solution (methyl n-monobutyrate)
were weighed separately and placed simultaneously into the reactor.

Residence time was determined by pump feed rate.

The rate of collection of the effluent reaction mixture was adjusted to match the rate of addition of fresh isobutane and catalyst.

The reaction effluent was transferred to a steel vessel where the catalyst solution was separated by gravity and collected.

The crude alkylated product was allowed to stand at room temperature to remove nearly all unreacted isobutane and ethylene before analysis of the alkylated product.

Reference Examples 2-7 A series of runs were conducted to ethylate isobutane using the general procedure described above.

In each run, conditions were varied within the range of reaction conditions described above.

If a co-catalyst was used, it was ethyl chloride. Process conditions, conversions, yields and unleaded research octane numbers are shown in Table 5.

The distribution of the alkylated products made in Reference Examples 2 and 3 is shown in the sixth column.
Shown in the table.

Another important use of the solutions of the invention is their use as catalyst solutions for olefin polymerization.

This will be explained using the following reference example.

Reference Example 8 Methyl 2-ethylhexanoate-AICl3 solution (AIC
The ratio of I3 to ester is 1.3:1) 8 g and 100 g of 1-decene are weighed separately and placed simultaneously into a flask equipped with addition tube, stirrer, thermometer and condenser for 55 minutes and maintained at 30°C. did.

After all ingredients were added, the mixture was held at 30°C for 1 hour.

The reaction mixture was quenched by pouring onto a mixture of ice and hydrochloric acid.

Transfer it to a separatory funnel and add petroleum ether (boiling point 30-6
0°C), washed with 100 ml of water, and diluted with 5% N
Washed with aHC03, water, neutralized, then anhydrous Na
Dry over 2SO4.

Monomer and dimer were removed by distillation under reduced pressure to obtain 87.6 g of oil and trimer having the following physical properties.

KV at 99°C 40.8cS KV at 38°C 420cS Reference Example 9 1-Decene was polymerized in the same manner as Reference Example 8.

However, instead of the methyl 2-ethylhexanoate solution, 6.8 g of methyl n-butyrate-AlCl3 solution (ratio of AlCl3 to ester was 1.3:1) was used, and the addition time was 4.
It was set to 1 minute.

76.5 g of trimer and oil with a viscosity of:

KV at 99°C 37.6cS KV at 38°C 379cS Reference Example 10 1-Decene was polymerized using the same method as Reference Example 8.

However, instead of the methyl 2-ethylhexanoate solution, use the methyl i-butyrate AICl3 solution (AICI3 to ester is 1.
3:1) 7.8 g was used, and the addition time was 44 minutes.

82.6 g of trimer and oil with a viscosity of:

KV at 99°C 34.05cS KV at 38°C 332cS Reference Example 11 Molar ratio of AICl3 to l-IJ methyl methyl acetate 1.
A solution of aluminum trichloride in trimethylmethyl acetate was prepared by dissolving the aluminum trichloride in a ratio of 3:1.

This solution (7.2.g) and 100g of 1-decene were weighed separately and placed simultaneously over 55 minutes into a flask equipped with an addition tube, thermometer, and condenser and maintained at 30°C.

After addition of all ingredients, the mixture was stirred at 30° C. for 1 hour.

The reaction was then cooled by pouring onto a mixture of ice and hydrochloric acid.

The mixture was then transferred to a separating funnel, washed with 100 ml of water and 100 ml of 5% NaHCOs, further washed with water until neutral, and dried.

The monomer and dimer were removed by distillation under reduced pressure to obtain an oil and trimer having the following viscosities.

KV (99℃), cst 3 6.8K
V (38°C), cSt376 except that methyl n-valerate, methyl i-monovalerate, methyl 2-methylvalerate, methyl n-hexanoate, or methyl 2-ethylbutyrate was used instead of methyl trimethylacetate as the solvent. performed the same procedure as above and obtained similar oils and trimers.

[Brief explanation of the drawing]

The diagrams show the kinematic viscosity at 100°F for a solution of 1.3 moles of AlCl3 in ethyl propionate (curve A) and a solution of 1.3 moles of AICl3 in methyl n-butyrate (curve B). ), a solution of 1.3 mol AIC13 in n-methyl valerate (curve C), and n-
Figure 2 is a curve on a semi-logarithmic scale showing the relationship between storage days for a solution of 1.3 moles of AIC13 in methyl hexanoate (curve D).

Claims (1)

[Claims] 1 n-butyric acid, n-monovaleric acid, n-hexanoic acid, i-valeric acid, trimethylacetic acid, 2-menalvaleric acid, 2-ethylbutyric acid in which aluminum chloride is dissolved in an amount of 1 mole or more per mole of ester. , or methyl ester of 2-ethylhegisanoic acid.