DE2345298A1 - LIQUID ALUMINUM HALOGENIDE CATALYST SOLUTION AND ITS USE FOR THE POLYMERIZATION OF OLEFINS - Google Patents

Description

The invention relates to a liquid aluminum halide catalyst solution and their use for the polymerization of olefins; it concerns in particular liquid aluminum halide catalysts that stable and pumpable liquids over long periods of time and excellent control, Uniformity and reproducibility of the reactions catalyzed by such an aluminum halide make possible.

It is known that aluminum halides, in particular aluminum chloride and bromide, are used in many reactions,

4098 U / 1 104

for example in polymerization, alkylation and isomerization, used as catalysts. There Aluminum chloride (just like aluminum bromide) is a solid while the reactants are liquid, it is difficult to control the reactions and obtain reproducible results. For example the polymerization of olefins is carried out by various methods, each of which It has disadvantages: (1) all of the olefin becomes the catalyst added, which leads to a non-controllable exothermic reaction; (2) the olefin becomes added slowly to the catalyst which causes the catalyst concentrate to remain during the run varies, adversely affecting reproducibility j (3) the catalyst and the olefin are metered separately and introduced into the reaction vessel in suitable proportions. The at However, problems encountered with the dosing of a solid material make maintaining the desired one Ratios of catalyst to olefin difficult. Another disadvantage of all of this What is common to the process is that it is difficult to distinguish between the solid catalyst and the liquid olefin to achieve uniform contact.

On the other hand, if both the catalyst and

409814/1104

even the reactants are liquid, becomes a more uniform Contact achieved and an exact dosage is possible. That way, the difficulties that came with the Use of solid aluminum chloride or bromide can be essentially eliminated when the aluminum chloride occurs or bromide could be obtained in a catalytically active liquid form. Ss was already proposed to use aluminum chloride or a complex thereof in various solvents, such as alcohols, Ethernfund methyl acetate, to dissolve, dissolve in every case however, there is less than 1 mole of aluminum chloride per mole of solvent. Such molar solution ratios were but not catalytically active.

In French Patent 1 433 373 it is indicated that catalyst solutions containing more than 1 mole of one Aluminum halide dissolved in certain esters can be used for the polymerization of olefins and that these solutions can be recycled for subsequent experiments. It has also already been suggested n-pentane using AlCl dissolved in ethyl acetate, to isomerize, to decant the reaction product and the catalyst solution again in the subsequent experiments (Ind. & Eng. Ghem., 42, 342 (1950)). By both polymerization and isomerization recycling processes mentioned above Ethyl acetate is used as solvent and all tests are carried out within 24 hours carried out.

4098U / 1 10 *.

On the basis of experimental tests has now been found that the AlCl "decomposed -Äthylacetat catalyst solution at temperatures of 20 to 25 ^0C within 24 to 30 hours with evolution of HCl to a hard solid. Therefore, the "catalyst solution" as it has been used up to now cannot be recycled over long periods of time of several days or months.

In French patent 1,433,373 there are ethyl propionate solutions of aluminum halide. However, it has been shown that solutions of more than 1 mol Aluminum halide in ethyl propionate, although they are about remain fluid and stable over long periods of time, have the disadvantage that their viscosity increases rapidly with time increases. For example, the viscosity of the solution doubles in less than 2 days at 38 C. Such an increase in viscosity makes accurate dosing difficult and, more seriously, increases that Pumping power requirements (lower pumpability) when using this solution. These factors, of course, worsen the effectiveness or the efficiency of a process in which such a catalyst solution is used will.

It has now been found that methyl ester of n-butyric acid, n-valeric acid, n-hexanoic acid, isovaleric acid, trimethylacetic acid, 2-methylvaleric acid, 2-ethyl butyric acid and 2-ethylhexanoic acid for the production of aluminum halide

409814/1104

Solutions can be used which have the disadvantages indicated above in relation to viscosity changes and do not have difficulties in handling.

The invention generally relates to a stable liquid aluminum halide catalyst for catalyzing Reactions normally catalyzed by aluminum chloride or aluminum bromide ^ and one catalytic Has activity corresponding to that of aluminum chloride or bromide alone, which is characterized is that it is a methyl ester of n-butyric acid, n-valeric acid, n-hexanoic acid, isovaleric acid, Trimethyl acetic acid, 2-methylvaleric acid, 2-ethyl acid or 2-ethylhexanoic acid, in which aluminum chloride or aluminum bromide in an amount of more than 1 mole is dissolved per mole of the ester.

The invention also relates to a method for carrying it out a reaction catalyzed by aluminum chloride or bromide, which is characterized in that the reaction is carried out in a reaction vessel under reaction conditions in the presence of a catalyst solution, the aluminum chloride or bromide dissolved in the above ester in an amount greater than 1 mole per mole Ester, contains, separates the catalyst solution from the effluent from the reaction vessel and they, preferably with supplement of the aluminum halide, recycled into the reaction vessel. -

4Q98U / 11CU

The accompanying drawing shows curves in a semi-logarithmic way Scale showing the relationship between the kinematic viscosity at 38 ° C (100 ° F) and the Time in days when storing solutions with 1.3 mol A1C1_, dissolved in ethyl propionate, methyl n-butyrate, methyl n-valerate and illustrate methyl n-hexanoate.

The catalyst according to the invention is a solution or a complex of an aluminum chloride or bromides in the above-mentioned ester. The solution contains more than 1 mole of aluminum chloride or bromide per mole Ester. Generally, the amount of aluminum chloride or bromide dissolved per mole of ester is between about 1.1 and about 1.4 mol. A 1 / <C molar solution has only a small one or no catalytic activity. The aluminum chloride or aluminum chloride present in excess of 1 mole in the solution -bromide appears to be the component that gives the catalyst solution the catalytic activity. The for the The amount of solution used to catalyze the reaction therefore depends only on the fact that a sufficient excess (more than 1 mole) of aluminum chloride or bromide is present to catalyze the desired reaction which normally occurs is catalyzed by solid aluminum halide.

The solution of aluminum chloride or bromide in the ester forms rapidly. Forms easily at room temperature an Is1 molar solution or a complex. This solution is able to produce additional aluminum at temperatures of 30 to 50 C

subsequently changed

409814/1 104

to dissolve inium chloride or bromide. To a hydrolysis due to the moisture avoiding the catalyst solution preferably in a dry, inert atmosphere, for example in nitrogen or more dry Air, produced.

In the case of the solvent ester used according to the invention it is the methyl ester of certain alkanoic acids. Examples of such esters are the methyl esters of n-butberic acid, n-valeric acid, n-hexanoic acid, isovaleric acid, trimethyl acetic acid, 2-methylvaleric acid, 2-ethylvaleric acid and 2-ethylhexanoic acid.

As indicated above, the catalyst solution according to the invention is suitable for the catalysis of any reaction which usually by solid, aluminum chloride or, bromide is catalyzed. Such reactions and their reaction conditions are known per se. These include alkylation of aromatic compounds with olefins or aliphatic halides, the hydrogenation of olefins and isomerization of paraffins.

Of particular interest is the continuous polymerization of olefins with recycling of the catalyst to give liquid polymers which can be used as synthetic lubricants. The invention is explained in more detail below with reference to this polymerization. The most varied of olefins can be polymerized with the stable catalyst solution according to the invention

A098U / 1 104

will. In general, they can and can contain from about 2 to about 25 carbon atoms per molecule straight or branched chain with or without aromatic ring substituents. Although the 1-olefins are preferred olefins, olefins with internal double bonds can also be used. The olefin reactant can be a single olefin or a mixture of olefins. Examples of suitable olefins are as follows: Ethylene; Butene-1; Isobutene; Hexenj Octene-2j 2-. Ethylhexene-1j decene-2; Decen-lj Undecen-Ij Dodecen-lj Hexadecene-lj octadecene-1; Octadecene-9; Eicosenj Tricosen-1} Tetracosen-1 and Triaconten-1.

The polymerization is carried out at temperatures between about 0 and about 100 ° C. for about 1 to about 3 hours. Usually it is carried out essentially at atmospheric pressure, but can, especially at lower olefins, also overpressures, which are sufficient to maintain the liquid phase, used with success will. The amount of catalyst used is generally from about 1 to about 5 percent by weight of the olefin, based on the excess aluminum chloride. In some processes, an inert to the polymerization Solvents can be used to make the polymer products less viscous and easy to handle. To suitable Solvents include kerosene and paraffins, e.g. heptane, octane, isooctane, decane and the like.

Since the catalyst solution according to the invention is a heavy

4098U / 11CU

Is liquid, the effluent from the reactor is allowed to stand still until the main amount of the catalyst solution is has separated in the form of a lower heavy layer. Alternatively, it can be used to speed up the separation a centrifuge can be used. This layer is recycled, optionally together with fresh aluminum chloride. Then the remaining polymer product can be washed free of any residual catalyst solution, dried and distilled from solvents and monomers! to be freed.

The following examples are intended to illustrate the invention, in particular the preparation of catalyst solutions of aluminum halide in various esters and 'their use for the polymerization of 1-olefins, explain in more detail without them .but to be limited to that.

example 1

A number of solutions have been prepared by dissolving AlCl «in various esters, using if necessary was heated slightly to a temperature above room temperature, in a molar ratio of 1.32 moles of AlCl, per Moles of ester. Each solution (or mixture) was tested for its physical state at room temperature, i.e. whether it was liquid (L), solid (S), liquid + solid (L + S), examined immediately after the addition of AlCl-, 1 hour later and 24 hours later. If in the examined range

409814/1 104

Ethyl propionate was the only effective solvent an examination was carried out 1 month later. The data obtained are in Table I below specified.

Table I. Physical condition 24 hours 1 month 1 H. later later Ester solvents after later L + S Encore L ₊ S - Ethyl formate L + S + S. Butyl formate L ⁺ L. L + S Ethyl acetate L. L ⁺ - Propyl acetate L ⁺ - S. Isopropyl acetate L ⁺ L ⁺ S - n-butyl acetate L. L ⁺ L ₊ S ⁺ Isobutyl acetate L ⁺ + S. sec-butyl acetate L ⁺ L ⁺ - n-pentyl acetate L ⁺ - L + S Phenyl acetate S. L + S L + S Benzyl acetate L + S L + S L L Phenethyl acetate L + S L. Ethyl propionate L. for a decomposition strong signs

Upon further investigation it was found that a class

4098U / 1

of esters in addition to ethyl propionate was able to form solutions that remain liquid for 3 days or more.

Example 2

By dissolving A1C1 “in various esters under gentle heating to a temperature above room temperature, if necessary, was carried out using a Molar ratio of 1.3 moles of AlCl “per mole of ester Set of solutions made. Each solution was initially tested for its physical appearance at room temperature examined. Those that were liquid were monitored periodically. Those given in Table II below Times indicate the length of time that each solution was monitored, but they do not indicated that the solution became unstable at this point as the length of the monitoring periods varied.

4098U / 1 1CU

Table II

acid

alcohol

Methyl-

* ·. Ethyl"

to

4 ^ n-propyl

Propionate n-butyrate Valerate n-hexanoate n-octanoate n-nonanoate fixed fluid
90 days fluid
20 days fluid
17 days fluid
30 days - fluid
30 days fluid
3 weeks - - fluid
2 weeks fluid
4 days fluid
10 days «. • Mt «· insoluble insoluble Ml MI insoluble unstable ■ Μ Μ mm * m mm «■

to

CO CO

As noted above, aluminum halide solutions occurred in methyl-n-butyrate and in methyl-n-v al erate only relatively small changes in viscosity on storage over long periods of time. on the other hand it increased considerably within a very short period of time for solutions in ethyl propionate. This is going through the following examples explain.

Examples 3 to 6

There were four solutions from A1G1_, each in a different one normal fatty acid ester, manufactured; each solution contained 1.3 moles of A1C1 “per mole of ester. The esters used are given in Table III below. Each solution was kept at 38 ° C for several days (100 F) and periodic cinematographic viscosity determinations were made at 38 ° C (100 ° F) (ASTM D445). The results of these determinations are given in Table III below.

Table III Methyl-n-
butyrate at 38 ° C (100 ° F) Kinematic viscosity 10.1
10.2.
10.4 Methyl-n-
valerate Methyl-n-
hexanoate time in
Days Ethylpro
pioneer 11.0
11.0
11.0. 12.4
12.5
12.6 0
1
2 8.5
43.1

A098U / 1 10A

Continuation from Table III Methyl-n-
butyrate at 38 ° C 2345298 - * Kinematic viscosity (100 ° F) - time in
Days Ethylpro-
pioneer 10.6 Methyl-η- methyl-n-
valerate hexanoate 13.7 4th 10.8 ■ M 14.1 5 585 10.9 - 14.4 6th 980 11.0 - mm 7th 1770 mm 11.3 - 8th 2174 12.5 11.5 - '9 - - 11.7 19th 5411 13.7 21 - 13.1 26th 7680

Based on the data in Table III above, curves were made showing the change in viscosity with show the time. The attached drawing shows in semi-logarithmic Scale curves showing the relationship between the kinematic viscosity at 38 C (100 ° F) and the time in days during storage of a solution of 1.3 moles of AlGl per mole of ethyl propionate (curve A), a solution of 1.3 moles of AlCl- per mole of methyl n-butyrate (Curve B), a solution of 1.3 moles of AlCl per mole of methyl n-valerate (Curve C) and a solution of 1.3 moles of A1C1_ per mole of methyl n-hexanoate (curve D) explain. From these It can be seen from the curves that a rapid increase in viscosity occurred in the case of the solution in ethyl propionate, while in the solution in the methyl esters these only

409814/1104

relatively little increase. For example, the viscosity increased

strength of the ethyl propionate solution within 5 days of about 8.5 to 585 cSt. On the other hand, the viscosity of the methyl n-butyrate solution increased from etxra within 5 days. 10 only to about 11 cSt.

As a result, aluminum halide solutions in ethyl propionate not be used for long periods of time without the requirements for the pump with which Help they are circulated, increase, i.e. they become less and less pumpable. On the other hand, solutions remained in methyl n-butyrate, methyl n-valerate and methyl nhexanoate pumpable. As a result, the procedure can be carried out much more effectively,

In previous applications of this series it has been found that the acid portion of the ester solvents is a normal acid have to be. It is generally assumed that branched-chain acids are ineffective, as indicated above it has been shown, however, that certain branched chain acid esters are effective, stable solvents that remain pumpable. This is shown by the following examples,

Examples 7-11

There were 5 solutions of AlCl-, each in a different one branched chain fatty acid ester; any solution

4098U / .1104

contained 1.3 moles of A1C1 “per mole of ester. The esters used are given in Table IV. Each solution was stored at 38 C (100 F) for several days and the kinematic viscosity at 38 C (100 F) (ASTM D445) was determined periodically. Those in these provisions The results obtained are shown in Table IV below.

4098U / 1 104

Table IV
Kinematic viscosity at 38 ° C (100 ° F) in cSt

Time in days

1 2 3 4 7 9

11 14 .15 16 "17 18 21 22 23 28 31

Methyl isovalerate

11.4 11.3 11.3 11.4 11.5

12.8 13.0 13.1 13.3 13.4 13.8 14.0 14.1 14.9 15.5

Methyl trimethyl acetate

14.9 14.6 14.7 14.7 14.7

14.9 15.0 15.0 15.0 15.0 15.0 15.0 15.1 15.2 15.2

Methyl-2-

methylvale-

advice

12.0 11.8 11.9

11.9 ·. 12.0

12.8 12.9 12.9 13.0 13.0 13.3 13.3 13.4 13.9 14.1

Methyl 1-2-ethyl butyrate

13.8

14.9

Methyl-2-

ethylhexa-

noat

17.4

13.9 17.2 13.8 17.4 13.8 17, '5 14.1 17.9 14.1 18.3 15.0 18.4 14.5 19.0

19.4

OI INJ CD OO

From the data in Table IV above it can be seen that solutions of aluminum halide in the specified Esters remain stable and pumpable over long periods of time. From this it can also be seen that if the Data of Table IV are recorded in the form of curves which are curves of the same order as the curves B, C and D of the accompanying drawing.

Another important field of application of the invention Catalyst solutions is the ethylation, i.e. the Alkylation of isobutane. It has been shown that considerable amounts of diisopsopyl in this ethylation (2,3-Dimethylbutane) arise, which has a high mixed octane number. It should be noted that such components with a high mixed octane number without the use of lead represent valuable components in unleaded petrol and therefore to reduce pollution that caused by leaded gasoline.

Diisopropyl is the kinetic product of the acid-catalyzed Ethylation of isobutane. However, if the reaction conditions are not controlled, secondary reactions occur on leading to the formation of Cg and higher paraffins to lead. Cracking also occurs with subsequent addition of ethylene to the fragments and the formation of Molecules with an odd number of carbon atoms. These secondary reactions are at the expense of the octane quality the total yield.

40981 A / 1 104

In the case of the catalysts according to the invention for this Ethylation process described is Solutions of aluminum chloride or aluminum bromide in a concentration of 1.1 to 1.4 moles of aluminum chloride per mole of ester. Examples of useful esters are given in Tables III and IV. Methyl n-butyrate and Methyl n-valerate are preferred.

Although not essential, an alkyl halogen promoter such as ethyl chloride, hydrogen chloride and t-butyl chloride can be used. The amount of promoter used is between about 0 and about 0.85 moles of promoter per mole of active aluminum halide catalyst. Denier term "active aluminum halide ¹¹ refers to the amount of aluminum halide, which is the ester present in the Esterlösungen in excess of 1 mole Äqualent.

Although the ethylation reaction can be carried out batchwise (batchwise), it is more convenient and more economical to do it in a continuous process. The inventive method is explained in more detail below on the basis of such a procedure.

The catalyst concentration varies between about 1.0 and about 5%, based on the isobutane introduced. the The alkylation temperature is between about 21 and 93 C (70 to 200 F). The residence time can be up to with stirring

4098U / 1 104

vary about 60 minutes. The molar ratio of isobutane to ethylene is between about 5 and about 10.

The continuous ethylation of isobutane described in the following examples was carried out in a 300 ml steel autoclave carried out. The reaction can expediently also be carried out in any other type of reactor ensures intimate mixing, for example in a thin film reactor. In all experiments the ethylene- (C ~) -Initial pressure and the reactor temperature are set. The ethylene flow rate was adjusted so that the initial ethylene pressure was maintained. then isobutane and the catalyst solution (methyl n-butyrate) were added separately in dosed form and at the same time in introduced the reactor. The residence times were adjusted by the pump speeds. The withdrawal speed the effluent from the reaction mixture was adjusted to match the rate of addition of fresh Isobutane and catalyst corresponded to the reaction effluent would be transferred to a steel kettle in which the catalyst solution is separated under the action of gravity and was withdrawn. The crude alkylate product was allowed to stand at room temperature so that almost all of the unreacted Isobutane and the ethylene were removed therefrom before alkylate analyzes were performed.

Examples 12-17

A number of attempts to ethylate iso-

A098U / 1104

butane carried out according to the general procedure described above. In each experiment, the experimental conditions were within the ranges given above the reaction conditions varied. If a promoter was used, it was ethyl chloride » The process used, the degree of conversion, the yields and the lead-free Research Octane Number (RON) are given in Table V below. In Table VI below is the product distribution of the alkylate formed in Examples 12 and 13 specified.

Table V

Example 12 13 14 15 16 17

Temperature in ⁰ C 22.8 22.2 93 53 49.5 49 (° F) (73) (72) (200) (128) (121) (120)

Outlet pressure "15.1 5.22 22.1 9.44 11.5 11.5 (C ₂ ⁵³ ) in kg / cm (200) (60) (300) (120) (150) (150) (psig)

Dwell time in minutes

Isobutane / C = molar ratio

G. free AlCl ,, / 100 g iC ₄

Molar ratio 0.25 0.26 0.28 0.51 0.25

Promoter / free

Stirrer (rpm) 600 600 600 600 600 1000

Ethylene wall 91.5 62.0 61.9 61.1 78.5 76.8

efficiency (% by weight)

4098 14/1104

30th 8th 30th 30th 30th 7th 30th 9 30th 9, 0 9.5 9.3 9, 6th 4, 0 5.0 5, 5.0 2.4 2, 5, 4.9

Continuation of Table V

C, in the alkylate 70.0 83.5 78.8 84.8 76.9 (8 wt .-% ^a )

Mini-Micro-RON, of course

99.2 301.8 99.5 101.8 -

(a) Gas chromatographic (G.C.) analysis of the washed Alkylate

Table VI Alkylate Composition (a) Example 12 Example 13

iC,

0.6-0.6

0.2-0.2

2.2 DMB 0.1 I ₁ O- 2.3 DMB 67.5 ₇ o ₀ 79.4 2 MP 4.0 -73.0 _5j4 Ζ-ι-τ 1.4, 2, Oj 2,2,3 TMB 0.2 " 2,3-DMP 0.1 - 2,4-DMP 2.0 -2.9 0.9 2-M hex 0.4 0.5 3-M hex 0.2j 2.5 DM hex 1.7- 1.3 " 2.3 DM Hex + 2M, 3EtP ι ', ο 0.9 2.4 DM Hex + 2.2.3 TMP 2.9 -16.7 1.7 2.2.4 TMP 7.7 3.6 2,3,4 TMP 1.2 0.5 2,3,3 TMP 2.2_ I.IJ

-87.8

-1.4

-9.1

4098U / 11OA

Continued from Table VI

Residue 6.8-6.8. 1.4 - 1.4

Alkylate RON, clear 99.2 101.8

(a) Gas chromatographic analysis of the bottom products

Example 14

8 g of a methyl 2-ethylhexanoate / AlCl solution (AlCl “/ ester ratio = 1.3 / 1) and 100 g of 1-decene were metered in separately over the course of 55 minutes and at the same time in one with addition tubes, a stirrer, a Introduced a thermometer and a condenser-equipped flask kept at 30 ° C. After all the components had been added, the mixture was kept at 30 ° C. for 1 hour. The reaction was quenched by pouring onto an ice-hydrochloric acid mixture. It was transferred to a separating funnel, diluted with petroleum ether (boiling point 30 to 60 ° C.), washed with 100 ml of water, 100 ml of 5% NaHCO 2 and with water until neutral and then over anhydrous Na _? S0, dried. The monomer and dimer were removed by distillation under reduced pressure to give 87.6 g of a trimer-plus oil having the following physical properties:

Kinematic viscosity (KV) at -93 C = 40.8 cSt KV at 38 ° C = 420 cSt

409ÖU / 1104

Example 15

In exactly the same way as in Example 14 was used 1-decene polymerized, this time with 6.8 g of a Methyl-n-bu ty rat / AlCl solution (AlCl / ester ratio = 1.3 / 1) was added within 41 minutes instead of the methyl 2-ethylhexanoate solution. It weighs 76.5 g of a trimer-plus oil with the following Obtaining viscosities:

KV at 99 ° C = 37.6 cSt KV at 38 ° C = 379 cSt

Example 16

1-Decene was polymerized in the same manner as in Example 14, but this time 7.8 g of a methyl isobutyrate / AlCl -Solution (AlCl / ester ratio = 1.3 / 1) instead of -the methyl 2-ethylhexanoate solution within 44 minutes was added. 82.6 g of a Trimerplus oil with the following viscosities were obtained:

KV at 99 ° C = 34.05 cSt KV at 38 ⁰ C = 332 cSt.

A098 1 small 1

Claims (5)

Claims 1. Liquid aluminum halide catalyst solution based on of aluminum chloride or aluminum bromide and one Ester of a carboxylic acid with a molar ratio of aluminum halide to ester of more than 1, thereby characterized in that it is a methyl ester of η-butyric acid, n-valeric acid, n-hexanoic acid, isovaleric acid, Contains trimethylessxgic acid, 2-methylvaleric acid, 2-ethyic acid or 2-ethylhexanoic acid. 2. Catalyst solution according to claim 1, characterized in that that the molar ratio of aluminum halide to ester is 1.1 to 1.4. 3. Use of the catalyst solution according to claim 1 or 2 for catalyzing a reaction caused by an aluminum halide is catalyzed. 4. Use according to claim 3, characterized in that the reaction is an olefin polymerization acts. 5. Use according to claim 3 _fi, characterized in that the reaction is the alkylation of isobutane with ethylene. naohträofloh | 40FSTA / 1104 changed Blank page