DE2147152C3 - Process for the preparation of trialkylaluminum complexes - Google Patents

Description

* 5 will be.

where P and X have the abovementioned meanings as well as the method of the invention.

have to be used with manure mainly to get out of the

R ' ₈ Al (III) chain growth processes incurred, not by distillation

converts separable mixtures of trialkylaluminum

2. The method according to claim 1, characterized in that ao formula R ' ₃ Al and higher olefins the Β' _Λ Λ 'Jurch distinguishes that at S.elle of R' ₃ A1 from a bond in complexes of the formula R ₃ Al · R ' ₃ A1 - NaX chain growth process by reacting to remove, where R ₃ A! becomes free, the mixture obtained easily by distillation R ₃ Al with lower olefins is separated off and used as starting material for the chain up of R ' ₃ A1 with olefins. wax can be used.

From this point of view, what is surprising is the easy and smooth isolability of compounds of the formula

R ₃ Al by reacting their 2: 1 complexes with a

Trialkylaluminum, least of which alkyl radicals contain more carbon atoms than the alkyl groups of the starting com-

The invention relates to a method for producing 30 plexes. The distillation residue separates smoothly

of Trialkylaluminiuri 'complex of formula in a first liquid phase, which is mainly composed of

R Al R 'Al NaX (I) consists of higher olefins, and a second, essentially

³³ * 'borrowed from trialkylaluminum complexes of the general

In which R is an alkyl radical with 2 ^ ε 4 carbon atoms, X is a phase consisting of _{my formula R 3} Al R ' _{3 A1 NaX,}

Fluoride or cyanide ion and R 'is an alkyl radical which is converted into a by reaction with lower olefins indicates, with at least some of these alkyl groups by distillation easily separable mixture of pre-

Has 8 to 30 carbon atoms. In order to produce these predominantly higher olefins and complexes of the formula plexes, the procedure according to the invention is such that 2R ₃ Al · NaX can be converted.

a trialkylaluminum complex of the formula The reaction of the invention becomes expedient

2RAl-NaX ίΐπ * ° ^ ^e ' ^emer temperature of about 0 bus 19O ⁰ C, a

³ pressure of about 0.35 to 7.00 ata and in one time

where R and X are as defined above, ranging from about 0.1 seconds to about one

performed with hour. From the reaction mixture is

R ' ₃ A1 (111) R ₃ Al at a temperature of about 80 to 175 ° C

45 and a pressure of about 1 to 70. orr easily broken down. Complexes of trialkylaluminum with alkali can be distilled, so that a metal fluoride, such as sodium fluoride or alkali complex of the formula I, remains as the distillation residue. If the monometal cyanides are known (US Pat. No. R ' ₃ A1 contains some R ₃ Al, this is stated in the 2,844,615 and British patent 779,874). The complex of the formula ϊ bound or superseded. Ratio of trialkyl aluminum to alkali fluoride 50 Preferably the reaction is carried in a may be 1: 1 and beiragen are for mixtures temperature range of about 75 to 150 ⁰ C, under between these values: 1, or second 2 A1 (C ₂ H ₅ ) ₃ · NaF is a pressure of about 0.7 to 1.4 ata and a very stable and not easy to split reaction time of about 0.5 seconds to 15 minutes complex. Surprisingly, however, it succeeds. Typical conditions are about 125 "C, to allow the process according to the invention to achieve a pressure of about atmospheric pressure and a reaction exchange within the complex in a time of about 5 minutes.

Formation of 2: 1 complexes, some of which are alkyl radicals The reaction can be carried out in a solution or

contain 8 to 30 carbon atoms. This had to be done in no thinners. Typical the-way predictable. ("ACS Monograph", Nf. 147, remedies like this are predominantly made from n-monoolefins P. 200 and U.S. Patent 3,415,862). 60 with from about 14 to about 30 carbon atoms in the

The method according to the invention can, for example, be a molecule consisting of liquids. Lighter olefins, such as butene-1 used in aluminochemical processes, can also be used as stripping agents. The chain growth process is typical for this, and the by-products are distilled off. Many of them drive, in the case of ethylene, higher alkyl complexes in triethylaluminum, even
is stored. The reaction mixture contains ia olefins 6 ₅ (C, H ₅ ) ₃ Al · (OcIyI) ₃ Al -NaCN,

and compounds of the type R ' ₃ A1. After a be ^{v 2 5/3 v J n}

Preferred embodiment of the invention are quite viscous and can make the use of man ? .. B. this mixture with compounds of all-diluents desirable.

Cm explanation of the method, a mixture of the complex 2 [(C, H,)., Al]. NeF minium prepared with Trioctylalu- 'and implemented, wherein Trlltfcylaluminium released and a new complex

( CH ")" A1 - (CH ) Al. NaF (C ₈ H ₁₇ J ₉ AI (C ₈ H ₆ J ₈ Al NaF,

is formed. The triethylaluminum formed is in to the extent »as it becomes free, under reduced pressure distilled from the mixture.

The flow diagram explained below shows a method in which the method according to the invention can be used. Vrf shown in the figure

ate method can be used. The method shown in the figure has a production stage 10 in which a chain growth process with conversion of R ₈ Al with z. B. ethylene or propylene is carried out. 2 [R »A1] · NaX or a compound of the formula R'VU with alkyl groups of medium length can possibly also be used as the starting compound. The reaction product of preparation stage 10, which contains trialkylaluminum of the formula R ' ₃ A1 and olefins with about 4 to about 30 carbon atoms in the molecule, is used to separate the light C ₂ -C ₁₂ olefins of distillation stage 11, preferably; ine flash Destillaüon supplied (final stage temperature usually between about 90 to 260 ⁰ C at about 2 to 40 Torr). The residue consisting of olefins of approximately tetradecene and higher and trialkylaluminum of the formula R ' ₃ A1 is fed to the combination stage 12, in which it is mixed with a trialkylaluminum complex of FonLl 2R ₃ Al-NaX, the components of which are R ₃ Al and NaX.

This is where the reaction according to the invention takes place, in which about half of the _{R 3 Al present in the trialkylaluminum complex of the formula 2R 3} Al · NaX is exchanged for R ' ₃ A1. When the alkyl groups in the complex are ethyl groups and when the number of moles of triethylaluminum in the complex used is approximately twice the number of moles of trialkylaluminum

sa = ¹ ίίΐΑΐ täxESXL temperature is about 90 mM between "" A ¹ and the pressure between about 2 and 20 Torr, ow athylaluminium are about UO ⁰ C ^ J ^ J preferable. Similar conditions for

gerem TrialkyUUuminium, einscnheßliob aluminum are 120 ⁰ C at 5 torr, ** heavy flöchtigerem TriaJkylaluramium lent tri-n-butylaluminum, 140 C at 2 ι orr. The distillation residue becomes the ν «α

«Level 14 fed, m which also em or

Olefins, such as ethylene or propylene, olefins with the same number of Molecule, like the alkyl groups of the. tion stage 12 supplied complex aer

t ₅ 2R ₃ Al · NaX are fed in. The K are with regression of 2 R3AI · ¹ T. The displacement is preferably bet a temperature of about 230-340 ⁰ C, a ° ⁰ ™ * ^D * ™ _to 3.5 to 35 ata and for about 0.1 to iu * ac.

ao carried out. The heavy olefins from aer un tion stage 13 pass through the Verdrangungssiu essentially unchanged. _{t n} s _m ii _c h

The product of the displacement .igsstu.eM ^ nam ^ regenerated complexes of the formula - ¹ ^ ''' _T A _en

> 5 olefins, which by displacing EP ™ ¹ « ¹ ^ '^ and heavy olefins becomes the desti |» α ° ηκ

fed, preferably a ^ ^en " ^l " p _{D k} method. (Temperature about 90 to JW u, about 2 to 40.) The distillation residue from mainly 16 and more K, freed ^{from toch1 ^ "', is left}

Molecule and the ™ f ^M j ^ H 2R ₃ Al-NaX about 5 to 30 minutes ^

Temperature of about 301 to 60 C, form smoothly into two liquid phases of little solubility for a long time . You get «" « _di

heavy olefins with 16 or more carbon atoms, α up to about ^% by weight J

Formula 2 contains R ₃ Al · NaX and a

^the

2R ₃ Al • NaX + R ' ₃ A1 ^ R ₃ Al • R' ₃ A1 • NaX + R ₃ Al

Because R ₃ Al can be removed overhead, the reaction can practically completely follow the formula
f _a ^e _u V _g ^O _{e leads}

So NaX is sang, _with the addition of grain

or se.ner consist te

TSttSÄ at a temperature of about tSS 0 to 190 ⁰ C, at a pressure of about 0.35 to 7.0 ata 50 z. B. with diluted jmdm about 0.1 seconds to an hour through- ™ g ^

For removal, for example by flash distillation, the invention is easily _explained by fl RAl and sodium hydroxide solution.

For removal, for example
lation of the trialkyl aluminum of the formula R ₃ Al under

saasssiässsiiss:

example 1

SSSSSi ₁ SSS

a release of olefins takes place. In general, the higher temperatures and / or other pressures within the specified ranges are required when the "more volatile" triacylaluminium, measurement of the ^
Fumes. Dtm

pder piston jur «^ n

Mixture was

Pressure approximately

2

Stirred for 10 minutes to form the complex 2At ₁ Al. NaF.

Then 35.3 grams (0.096 moles) of trioctylaluminum was added and the flask evacuated to 5 torr would.

The mixture was then left without rectification at an oil bath temperature of 140 to. 145 ^C C and a steam temperature of 100 to RO ⁰ C at about 5 Torr distilled. This gave 13.9 g of distillate, which consisted of 94.3 Μοίρτοζβηΐ AI ₃ AI and 5.7 mol percent entrained trioctylaluminum.

This distillate thus contained 10.7 ρ triethylaluminum (0.093 mol). _{(C, H 2) S} A1 · (CiHs) ₃ Al · NaF remained in the flask as the process product, as was shown by nuclear magnetic resonance analyzes.

Example 2

Example 1 was repeated with 4.5 g (0.093 mol) of NaCN instead of NaF. This gave 13 g of distillate which contained 90.0 mol% of triethylaluminum and 10 mol% of trioctylaluminum, corresponding to 0.085 mol of distilled triethylaluminum. The residue in the flask was analyzed by KMR and consisted of (CH _n ) JAl- (C ₂ H ₅ I ₁ Al-NaCN. Which was contaminated with a small amount of free (C ₂ H _S ) _; , Al.

Example 3

IO Example 2 was repeated with 70.6 g (0.193 mol) of trioctyl aluminum. This also gave 13 g of distillate with a content of 90 mol percent triethylaluminum and 10 mol percent trioctylaluminum, corresponding to 0.0-5 mol of distilled triethylaluminum. From this result it can be seen that regardless of the amount of trioctylaluminum used, a maximum of 1 mole of triethylaluminum is freed from the complex of the formula II.

1 sheet of drawings

Claims (1)

t 2 common formula 2 R9Al · NaX implement (X, R and R '. Patent claims; here have the aforementioned meaning). In this way it is possible, for. B., compounds of general 1. To fix the condensation for the production of TrialkylaJu FormU R ' ₈ Al. The resulting reaction mini-unicoroplexes of the formula 5 product [R ₈ Al · R ' ₈ Al] NaX can, for example, be a »Αϊ» 'At WY m be subjected to a displacement reaction with ethylene RiWR (^ CWWi IU _{dwjj wodurcb} besides higher and R'-olefins of the in which R is an alkyl radical with 2 to 4 carbon atoms, complex 2R ₈ Al-NaX is recovered. This X is a fluoride or cyanide anion and R 'is a complex can now again with mixtures of olefin Alkyl radical, where at least a part w önen and compounds of the general formula R '^ Al this alkyl group has 8 to 30 carbon atoms, d a- in the manner according to the invention for the preparation of characterized in that a compound of the formula R ₈ Al · R ' ₃ Al · NaX is converted Trialkylalurainiumcompiex of the formula. That which is obtained as a by-product ·> Ώ αϊ MaY / m RjAl can be introduced into the chain growth process