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Патент USA US3086047

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United States atent O "ice
’ Patented Apr. 16, 1963
materials of a the ‘sesquichloride type, and particularly
wherein the alkyl groups contain two to about six
carbon atoms. An additional object of the invention is
to provide a new class of novel complex compounds suit
Merle L. Gould, Baton Rouge, La., assignor to Ethyl:
able for conversion to the desired alkyl aluminum chlo
‘Clorporation, New York, N.Y., a corporation of
ride products. An additional object of certain embodi
No Drawing. Filed Mar. 29, 1960, Ser. No. 18,251
ments is to provide a process for making alkyl aluminum
12 Claims. (Cl. 260-448)
sesquichloride compounds wherein the alkyl groups can
include at least two diiferent alkyl radicals, and further,
This invention relates to the manufacture of organo 10 wherein the identity of alkyl groups can be rigorously
controlled or directed. Still another object of certain
aluminum compounds. More particularly, the invention
relates to the manufacture of a new and novel complex
material, and also a new and improved process for the
embodiments of the invention is to provide a novel proc
ess wherein a mixture of a trialkyl aluminum with a
of this nature hasbeen ethyl aluminum sesquichloride
(C2H5)3A12C13. This versatile material is useful in its
a dialkyl aluminum hydride and aluminum chloride.
The products are homogeneous, clear liquids, except when ;
of other materials. Ethyl aluminum sesquichloride can
be reacted readily with aluminum chloride to provide
from ambient temperatures to moderately elevated
dialkyl aluminum hydride, is converted to high purity
manufacture of alkyl aluminum sesquichloride com
15 trialkyl aluminum.
pounds and other aluminum alkyl materials.
In all forms of the process, a new composition is ?rst
Organoaluminum compounds have, in recent years,
produced, having the formula RzAlaClal-l wherein R is
grown in commercial importance. Thus, organoalu
a lower alkyl radical, that is, having from one to, usually,
minum compounds have been employed extensively as
about six carbon atoms, although higher alkyl groups
components of catalysts for the generation of polyole?n
20 are permissive‘. Such compositions are produced by re
resinous material, or as alkylation catalysts.
acting together approximately equimolal proportions of
Outstanding among the organoaluminum compounds
the alkyl groups all have ?ve or more carbon atoms, in
own right, as a component of catalysts, for example, and
also as a highly e?ective intermediate for the production 25 which cases, the compounds have melting points ranging
These new materials can then be further reacted, by
treating with an ole?n, particularly a l-alkene', thus
ethyl aluminum dichloride, (C2H5)AlCl3. Alternatively
it can be reacted with triethyl aluminum to provide
diethyl aluminum chloride, (C2H5)2A-lCl. Ethyl alu
producing an alkyl aluminum sesquichloride, RSAIQCIS.
minum sesquichloride can also be readily reduced with‘
an alkali metal to provide a high purity triethyl alu
ferent than the two alkyl groups in the new composition.
The alkyl group thus established may be the same as or dif
The best mode of operations of the several embodi
minum. In the preparation of ethyl aluminum sesqui
chloride, heretofore, metallic aluminum has been directly 35 ments of the present invention will be clearly understood
from the detailed examples below and the detailed de
reacted with ethyl chloride at elevated temperatures to
scription hereinafter, wherein all parts and concentra
form the ethyl aluminum sesquichloride.
tions are by weight, unless otherwise noted.
While the foregoing reaction of ethyl chloride and
aluminum is quite effective, it suifersfrom the disadvan
Example I
tages that relatively expensive ethyl chloride is required 40
A relatively pure fraction of diethyl aluminum hydride,
as a reagent. This disadvantage is more pronounced
(CQHQZAIH, is reacted with ?nely subdivided anhydrous
when production of higher alkyl compounds is desired.
aluminum chloride, in the proportions of 150 parts of ,
In such instances, the alkyl chlorides are, apparently, for
aluminum chloride to 100 parts of the diethyl aluminum
alkyl bromides or alkyl iodides appear to be essential. 45 hydride, or approximately in a 1:1 mole ratio. The two
materials were vigorously mixed and combination oc
In other words, materials such as n-propyl aluminum
curred with the evolution of a small amount of heat, a
sesquichloride, isobutyl aluminum sesquichloride, and
all practical purposes, inoperable, and the quite expensive
clear, viscous liquid being produced. Analysis of a por
tion of this liquid shows the composition corresponding
minum iodide have been reported. It is thus apparent 50 to diethyl dialuminum trichlorohydride (C,H,),A1,C1,H.
higher alkyl aluminum sesquichlorides have not been
prepared, although products such as di-n-propyl alu
that a more efficient procedure for the manufacture of
The product of the foregoing operation, diethyl dialu
the alkyl aluminum sesquichlorides is desirable, not only
minum trichlorohydride, is a clear, mobile liquid. Upon
standing, however, gelling sometimes occurs.
Aliquot portions of this product were then taken and
to provide utilization of lower price raw materials, but
also to make it possible to effectively manufacture such
compounds having more than two carbon atoms in the 55 reacted with alpha ole?n gases as follows:
Ethylene-a pressure of, initially, about 150 pounds
alkyl group. Ruthru?, in US. Patent 2,271,956, de
per square inch of ethylene was applied and was rapidly
scribes a process wherein an ole?n, hydrogen, and an
absorbed in proportions corresponding to 1 mole per
aluminum halide is reacted with metallic aluminum
ostensibly to produce alkyl aluminum halides.
ever, no illustration shows a good production of the al
mole of the diethyl dialuminum trichlorohydride form
ing ethyl aluminum sesquichloride therefrom in good
leged compounds, and in fact, it appears that signi?cant
polymerization of the ole?n involved would occur. Sig
ni?cant need has thus existed for a'more direct and
about 125° C.
The process is carried out at a temperature of
Propylene—in this operation a similar technique is
employed, and a good conversion to diethyl propyl' dialu
effective process for producing alkyl aluminum sesqui
chloride compounds, without being restricted to two 65 minum trichloride is provided.
Other ole?ns-when n-butene, isobutylene, hexene, or
carbon atom alkyl radicals, and without necessitating the
other lower alpha ole?ns are reacted with the diethyl di
employment of expensive alkyl halides.
aluminum trichlorohydride, as above, comparable reaction
A general object of the present invention is to provide
is encountered and ari alkyl aluminum sesquichloride is
a new and more direct process for the manufacture of
alkyl aluminum chloride materials. More particularly, 70 produced, wherein one of the three alkyl groups, is of
an object of the present invention is to provide a process
course, corresponding to the ole?n reacted.
which is capable of producing alkyl aluminum chloride
of reacting alpha ole?ns of normally liquid character, the
In the case
proportionate quantity is mixed with the diethyl dialumi
occurs“ Accordingly, the present process" alfords ahighly I
num trichlorohydride, the reaction vessel closed and heat .'
ef?cient route to producing a very pure grade of triethyl '
aluminum without the necessity of utilizing ethyl chloride .
is applied to initiate reaction.
' as a starting material.
Example I!
In this operation a supply of dimethyl aluminum hy
Example V _
dride, 100 parts, is-mix‘ed with 235 parts of ‘aluminum
In this operation, the reactants are di-n-pentyl alumi
chloride, and a smooth, heat evolving, reaction occurs,
hydrideand aluminum chloride.‘ Upon reacting this
similar to the reaction in Example I, resulting in forma
with anhydrous aluminum chloride in equimolal
tion of dimethyl dialuminum trichlorohydride. Treat 10 proportions,
a good yield of di-n-pentyl dialuminum tri
' ment of aliquot portions of this compound with ethylene,
chlorohydride is obtained. This product reacts readily
propylene, n-butene, and other alpha ole?ns as in Ex
with ole?nic hydrocarbons, as is the case with the other
ample I above, results in comparable generation of di
vmethyl alkyl dialuminum trichloride materials.
Example III
dialkyl dialuminum trichlorohydride compounds available
by this process.
The step of forming the new compounds of the present
invention, viz., the dialkyl dialuminum trichlorohydride
compounds, is relatively simple. In virtually all instances
In this embodiment 96 parts of anhydrous aluminum
chloride is reacted with 100 parts of diisobutyl aluminum
the dialkyl aluminum hydride and aluminum chloride are
diisobutyl dialuminum trichlorohydride, which is succpti 20 ‘fed together in approximately equimolecular proportions.
The aluminum chloride should be an anhydrous material, ,
ble to prompt and efficient reaction with ethylene, n-bu—
preferably ?nely divided. In continuous operations a
tene, n-pentene-l, n-hexene-l, propylene and other lower
slight excess or de?ciency of any individual component
alpha ole?ns to make the corresponding trialkyl dialumi
present in the reaction zone at one time is not particularly
num trichloro compounds, or alkyl aluminum sesquichlo
rides wherein one of the alkyl groups corresponds to the 25 deleterious to the operation, the overall consumption being
almost identically on an equimol-al basis. . Normally, un
ole?n mentioned.
less production rates are quite high, it is most convenient
As previously indicated, one of the most signi?cant bene
hydride, again resulting in relatively rapid production of
to carry out the preparation in a batch manner, viz., by
?ts of the present invention is its application to a mixture
of a dialkyl aluminum hydride with a corresponding tri
alkyl aluminum compound. Such mixtures are the prod
uct of certain synthesis processes, involving the direct
combination of aluminum metal, hydrogen, and an ole?n,
usually carried out in the presence of a reaction medium
which includes at least some corresponding alkyl alumi
num compound as a component.
Example IV
In this operation, ?nely subdivided aluminum metal is
provided in a reaction zone suspended in a liquid system
comprising approximately equimolar proportions of tri
ethyl aluminum and diethyl aluminum hydride. Ethylene
and hydrogen pressure are applied to the system jointly,
while vigorously stirring and maintaining the liquid phase
at a temperature of about 140° C.
Concurrent reac
tion of these components results in the formation of ad
feeding together batch quantities of aluminum chloride
and the dialkyl aluminum hydride, and vigorously agitat
ing while heating atimoderate temperatures. It will be‘
readily apparent that, if desired, a plurality of dialkyl
aluminum hydride feed components can ‘be provided,
whereby a corresponding plurality of dialkyl dialuminum
trichlorohydride components are obtained.
The reaction is carried out at temperatures from about
ambient conditions to about 130° C., in the ordinary op- '
cration, but the temperatures are not thus limited. It is
ordinarily preferred not to exceed a temperature of about
100° C., and in some instances pressure operation will be '
40 necessary to accomplish the desired reaction.
agitation is highly desirable, as the aluminum chloridef
component is normally fed as a subdivided solid. In ad
' dition, adequate cooling is necessarily provided, as the
reactions are exothermic in character.
ditional quantities of triethyl aluminum and diethyl alumi 45 In those operations wherein the formation of the di
alkyl dialuminum trichlorohydride is followed by its
num hydride, in approximately equimolar proportions,
reaction with an ole?n hydrocarbon, the particular oper
resulting in additional production of a liquid phase, where
ating conditions will vary with the identity of the com
in the triethyl aluminum concentration is of the order of
ponents or reactants involved. In the case of the lower
60 percent and the diethyl aluminum hydride in the pro
50 ole?ns, which are normally gaseous, pressure operation
portions of about 40 percent.
is desired. Pressures of about 50 to 500 pounds per
The liquid phase is withdrawn, and separated from
square inch are usually employed, at temperatures of 50
any unreacted solid aluminum present by ?ltration or
up to about 140 or 150° C. The temperature is not as
sedimentation and decanting. The components are sep
critical in the present process, employing ethylene, as in
arated into relatively pure diethyl aluminum hydride and
triethyl aluminum by fractionation at a pressure of below 55 other processes in which ethylene is added to a dialkyl
aluminum hydride. In the latter case, ethylene is well
10 mm. mercury, and at a temperature of from 60 to
known to exhibit a tendency to form higher alkyl groups
100° C. and this tendency is affected by the temperature of opera
~"I‘he diethyl aluminum hydride fraction is then reacted
tion. In the present process, ethylene exhibits virtually
with aluminum chloride in equimolar proportions, re
sulting in a virtually stoichiometric yield of diethyl di 60 no tendency to “chain grow” or form longer alkyl groups.
In addition to the peculiar utility of the new compounds
aluminum trichlorohydride, which is then reacted with
of the invention, with respect to the ellicient and eco~
ethylene as in Example I, forming ethyl aluminum sesqui
nomical formation of an alkyl aluminum sesquichloride,
chloride, (Cilli), Al=Cl,. This product is then treated
these materials are highly suitable as economical and
with ?nely subdivided alkali metal, resulting in the re
convenient sources of organoaluminum materials for pur
duction thereof to a pure grade of triethyl aluminum,
which is combined or mixed with the triethyl aluminum
fraction from the original operation, if ‘desired, providing
poses such as components of polymerization catalysts, re
ducing agents, and for organic syntheses generally. As
already noted, a particular and highly advantageous
a good overall yield of pure triethyl aluminum.
utility is their use as intermediates in an overall process
In contrast, when the equimolar mixture of triethyl
aluminum and diethyl aluminum hydride, for the ?rst 70 for producing a highly selective and puri?ed grade of
a tialkyl aluminum by a sequence of operations as in
step of the operation, is treated, as is, with ethylene pres
Example IV. In addition to the formation of, for ex
sure, it is found that a substantial quantity of higher alkyl
ample, a very pure grade of triethyl aluminum, the re
substituents are produced in the product. 0n the other
action of the dialkyl dialuminum trichlorohydrides with
hand, when ethylene is reacted with the separated diethyl
dialuminum trichlorohydride, virtually no chain growth 75 ole?n having an odd number of carbon groups provides
a highly effective route to the formation of straight chain
substituents having an odd number of carbon atoms.
In addition to the technique illustrated by Example
IV wherein the trialkyl aluminum and dialkyl aluminum
hydride of a ?rst synthesis operation are separated, for
separate formation, from the latter, of a dialkyl d-ialu
minum trichlorohydride, this operation can be conducted
without such a separatory step. In such instances, suf
?cient aluminum chloride is mixed with the ?rst step
product mixture to correspond to the dialkyl aluminum 10
dialkyl aluminum hydride is di-n-pentyl aluminum hy
6. The process of making an alkyl aluminum sesqui
chloride having alkyl groups of from one to ?ve car
bon atoms, comprising reacting together, in approxi
mately equimolal proportions, and at a temperature of
not over about 130° 0., aluminum chloride and a dialkyl
aluminum hydride having alkyl groups of from one to
?ve carbons atoms, and forming thereby a homogeneous
liquid composition having the empirical formula
hydride, whereby a mixture including the trialkyl alu
minum and dialkyl dialuminum trichlorohydride is pro
Some of the aluminum chloride will also com
plex with the trialkyl aluminum. Reaction of this mix
wherein R represents the alkyl groups of the dialkyl
aluminum hydride, and then reacting said composition
ture with a desired ole?n results in a selective, or partly 15 with an ole?n having up to ?ve carbon atoms, and form
selective reaction thereof with the dialkyl dialuminum
trichlorohydride component, resulting in a mixture in
cluding the trialkyl aluminum with alkyl aluminum chlo
rides, the composition of which is determined by the
starting material compositions. In the case of ethylene, 20
ing the alkyl aluminum sesquichloride.
7. The process of claim 6 further de?ned in that the
dialkyl aluminum hydride is diethyl aluminum hydride
and the ole?n is ethylene.
8. A process for making triethyl aluminum substan
as the added ole?n, there is some tendency for reaction
to also occur with the trialkyl aluminum component,
tially free of hydrocarbon radicals of more than 2 car
desired. Thus butene-2, isobutylene, pentene-Z, Z-methyl
butene-l, 2-methyl butene-2, 2-methyl pentene-l, 2-ethyl'
alkaline reducing metal.
employed as reactants.
in R is an alkyl radical of 1 to 5 carbon atoms.
bon atoms, comprising forming a mixture of diethyl alu
minum hydride and triethyl aluminum by the direct re
forming longer alkyl substituent groups. When the added
action of aluminum, hydrogen and ethylene, then sepa
ole?n is, however, a higher ole?n, this tendency is much
25 rating the diethyl aluminum hydride of said mixture and
less apparent.
reacting with aluminum chloride in approximately equi
With respect to the ole?ns suitable for reacting with
molecular proportions thereto, forming thereby a cor
the dialkyl dialuminum trichlorohydride compounds, the
responding quantity of a composition having the empirical
simple lower alkene compounds are most common, such
formula of (C2H5)2AlzCl3H, and then reacting said
as ethylene, propylene, butene-l, pentene-l, hexene-l
and the like. However, alpha branched chain ole?ns, 30 composition with ethylene and producing thereby ethyl
aluminum sesquichloride, and then reducing said ethyl
or internal ole?ns, both straight and branched, are also
aluminum sesquichloride to triethyl aluminum with an
fully operable when the corresponding alkyl groups are
9. As a new composition, a homogeneous liquid ma
hexene-l, and other ole?n hydrocarbons can be effectively 35 terial having the empirical composition R2Al2Cl3H, where
10. As a new composition, the homogeneous liquid
Having fully described the invention and the best mode
having the empirical formula (C2H5)2Al2Cl3H.
of working the several embodiments thereof, what is
11. As a new composition, the homogeneous liquid
claimed is:
1. The process of making a composition having the 40 having the empirical formula (CHahAlaClsH.
12. As a new composition, the homogeneous liquid
empirical formula RgAlgClgH, wherein R is an alkyl hy
having the empirical formula (i-C4H9)2Al2Cl3H.
drocarbon radical having from 1 to 5 carbon atoms,
comprising reacting together, at a temperature of not over
References Cited in the ?le of this patent
about 130° C., a. dialkyl aluminum hydride, wherein the 45
alkyl radicals correspond to said R, and aluminum chlo
ride, in approximately equimolal proportions.
2. The process of claim 1 further de?ned in that the
dialkyl aluminum hydride is diethyl aluminum hydride.
Ziegler et al ___________ .... Mar. 26, 1957
Ziegler et al ___________ __ Mar. 11, 1958
Ziegler et al _____ __.‘ ____ __ May 20, 1958
3. The process of claim 1 further de?ned in that the 50
dialkyl aluminum hydride is dirnethyl aluminum hydride.
4. The process of claim 1 further de?ned in that the
dialkyl aluminum hydride is di-isobutyl aluminum hydride.
5. The process of claim 1 further de?ned in that the
Grosse et al.: J. Organic Chemistry, vol. 5 (1940),
pp. ‘109-111.
Coates: “Organo-Metallic Compounds” (1956), p. 81.
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