Title: Manufacture of trialkylaluminum compounds and .alpha.-alcohols
Abstract: Higher trialkylaluminum compounds may be made by forming .alpha.-olefin by oligomerizing ethylene using a transition metal containing catalyst, reacting the .alpha.-olefins formed with a lower trialkylaluminum compound to form higher trialkylaluminum compound(s) These may optionally be oxidized, as with oxygen, to form higher trialkoxyaluminum compound, which in turn may be hydrolyzed to .alpha.-alcohols. In one variation of the process lower .alpha.-olefins and higher (relatively) .alpha.-alcohols may be formed and isolated. Higher trialkylaluminum compounds and .alpha.-alcohols are useful as chemical intermediates, while lower .alpha.-olefins are useful as monomers for polyolefins.
Patent Number: 6,861,545 Issued on 03/01/2005 to Citron
| Inventors:
|
Citron; Joel David (Wilmington, DE)
|
| Assignee:
|
E. I. du Pont de Nemours and Company (Wilmington, DE)
|
| Appl. No.:
|
494060 |
| Filed:
|
April 28, 2004 |
| PCT Filed:
|
December 12, 2002
|
| PCT NO:
|
PCT/US02/39635
|
| 371 Date:
|
April 28, 2004
|
| 102(e) Date:
|
April 28, 2004
|
| PCT PUB.NO.:
|
WO03/05388 |
| PCT PUB. Date:
|
July 3, 2003 |
| Current U.S. Class: |
556/187; 556/190; 568/840; 568/911; 568/922 |
| Intern'l Class: |
C07F 005//06; C07C 027//00 |
| Field of Search: |
556/187,190
568/840,911,922
|
References Cited [Referenced By]
U.S. Patent Documents
| 2959607 | Nov., 1960 | Werber et al.
| |
| 3180881 | Apr., 1965 | Zosel et al.
| |
| 3207770 | Sep., 1965 | Zieglet et al.
| |
| 3388143 | Jun., 1968 | Rose.
| |
| 3389161 | Jun., 1968 | Kottong et al.
| |
| 3474122 | Oct., 1969 | Ichiki et al.
| |
| 3487097 | Dec., 1969 | Davis.
| |
| 3494948 | Feb., 1970 | Ichiki et al.
| |
| 3644564 | Feb., 1972 | van Zwet et al.
| |
| 3775456 | Nov., 1973 | Acciarri et al.
| |
| 3829520 | Aug., 1974 | Ferrell.
| |
| 4689437 | Aug., 1987 | Murray.
| |
| 4918254 | Apr., 1990 | Diefenbach et al.
| |
| 5210338 | May., 1993 | Samsel.
| |
| 5276220 | Jan., 1994 | Samsel et al.
| |
| 5278330 | Jan., 1994 | Lin et al.
| |
| 5382738 | Jan., 1995 | Reagen et al.
| |
| 5430165 | Jul., 1995 | Cox et al.
| |
| 5536859 | Jul., 1996 | Lin et al.
| |
| 6103946 | Aug., 2000 | Brookhart, III et al.
| |
Other References
J. I. Kroschwitz, et al., Ed., Encyclopedia of Chemical Technology, 4th
Ed., vol. 1, John Wiley & Sons, New York, 1991, p. 834-903.
B. Elvers, et al., Ed., Ullmann's Encycolpedia of Industrial Chemistry, 5th
Ed., vol. A28, 1996, p. 505-508.
W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry,
5th Ed., vol. A1, VCH Verlagsgesellschaft mbH, Weinheim, 1985, p. 545-549.
PCT/US02/39635 International Search Report dated Jun. 16, 2003.
|
Primary Examiner: Nazario-Gonzalez; Porfirio
Parent Case Text
This application claims the benefit of Provisional Application No.
60/340,443, filed Dec. 12, 2001.
Claims
What is claimed is:
1. A process for the manufacture of higher trialkylaluminum compounds,
comprising, forming an .alpha.-olefin or mixture of .alpha.-olefins by
oligomerization of ethylene using a transition metal containing
oligomerization catalyst system, then contacting said .alpha.-olefin or
said mixture of .alpha.-olefins with a lower trialkylaluminum compound at
a sufficient temperature, for a sufficient amount of time, to form a
higher trialkylaluminum compound.
2. A process for the manufacture of .alpha.-alcohols, comprising:
(1) forming an .alpha.-olefin or mixture of .alpha.-olefins by
oligomerization of ethylene using a transition metal containing
oligomerization catalyst system;
(2) contacting said .alpha.-olefin or said mixture of .alpha.-olefins with
a lower trialkylaluminum compound at a sufficient temperature, for a
sufficient amount of time, to form a higher trialkylaluminum compound or a
mixture thereof;
(3) contacting said higher trialkylaluminum compound or a mixture thereof
with oxygen or other suitable oxidizing agent to form a higher
trialkoxyaluminum compound or a mixture thereof; and
(4) hydrolyzing said higher trialkoxyaluminum compound or a mixture thereof
to form an .alpha.-alcohol or a mixture thereof.
3. The process as recited in claim 1 or 2 wherein said mixture of olefins
is used and is a homologous series of .alpha.-olefins.
4. The process as recited in claim 1 or 2 wherein said homologous series of
.alpha.-olefins is produced in an oligomerization reaction which has a
Schulz-Flory constant of about 0.6 to about 0.8.
5. The process as recited in claim 1, 2, 3 or 4 wherein said transition
metal containing oligomerization catalyst system comprises an iron complex
of a diimine of a 2,6-diacylpyridine or a 2,6-pyridinedicarboxaldehyde.
6. The process as recited in claim 5 wherein said iron complex is a
compound of the formula
##STR9##
wherein:
R.sup.1, R.sup.2 and R.sup.3 are each independently hydrogen, hydrocarbyl,
substituted hydrocarbyl or an inert functional group, provided that any
two of R.sup.1, R.sup.2 and R.sup.3 vicinal to one another taken together
may form a ring;
R.sup.4 and R.sup.5 are each independently hydrogen, hydrocarbyl,
substituted hydrocarbyl or an inert functional group;
R.sup.6 and R.sup.7 are each independently a substituted aryl having a
first ring atom bound to the imino nitrogen, provided that:
in R.sup.6, a second ring atom adjacent to said first ring atom is bound to
a halogen, a primary carbon group, a secondary carbon group or a tertiary
carbon group; and further provided that
in R.sup.6, when said second ring atom is bound to a halogen or a primary
carbon group, none, one or two of the other ring atoms in R.sup.6 and
R.sup.7 adjacent to said first ring atom are bound to a halogen or a
primary carbon group, with the remainder of the ring atoms adjacent to
said first ring atom being bound to a hydrogen atom; or
in R.sup.6, when said second ring atom is bound to a secondary carbon
group, none, one or two of the other ring atoms in R.sup.6 and R.sup.7
adjacent to said first ring atom are bound to a halogen, a primary carbon
group or a secondary carbon group, with the remainder of the ring atoms
adjacent to said first ring atom being bound to a hydrogen atom; or
in R.sup.6, when said second ring atom is bound to a tertiary carbon group,
none or one of the other ring atoms in R.sup.6 and R.sup.7 adjacent to
said first ring atom are bound to a tertiary carbon group, with the
remainder of the ring atoms adjacent to said first ring atom being bound
to a hydrogen atom.
7. The process as recited in claim 1 or 2 wherein a single .alpha.-olefin
is used.
Description
FIELD OF THE INVENTION
.alpha.-Olefins are manufactured by oligomerizing ethylene using a
transition metal containing catalyst, the .alpha.-olefins are converted to
higher trialkylaluminum compounds by contacting the .alpha.-olefins with a
lower trialkylaluminum compound usually with heating. The higher
trialkylaluminum compounds which are formed may be reacted with oxygen to
form the corresponding trialkoxyaluminum compounds, which can be
hydrolyzed to form .alpha.-alcohols.
TECHNICAL BACKGROUND
Higher trialkylaluminum compounds (HTAC), R.sup.30.sub.3 Al (I), in which
the alkyl groups contain more than 4 carbon atoms, are useful particularly
as chemical intermediates for the synthesis of .alpha.-alcohols of the
formula R.sup.32 R.sup.33 CHCH.sub.2 OH (II) wherein R.sup.32 is hydrogen
or alkyl and R.sup.33 is alkyl. .alpha.-Alcohols containing 10 to 20
carbon atoms are useful as intermediates for the synthesis of detergents
and other surfactants. Therefore improved methods of making (I) and/or
(II) are commercial interest.
Generally speaking, linear .alpha.-alcohols are often made utilizing the
following steps, see for instance B. Elvers, et al., Ed., Ullmann's
Encyclopedia of Industrial Chemistry, 5.sup.th Ed., Vol. A28, 1996, p.
505-508 and references therein, and J. I. Kroschwitz, et al., Ed,
Encyclopedia of Chemical Technology, 4.sup.th Ed., Vol. 1, John Wiley &
Sons, New York, p. 894-903 and references therein, both of which are
hereby included by reference.
(a) Triethylaluminum is produced by contacting under relatively high
pressure and temperature a mixture of aluminum, hydrogen, ethylene and
triethylaluminum (TEA). "New" TEA is produced in the reactor. The liquid
product is removed from the reactor, filtered and some is recycled back to
the TEA reactor and some is used in the next step.
(b) The TEA used in the next step is now mixed with more ethylene under
high pressure and with heating. The ethylene adds sequentially
(oligomerizes) to each of the original ethyl groups in the TEA, forming
HTACs.
(c) The product of the previous step is mixed with oxygen (a highly
exothermic reaction) to form the corresponding trialkoxyaluminum
compounds.
(d) The trialkoxyaluminum compounds are hydrolyzed to form an alpha-alcohol
mixture and alumina.
This process is effective but requires the use of high temperatures and
pressures in two steps, and in these two steps pyrophoric alkylaluminum
compounds are present, and so these steps must be done very carefully to
protect the plant and workers safety. This adds to the cost of the overall
process. Processes which would minimize such steps, and/or require less
capital investment, and/or have lower operating costs, would therefore be
favored.
U.S. Pat. No. 3,207,770 and W. Gerhartz, et al., Ed., Ullmann's
Encyclopedia of Industrial Chemistry, 5.sup.th Ed., Vol. A1, VCH
Verlagsgesellschaft mbH, Weinheim, 1985, p. 545-549, describe the reaction
of lower trialkylaluminum compounds (LTAC) with (usually) higher olefins.
The use of higher olefins made with transition metal containing ethylene
oligomerization catalysts is not mentioned.
U.S. Pat. Nos. 6,103,946,4,689,437, 3,644,564 and 5,382,738, which are all
hereby included by reference, describe the use of various transition metal
containing catalysts to make olefins or mixtures of olefins by
oligomerizing ethylene. No mention is made of making trialkylaluminum
compounds or .alpha.-alcohols from those trialkylaluminum compounds.
B. Elvers, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry,
5.sup.th Ed., Vol. A28, VCH Verlagsgesellschaft mbH, Weinheim, 1996, p.
505-508 and references therein, describe the overall commercial synthesis
processes for making .alpha.-alcohols, including the synthesis processes
for making HTACs.
U.S. Pat. Nos. 2,959,607, 3,180,881,3,389,161, 3,474,122,
3,494,948,4,918,254 and 5,278,330 describe a process for the production of
higher alkylaluminum compounds from (relatively) lower alkylaluminum
compounds and one or more higher olefins. The use of a transition metal
containing ethylene oligomerization catalyst to form olefins is not
described. U.S. Pat. Nos. 2,959,607 and 5,278,330 also describe the steps
of oxidation of trialkylaluminums and the hydrolysis of the resulting
trialkoxyaluminum compounds.
SUMMARY OF THE INVENTION
This invention concerns, a process for the manufacture of higher
trialkylaluminum compounds, comprising, forming an .alpha.-olefin or
mixture of o-olefins by oligomerization of ethylene using a transition
metal containing oligomerization catalyst system, then contacting said
.alpha.-olefin or said mixture of .alpha.-olefins with a lower
trialkylaluminum compound at a sufficient temperature, for a sufficient
amount of time, to form a higher trialkylaluminum compound.
This invention also concerns a process for the manufacture of
.alpha.-alcohols, comprising:
(1) forming an .alpha.-olefin or mixture of .alpha.-olefins by
oligomerization of ethylene using a transition metal containing
oligomerization catalyst system;
(2) contacting said .alpha.-olefin or said mixture of .alpha.-olefins with
a lower trialkylaluminum compound at a sufficient temperature, for a
sufficient amount of time, to form a higher trialkylaluminum compound or a
mixture thereof;
(3) contacting said higher trialkylaluminum compound or a mixture thereof
with oxygen or other suitable oxidizing agent to form a higher
trialkoxyaluminum compound or a mixture thereof; and
(4) hydrolyzing said higher trialkoxyaluminum compound or a mixture thereof
to form an .alpha.-alcohol or a mixture thereof.
DETAILS OF THE INVENTION
Herein certain terms are used, and some of them are defined below:
By a "lower trialkylaluminum compound" (LTAC) is meant a compound of the
formula R.sup.36.sub.3 Al (VI), in which each of R.sup.36 contains 6 or
fewer carbon atoms, preferably 2-4 carbon atoms, and each R.sup.36 is
independently alkyl. It is to be understood that the LTAC may contain
impurities such as hydrogen bound to aluminum. Preferred LTACs are
triethylaluminum and tri-i-butylaluminum.
By a "higher trialkylaluminum compound" (HTAC) is meant a compound of the
formula R.sup.31.sub.3 Al (I), in which each of R.sup.31 contains 6 or
more carbon atoms, preferably 8 or more carbon atoms, each R.sup.1 is
Independently R.sup.32 R.sup.33 CHCH.sub.2 -- wherein R.sup.32 is hydrogen
or alkyl, R33 is alkyl, and each R.sup.31 contains an even number of
carbon atoms. Preferably R.sup.32 is hydrogen and/or R33 is n-alkyl. It is
to be understood that the HTAC may contain impurities such as hydrogen
bound to aluminum or alkyl groups having less than 4 carbon atoms bound to
aluminum, but at least 50 mole percent, more preferably at least 75 mole
percent, and especially preferably at least 90 mole percent of the groups
bound to aluminum are R.sup.31 --.
By a "higher trialkoxyaluminum compound" (HTAC) is meant a compound of the
formula (R.sup.31 O).sub.3 Al (III), in which each of R.sup.31 contains 4
or more carbon atoms, preferably 6 or more carbon atoms, each R.sup.31 is
independently R.sup.32 R33CHCH.sub.2 -- wherein R.sup.32 is hydrogen or
alkyl, R.sup.33 is alkyl, and each R.sup.31 contains an even number of
carbon atoms. Preferably R.sup.32 is hydrogen and/or R.sup.33 is n-alkyl.
It is to be understood that the higher trialkoxyaluminum compound(s) may
contain impurities such as alkoxy groups having less than 4 carbon atoms
bound to aluminum, but at least 50 mole percent, more preferably at least
75 mole percent, and especially preferably at least 90 mole percent of the
groups bound to aluminum are R.sup.31 O--.
By an .alpha.-alcohol is meant a compound of the formula R.sup.32 R.sup.33
CHCH.sub.2 OH (II), wherein R.sup.32 is hydrogen or alkyl, R.sup.33 is
alkyl, and (II) contains an even number of carbon atoms. Preferably
R.sup.32 is hydrogen and/or R.sup.33 is n-alkyl.
By a transition metal containing ethylene oligomerizaton catalyst is meant
a catalyst system which contains an element of Groups 3-12 (IUPAC
notation) in the catalyst system, and which Is capable of oligomerizing
ethylene to an .alpha.-olefin. Transition metal containing "inert"
supports are not considered part of the catalyst system. By "inert" in
this context is meant that the support is believed to function merely as a
physical support and does not actually take part chemically in the
oligomerization process.
By an ".alpha.-olefin" is meant a compound of the formula H.sub.2
C.dbd.CR.sup.32 R.sup.33 (IV) wherein R.sup.32 is hydrogen or alkyl,
R.sup.33 is alkyl, and (IV) contains an even number of carbon atoms. It is
preferred than R.sup.32 is hydrogen and/or R.sup.33 is n-alkyl.
Transition metal containing catalysts that oligomerize ethylene to
.alpha.-olefins may be divided into two classes, those that produce a
mbdure of c-olefins and those that produce (mostly) a single
.alpha.-olefin. The former are exemplified by those catalysts found in
U.S. Pat. Nos. 6,103,946,2,787,626, 3,032,574, 3,207,770, 3,644,564,
3,647,915 and 3,647,915, all of which are hereby included by reference.
These oligomerizations herein may be run under conditions described in
these references and in other references for other such types of
catalysts. Typically these catalysts produce a homologous series of
.alpha.-olefins that differ by two carbon atoms. The amounts of each
olefin in the homologous series typically follow a so called Schulz-Flory
distribution, which uses a factor K from the Schulz-Flory theory (see for
instance B. Elvers, et al., Ed. Ullmann's Encyclopedia of Industrial
Chemistry, Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p.
243-247 and 275-276, which is hereby included by reference). This is
defined as:
K=n(C.sub.n+2 olefin)/n(C.sub.n olefin)
wherein n(C.sub.n olefin) is the number of moles of olefin containing n
carbon atoms, and n(C.sub.n+2 olefin) is the number of moles of olefin
containing n+2 carbon atoms, or in other words the next higher oligomer of
C.sub.n olefin. From this can be determined the weight (mass) fractions of
the various olefins in the resulting oligomeric reaction product mixture.
The K factor is preferred to be in the range of about 0.6 to about 0.8
A preferred type of ethylene oligomerization catalyst is described in U.S.
Pat. No. 6,103,946 and World Patent Applications 01/58874, 00/42123,
00/76659 and 01/19513, all of which are hereby included by reference, and
similar iron tridentate catalysts which result in the formation of
.alpha.-olefins. These catalysts utilize selected diimines of
2,6-diacylpyridines or 2,6-pyridinedicarboxaldehydes as part of the
ethylene oligomerization catalyst system, particularly as iron complexes.
Such a preferred active ethylene oligomerization catalyst comprises an iron
complex of a compound of the formula
##STR1##
wherein:
R.sup.1, R.sup.2 and R.sup.3 are each independently hydrogen, hydrocarbyl,
substituted hydrocarbyl or an inert functional group, provided that any
two of R.sup.1, R.sup.2 and R.sup.3 vicinal to one another taken together
may form a ring;
R.sup.4 and R.sup.5 are each independently hydrogen, hydrocarbyl,
substituted hydrocarbyl or an inert functional group;
R.sup.6 and R.sup.7 are each independently a substituted aryl having a
first ring atom bound to the imino nitrogen, provided that:
in R.sup.6, a second ring atom adjacent to said first ring atom is bound to
a halogen, a primary carbon group, a secondary carbon group or a tertiary
carbon group; and further provided that
in R.sup.6, when said second ring atom is bound to a halogen or a primary
carbon group, none, one or two of the other ring atoms in R.sup.6 and
R.sup.7 adjacent to said first ring atom are bound to a halogen or a
primary carbon group, with the remainder of the ring atoms adjacent to
said first ring atom being bound to a hydrogen atom; or
in R.sup.6, when said second ring atom is bound to a secondary carbon
group, none, one or two of the other ring atoms in R.sup.6 and R.sup.7
adjacent to said first ring atom are bound to a halogen, a primary carbon
group or a secondary carbon group, with the remainder of the ring atoms
adjacent to said first ring atom being bound to a hydrogen atom; or
in R.sup.6, when said second ring atom is bound to a tertiary carbon group,
none or one of the other ring atoms in R.sup.6 and R.sup.7 adjacent to
said first ring atom are bound to a tertiary carbon group, with the
remainder of the ring atoms adjacent to said first ring atom being bound
to a hydrogen atom.
A "hydrocarbyl group" is a univalent group containing only carbon and
hydrogen. As examples of hydrocarbyls may be mentioned unsubstituted
alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred
that hydrocarbyl groups (and alkyl groups) herein contain 1 to about 30
carbon atoms.
By "substituted hydrocarbyl" herein is meant a hydrocarbyl group that
contains one or more substituent groups which are inert under the process
conditions to which the compound containing these groups is subjected
(e.g., an inert functional group, see below). The substituent groups also
do not substantially detrimentally interfere with the oligomerization
process or operation of the oligomerization catalyst, system. If not
otherwise stated, it is preferred that substituted hydrocarbyl groups
herein contain 1 to about 30 carbon atoms. Included in the meaning of
"substituted" are rings containing one or more heteroatoms, such as
nitrogen, oxygen and/or sulfur. In a substituted hydrocarbyl, all of the
hydrogens may be substituted, as in trifluoromethyl.
By "(inert) functional group" herein is meant a group, other than
hydrocarbyl or substituted hydrocarbyl, which is inert under the process
conditions to which the compound containing the group is subjected. The
functional groups also do not substantially deleteriously interfere with
any process described herein that the compound in which they are present
may take part in. Examples of functional groups include halo (fluoro,
chloro, bromo and iodo), and ether such as --OR.sup.50 wherein R.sup.50 is
hydrocarbyl or substituted hydrocarbyl. In cases in which the functional
group may be near a transition metal atom, the functional group alone
should not coordinate to the metal atom more strongly than the groups in
those compounds that are shown as coordinating to the metal atom, that is
they should not displace the desired coordinating group.
By a "primary carbon group" herein is meant a group of the formula
--CH.sub.2 - - - , wherein the free valence - - - is to any other atom,
and the bond represented by the solid line is to a ring atom of a
substituted aryl to which the primary carbon group is attached. Thus the
free valence - - - may be bonded to a hydrogen atom, a halogen atom, a
carbon atom, an oxygen atom, a sulfur atom, etc. In other words, the free
valence - - - may be to hydrogen, hydrocarbyl, substituted hydrocarbyl or
a functional group. Examples of primary carbon groups include --CH.sub.3,
--CH.sub.2 CH(CH.sub.3).sub.2, --CH.sub.2 Cl, --CH.sub.2 C.sub.6 H.sub.5,
--OCH.sub.3 and --CH.sub.2 OCH.sub.3.
By a secondary carbon group is meant the group
##STR2##
wherein the bond represented by the solid line is to a ring atom of a
substituted aryl to which the secondary carbon group is attached, and both
free bonds represented by the dashed lines are to an atom or atoms other
than hydrogen. These atoms or groups may be the same or different. In
other words the free valences represented by the dashed lines may be
hydrocarbyl, substituted hydrocarbyl or inert functional groups. Examples
of secondary carbon groups include --CH(CH.sub.3).sub.2, --CHCl.sub.2,
--CH(C.sub.6 H.sub.5).sub.2, cyclohexyl, --CH(CH.sub.3)OCH.sub.3, and
--CH.dbd.CCH.sub.3.
By a "tertiary carbon group" is meant a group of the formula
##STR3##
wherein the bond represented by the solid line is to a ring atom of a
substituted aryl to which the tertiary carbon group is attached, and the
three free bonds represented by the dashed lines are to an atom or atoms
other than hydrogen. In other words, the bonds represented by the dashed
lines are to hydrocarbyl, substituted hydrocarbyl or inert functional
groups. Examples of tetiary carbon groups include --C(CH.sub.3).sub.3,
--C(C.sub.6 H.sub.5).sub.3, --CC.sub.3, --CF.sub.3,
--C(CH.sub.3)OCH.sub.3, --C.ident.CH, --C(CH.sub.3).sub.2 CH.dbd.CH.sub.2,
aryl and substituted aryl such as phenyl and 1-adamantyl.
By "aryl" is meant a monovalent aromatic group in which the free valence is
to the carbon atom of an aromatic ring. An aryl may have one or more
aromatic rings which may be fused, connected by single bonds or other
groups.
By "substituted aryl" is meant a monovalent aromatic group substituted as
set forth in the above definition of "substituted hydrocarbyl".
Similar to an aryl, a substituted aryl may have one or more aromatic rings
which may be fused, connected by single bonds or other groups; however, is
when the substituted aryl has a heteroaromatic ring, the free valence in
the substituted aryl group can be to a heteroatom (such as nitrogen) of
the heteroaromatic ring instead of a carbon.
By a "first ring atom in R.sup.6 and R.sup.7 bound to an imino nitrogen
atom" is meant the ring atom in these groups bound to an imino nitrogen
shown in (I), for example
##STR4##
the atoms shown in the 1-position in the rings in (II) and (III) are the
first ring atoms bound to an imino carbon atom (other groups which may be
substituted on the aryl groups are not shown). Ring atoms adjacent to the
first ring atoms are shown, for example, in (IV) and (V), where the open
valencies to these adjacent atoms are shown by dashed lines (the
2,6-positions in (IV) and the 2,6positions in (V)).
##STR5##
In one preferred embodiment of (I), R.sup.6 is
##STR6##
and R.sup.7 is
##STR7##
wherein:
R.sup.8 is a halogen, a primary carbon group, a secondary carbon group or a
tertiary carbon group; and
R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 are
each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a
functional group; provided that:
when R.sup.8 is a halogen or primary carbon group none, one or two of
R.sup.12, R.sup.13 and R.sup.17 are a halogen or a primary carbon group,
with the remainder of R.sup.12, R.sup.13 and R.sup.17 being hydrogen; or
when R.sup.8 is a secondary carbon group, none or one of R.sup.12, R.sup.13
and R.sup.17 is a halogen, a primary carbon group or a secondary carbon
group, with the remainder of R.sup.12, R.sup.13 and R.sup.17 being
hydrogen; or
when R.sup.8 is a tertiary carbon group, none or one of R.sup.12, R.sup.13
and R.sup.17 is tertiary carbon group, with the remainder of R.sup.12,
R.sup.13 and R.sup.17 being hydrogen;
and further provided that any two of R.sup.8, R.sup.9, R.sup.10, R.sup.11,
R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 vicinal to
one another, taken together may form a ring.
In the above formulas (VI) and (VII), R.sup.8 corresponds to the second
ring atom adjacent to the first ring atom bound to the imino nitrogen, and
R.sup.12, R.sup.13 and R.sup.17 correspond to the other ring atoms
adjacent to the first ring atom.
In compounds (I) containing (VI) and (VII), it is particularly preferred
that:
if R.sup.8 is a primary carbon group, R.sup.13 is a primary carbon group,
and R.sup.12 and R.sup.17 are hydrogen; or
if R.sup.8 is a secondary carbon group, R.sup.13 is a primary carbon group
or a secondary carbon group, more preferably a secondary carbon group, and
R.sup.12 and R.sup.17 are hydrogen; or
if R.sup.8 is a tertiary carbon group (more preferably a trihalo tertiary
carbon group such as a trihalomethyl), R.sup.13 is a tertiary carbon group
(more preferably a trihalotertiary group such as a trihalomethyl), and
R.sup.12 and R.sup.17 are hydrogen; or
if R.sup.8 is a halogen, R.sup.13 is a halogen, and R.sup.12 and R.sup.17
are hydrogen.
In all specific preferred compounds (I) in which (VI) and (VII) appear, it
is preferred that R.sup.1, R.sup.2 and R.sup.3 are hydrogen; and/or
R.sup.4 and R.sup.5 are methyl. It is further preferred that:
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and
R.sup.17 are all hydrogen; R.sup.13 is methyl; and R.sup.8 is a primary
carbon group, more preferably methyl; or
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and
R.sup.17 are all hydrogen; R.sup.13 is ethyl; and R.sup.8 is a primary
carbon group, more preferably ethyl; or
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and
R.sup.17 are all hydrogen; R.sup.13 is isopropyl; and R.sup.8 is a primary
carbon group, more preferably isopropyl; or
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and
R.sup.17 are all hydrogen; R.sup.13 is n-propyl; and R.sup.8 is a primary
carbon group, more preferably n-propyl; or
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and
R.sup.17 are all hydrogen; R.sup.13 is chloro; and R.sup.8 is a halogen,
more preferably chloro; or
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and
R.sup.17 are all hydrogen; R.sup.13 is trihalomethyl, more preferably
trifluoromethyl; and R.sup.8 is a trihalomethyl, more preferably
trifluoromethyl.
In another preferred embodiment of (I), R.sup.6 and R.sup.7 are,
respectively
##STR8##
wherein:
R.sup.18 is a halogen, a primary carbon group, a secondary carbon group or
a tertiary carbon group; and
R.sup.19, R.sup.20, R.sup.23 and R.sup.24 are each independently hydrogen,
hydrocarbyl, substituted hydrocarbyl or a functional group;
Provided that:
when R.sup.18 is a halogen or primary carbon group none, one or two of
R.sup.21, R.sup.22 and R.sup.25 are a halogen or a primary carbon group,
with the remainder of R.sup.21, R.sup.22 and R.sup.25 being hydrogen;
when R.sup.18 is a secondary carbon group, none or one of R.sup.21, R.sup.2
and R.sup.25 is a halogen, a primary carbon group or a secondary carbon
group, with the remainder of R.sup.21, R.sup.22 and R.sup.25 being
hydrogen;
when R.sup.18 is a tertiary carbon group, none or one of R.sup.21, R.sup.22
and R.sup.25 is a tertiary carbon group, with the remainder of R.sup.21,
R.sup.22 and R.sup.25 being hydrogen;
and further provided that any two of R.sup.18, R.sup.19, R.sup.20,
R.sup.21, R.sup.22, R.sup.23, R.sup.24 and R.sup.25 vicinal to one
another, taken together may form a ring.
In the above formulas (VII) and (IX), R.sup.18 corresponds to the second
ring atom adjacent to the first ring atom bound to the imino nitrogen, and
R.sup.21, r.sup.22 and R.sup.25 correspond to the other ring atoms
adjacent to the first ring atom.
In compounds (I) containing (VIII) and (IX), it is particularly preferred
that
if R.sup.18 is a primary carbon group, R.sup.22 is a primary carbon group,
and R.sup.21 and R.sup.25 are hydrogen; or
if R.sup.18 is a secondary carbon group, R.sup.22 is a primary carbon group
or a secondary carbon group, more preferably a secondary carbon group, and
R.sup.21 and R.sup.25 are hydrogen; or
if R.sup.18 is a tertiary carbon group (more preferably a trihalo tertiary
carbon group such as a trihalomethyl), R.sup.22 is a tertiary carbon group
(more preferably a trihalotertiary group such as a trihalomethyl), and
R.sup.21 and R.sup.5 are hydrogen; or
if R.sup.18 is a halogen, R.sup.22 is a halogen, and R.sup.21 and R.sup.25
are hydrogen.
In all specific preferred compounds (I) in which (VIII) and (IX) appear, it
is preferred that R.sup.1, R.sup.2 and R.sup.3 are hydrogen; and/or
R.sup.4 and R.sup.5 are methyl. It is further preferred that:
R.sup.19, R.sup.20, R.sup.21, R.sup.23 and R.sup.24 are all hydrogen;
R.sup.22 is methyl; and R.sup.18 is a primary carbon group, more
preferably methyl; or
R.sup.19, R.sup.20, R.sup.21, R.sup.23 and R.sup.24 are all hydrogen;
R.sup.22 is ethyl; and R.sup.18 is a primary carbon group, more preferably
ethyl; or
R.sup.19, R.sup.20, R.sup.21, R.sup.23 and R.sup.24 are all hydrogen;
R.sup.22 is isopropyl; and R.sup.18 is a primary carbon group, more
preferably isopropyl; or
R.sup.19, R.sup.20, R.sup.21, R.sup.23 and R.sup.24 are all hydrogen;
R.sup.22 is n-propyl; and R.sup.18 is a primary carbon group, more
preferably n-propyl; or
R.sup.19, R.sup.20, R.sup.21, R.sup.23 and R.sup.24 are all hydrogen;
R.sup.22 is chloro or bromo;
and R.sup.18 is a halogen, more preferably chloro or bromo.
The other type of ethylene olgimerization catalyst is typified by that
described in U.S. Pat. No. 5,382,738. Typically these types of catalysts
produce (predominantly) a single olefin having a relatively low number of
carbon atoms, such as 1-hexene or 1-octene. These types of catalysts may
also be used in the present processes to oligomerize ethylene as described
in the references concerning these catalysts.
It is preferred that an ethylene oligomerization catalyst system that
produces a homologous series of o-olefins be used. It is also preferred
that this catalyst system produces a product with a high molar percentage
(at least about 80 mole percent preferably at least about 90 mole percent)
of olefins of the formula H(CH.sub.2 CH.sub.2).sub.n CH.dbd.CH.sub.2 (V),
wherein n is 1 or more.
The production of the HTAC from an LTAC and the .alpha.-olefin(s) can be
carried out by methods known in the art, see for instance U.S. Pat. Nos.
2,959,607, 3,180,881, 3,207,770, 3,389,161, 3,474,122,3,494,948, 4,918,254
and 5,278,330 and W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of
Industrial Chemistry, 5th Ed., Vol. A1, VCH Verlagsgesellschaft mbH,
Weinheim, 1985, p. 545-549, both of which are hereby included by
reference. Typical reaction temperatures are 80.degree. C. to 150.degree.
C. for a period of about 1 hour to about 24 hours. In this reaction it is
sometimes preferred to use an LTAC whose alkyl groups are branched, since
these often are more reactive than LTACs having unbranched alkyl groups.
It is believed that the reaction of the higher olefins with an LTAC is an
equilibrium reaction, for example the reaction between TEA and 1-dodecene
may be written as:
(C.sub.2 H.sub.5).sub.3 A1+3H.sub.3 C(CH.sub.2).sub.9 CH.dbd.CH.sub.2
{character pullout}3H.sub.2 C.dbd.CH.sub.2 +[H.sub.3 C(CH.sub.2).sub.11
].sub.3 Al 1)
During the reaction, which is run at, say, 100.degree. C., the ethylene is
usually volatilized, thereby driving the equilibrium to the right and
resulting in (principally) tri-1-dodecylaluminum. Thus in these reaction
it is preferred to run the reaction above the boiling point of the alkene
which may be derived from the alkyl group of the LTAC. If olefins are
present in the olefin mixture made during the oligomerization of ethylene
which also have low boiling points, they too may be distilled.
This points out an interesting variation of this process which can be used
to make a combination of lower .alpha.-olefins and higher
.alpha.-alcohols. Lower .alpha.-olefin are desirable for use as
comonomers, while it is often the .alpha.-alcohols which contain 10 or
more carbon atoms which are desired. For example if one wanted to isolate
octenes and lower molecular weight .alpha.-olefins from this process, one
would use approximately only enough LTAC only to react with the total
amount of .alpha.-olefins having 10 or more carbon atoms, and the reaction
temperature would be controlled so that it would be above the boiling
point of 1-octene (121.degree. C. at atmospheric pressure), so as to
distill off 1-octene and lower olefins, including the olefin formed from
the LTAC. Conveniently this can be done by using a moderate amount of an
inert solvent (see below), which preferably can be separated from the
.alpha.-alcohols which will eventually be formed by distillation. In this
instance a convenient solvent may be m-xylene (boiling point 139.degree.
C. at atmospheric pressure), much below the atmospheric boiling point of
1-decanol of 229.degree. .degree. C. Thus the overall process may produce
HTAC(s), .alpha.-alcohols, or a mixture of higher .alpha.-alcohols and
(relatively) lower .alpha.-olefins.
It should be pointed out however that the reaction shown in equation 1
above is an ideal one, and other side reactions may take place. For
example one or more of the alkyl groups on the aluminum may be a 2-dodecyl
group instead of a 1-dodecyl group, or 1-dodecene may insert in an already
formed C-Al bond of a 1-dodecyl group to give a branched C.sub.24 alkyl
group attached to aluminum. These are usually relatively minor reactions
when the process is run at optimum conditions (temperature for instance).
So it is possible that changing from the optimum temperature to make the
desired HTAC to also isolate some lower .alpha.-olefins may cause the
HTAC(s) isolated to have a somewhat different composition (more branching
in the alkyl groups for example). These factors may be worked out by
relatively simple experimentation.
Preferably the .alpha.-olefin(s) from the ethylene oligomerization reaction
undergo little or no purification before being put into the process to
make the HTAC If a mixture of .alpha.-olefins are produced they are
preferably not separated. The ethylene oligomerization catalyst may be
deactivated or not (if present it may be deactivated by the usually higher
temperatures of the HTAC forming process). A solvent may be used in the
ethylene oligomerization reaction, and preferably it does not contain
active hydrogen compounds such as water, alcohols or carboxylic acids. If
the solvent does not contain active hydrogen compounds it does not need to
be separated before the reactions to form the HTAC. The solvent may also
be added to the process in which the HTAC is formed. Preferred solvents in
the oligomerization and/or HTAC forming reactions, if any, are nonolefinic
hydrocarbons such as toluene, xylene, octane, cyclohexane, and the like.
The composition of the HTAC(s) produced will depend on the composition of
the .alpha.-olefin (mixture) added to the HTAC forming reaction, and as
noted above the stoichiometry of the HTAC forming reaction and the
temperature at which it is run.
Reaction of the HTAC(s) with oxygen or other oxidizing agent to form higher
trialkoxyaluminum compounds can be carried out as known in the art, see
for instance Elvers, et al., Ed., Ullmann's Encyclopedia of Industrial
Chemistry, 5.sup.th Ed., Vol. A28, VCH Verlagsgesellschaft mbH, Weinheim,
1996, p. 505-508 and references therein, and U.S. Pat. No. 5,278,330 which
is hereby included by reference. Likewise, the hydrolysis of the higher
trialkoxyaluminum compound to form .alpha.-alcohols may be carried out by
methods known in the literature, see for instance Elvers, et al., Ed.,
Ullmann's Encyclopedia of Industrial Chemistry, 5.sup.th Ed., Vol. A28,
VCH Verlagsgesellschaft mbH, Weinheim, 1996, p. 505-508 and references
therein. These methods for oxidation and hydrolysis to form
.alpha.-alcohols are known in the art.
The present process form making the HTAC(s) and/or .alpha.-alcohols result
in less handling of pyrophoric alkylaluminum compounds at high
temperatures and/or pressure, thereby making the process safer and/or
lowering operating cost, and/or lowering investment need for the plant,
when compared to the conventional methods of manufacturing these types of
compounds. Assuming a mixture of homologous .alpha.-olefins is used to
make the HTAC, the product mixture resulting, for example, from making
.alpha.-alcohols may be similar to that obtained with current
manufacturing methods.
The .alpha.-alcohols and .alpha.-olefins (from the reaction forming the
HTAC) produced may be fully or completely purified (separated) by
distillation, as is known in the art.
*
