U.S. patent application number 13/109219 was filed with the patent office on 2011-11-24 for process for oligomerization of olefins that uses a catalytic composition that comprises an organometallic complex that contains an alkoxy ligand that is functionalized by a heteroatom.
This patent application is currently assigned to IFP ENERGIES NOUVELLES. Invention is credited to Fabien GRASSET, Stephane HARRY, Lionel MAGNA, David PRORIOL.
Application Number | 20110287927 13/109219 |
Document ID | / |
Family ID | 43242993 |
Filed Date | 2011-11-24 |
United States Patent
Application |
20110287927 |
Kind Code |
A1 |
GRASSET; Fabien ; et
al. |
November 24, 2011 |
PROCESS FOR OLIGOMERIZATION OF OLEFINS THAT USES A CATALYTIC
COMPOSITION THAT COMPRISES AN ORGANOMETALLIC COMPLEX THAT CONTAINS
AN ALKOXY LIGAND THAT IS FUNCTIONALIZED BY A HETEROATOM
Abstract
The invention describes a process for oligomerization of olefins
into compounds or into a mixture of compounds of general formula
CpH2p with 4.ltoreq.p.ltoreq.80 that employs a catalytic
composition that comprises at least one organometallic complex of
an element of group IV that is selected from among titanium,
zirconium, or hafnium, whereby said organometallic complex contains
at least one alkoxy-type ligand that is functionalized by a
heteroatom that is selected from among nitrogen, oxygen, phosphorus
or sulfur, or by an aromatic group.
Inventors: |
GRASSET; Fabien; (Bron,
FR) ; HARRY; Stephane; (Jardin, FR) ; PRORIOL;
David; (Brignais, FR) ; MAGNA; Lionel; (Lyon,
FR) |
Assignee: |
IFP ENERGIES NOUVELLES
RUEIL-MALMAISON CEDEX
FR
|
Family ID: |
43242993 |
Appl. No.: |
13/109219 |
Filed: |
May 17, 2011 |
Current U.S.
Class: |
502/117 ;
502/103; 546/6; 549/210; 549/3; 556/21; 556/54; 585/513 |
Current CPC
Class: |
C07C 2531/14 20130101;
B01J 2531/46 20130101; B01J 31/0212 20130101; C07C 2531/22
20130101; B01J 2231/20 20130101; C07C 2/34 20130101; C07C 2/36
20130101; C07C 2/32 20130101; Y02P 20/52 20151101; C07C 11/02
20130101; C07C 11/02 20130101; C07C 2531/24 20130101; C07C 2/32
20130101; C07C 2/36 20130101; B01J 2531/48 20130101; B01J 2531/49
20130101 |
Class at
Publication: |
502/117 ;
549/210; 556/54; 549/3; 556/21; 546/6; 502/103; 585/513 |
International
Class: |
B01J 31/22 20060101
B01J031/22; C07F 7/00 20060101 C07F007/00; C07C 2/24 20060101
C07C002/24; C07F 7/28 20060101 C07F007/28 |
Foreign Application Data
Date |
Code |
Application Number |
May 18, 2010 |
FR |
10/02.090 |
Claims
1. Catalytic composition comprising at least one organometallic
complex of an element of group IV that is selected from among
titanium, zirconium or hafnium, whereby said organometallic complex
contains at least one alkoxy-type ligand that is functionalized by
a heteroatom that is selected from among nitrogen, oxygen,
phosphorus or sulfur or by an aromatic group, and has the following
for a general formula: [M(OR).sub.nY.sub.(4-n)] in which: M is an
element from group IV that is selected from among titanium,
zirconium, and hafnium, Y is an atom of chlorine or bromine, a
hydrocarbyl radical that comprises 1 to 30 carbon atoms, or a
radical that is selected from the group that is formed by the
alkoxies R'O--, the amidos R'2N--, or the carboxylates R'COO--,
where R' is a hydrocarbyl radical that comprises 1 to 30 carbon
atoms, n can assume the integer values of 1 to 4, The ligand --OR
is an organic compound that is selected from the family of alkoxy
ligands whose general structure is as follows:
O--(CR.sup.10R.sup.11).sub.n--X-L in which: The functional group L
is a group that comprises a heteroatom or an aromatic group,
whereby said group that comprises a heteroatom is selected from
among the groups --NR.sup.1R.sup.2, --OR.sup.3, --PR.sup.4R.sup.5,
and --SR.sup.6, The group X represents a hydrocarbon group
(CR.sup.7R.sup.8), an oxygen atom, or a group that comprises a
nitrogen atom --NR.sup.9, The groups R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and
R.sup.11 represent a hydrogen atom or a hydrocarbon chain that may
or may not be cyclic, comprising 1 to 30 carbon atoms, n can assume
the integer values of 0 to 30.
2. Catalytic composition according to claim 1, in which said
catalytic composition comprises a hydrocarbyl aluminum compound,
called an activating agent, selected from the group that is formed
by the tris(hydrocarbyl)aluminum compounds, the chlorinated or
brominated hydrocarbyl aluminum compounds, and the
aluminoxanes.
3. Catalytic composition according to claim 1, in which said group
(CR.sup.10R.sup.11).sub.n is selected from among the following
groups: --CH.sub.2--, --(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--,
--(CH.sub.2).sub.4--, --(CH.sub.2).sub.5--, --C(CH.sub.3).sub.2--,
--C(CH.sub.3).sub.2--CH.sub.2--,
--C(CH.sub.3).sub.2--CH.sub.2--CH.sub.2--, --C(CF.sub.3).sub.2--,
--C(CF.sub.3).sub.2--CH.sub.2-- and
--C(CF.sub.3).sub.2--CH.sub.2--CH.sub.2--.
4. Catalytic composition according to claim 1, in which said
functional group L is selected from among the following groups:
methoxy (--OMe), butoxy (--OBu), dimethylamino (--NMe.sub.2),
pyrrolidino (C.sub.4H.sub.8N), pyridino (--C.sub.5H.sub.4N),
phosphino (--PR.sub.2), in which R is an alkyl or aryl group that
may or may not be substituted, thiofene (--C.sub.4H.sub.3S),
tetrahydrofuran (--C.sub.4H.sub.7O), furan (--C.sub.4H.sub.3O), and
phenyl (--C.sub.6H.sub.5), whereby said groups may or may not be
substituted.
5. Catalytic composition according to claim 4, in which said group
L is the phosphino group (--PR.sub.2), in which R is an alkyl or
aryl group that may or may not be substituted.
6. Catalytic composition according to claim 1, in which M is an
element of group IV that is selected from among titanium and
zirconium.
7. Catalytic composition according to claim 1, in which Y is a
radical that is selected from the group that is formed by the
alkoxies R'O--, where R' is a hydrocarbyl radical that comprises 1
to 30 carbon atoms.
8. Process for oligomerization of olefins into compounds or into a
mixture of compounds of general formula CpH2p with
4.ltoreq.p.ltoreq.80 that employs a catalytic composition according
to claim 1.
9. Process for oligomerization of olefins according to claim 8, in
which p is between 4 and 14.
10. Process for oligomerization of olefins according to claim 8, in
which the feedstock is ethylene.
11. Process for oligomerization of olefins according to claim 8, in
which the process is a process for dimerization of ethylene, in the
case where the element M of group IV is titanium.
12. Process for oligomerization of olefins according to claim 11,
in which the process is a process for selective dimerization of
ethylene into butene-1, in the case where the element M of group IV
is titanium.
13. Process for oligomerization of olefins according to claim 11,
in which titanium is used as a metal, triethyl aluminum is used as
an activating agent, and an activating agent to organometallic
complex molar ratio of between 1 and 5 is used for the dimerization
of ethylene.
14. Process for oligomerization of olefins according to claim 1, in
which zirconium is used as metal, ethyl aluminum sesquichloride is
used as an activating agent, and an activating agent to
organometallic complex molar ratio of between 6 and 30 is used for
the oligomerization of ethylene.
Description
[0001] This invention relates to the oligomerization of olefins, in
particular ethylene. The oligomerization is defined as the
transformation of a monomeric unit into a compound or a mixture of
compounds of general formula C.sub.pH.sub.2p such as
4.ltoreq.p.ltoreq.80.
[0002] One object of the invention is to provide a process for
oligomerization of olefins, preferably of ethylene, propylene and
butene, and in a preferred manner of ethylene, using a particular
catalytic composition.
[0003] It is well known that the monoolefins-.alpha., such as
ethylene, propylene or butene-1, can be oligomerized with catalytic
systems based on transition metals, such as nickel, chromium,
titanium, zirconium or other metals, in the presence of a
co-catalyst such as a hydrocarbyl aluminum compound, a hydrocarbyl
aluminum halide, or an aluminoxane.
[0004] Several types of ligands have been described for stabilizing
the catalytic radical and orienting the selectivity of the
oligomerization reaction.
[0005] The U.S. Pat. No. 3,660,519 describes a catalytic
composition for oligomerizing the ethylene that limits the
proportion of oligomers that are greater than C22. This catalytic
composition comprises: (a) a titanium compound of formula
[Ti(OR).sub.n(Cl).sub.4-n] (with n=1 to 4, and with R being an
alkyl group that has 1 to 8 carbon atoms); (b) an electron-donor
organic compound that contains at least one oxygen or a nitrogen or
a phosphorus, (c) a chloro-alkyl aluminum compound, and (d) another
organic compound that contains sulfur. The organic additives that
are proposed in this composition make it possible to monitor the
distribution of the oligomers that are produced by limiting those
that are greater than C22.
[0006] The U.S. Pat. No. 3,584,071 claims a catalytic composition
for the oligomerization of ethylene, comprising diphenyl ether that
is combined with titanium tetrachloride and ethyl aluminum
sesquichloride to increase the proportion of oligomers from C10 to
C18.
[0007] In the patent EP 0,722,922 B1, the IPCL Company claims a
catalytic composition that comprises a tetraphenoxy titanium
compound Ti(OAr).sub.4, in which OAr is a phenoxy group that is
ortho-substituted or para-substituted or both by alkyl chains,
whereby the activator is an alkyl aluminum and in particular ethyl
aluminum sesquichloride, for oligomerizing the ethylene into a
mixture of C4 to C36 alpha-olefins. The addition of an organic
compound that contains a heteroatom that is based on sulfur, oxygen
or phosphorus makes it possible to improve the monitoring of the
distribution of olefins.
[0008] Other compounds of titanium or zirconium that comprise two
alkoxy or aryloxy entities that may or may not be linked to one
another are known for catalyzing the polymerization of ethylene in
the presence of various activators including methylaluminoxane,
whereby the polymerization of ethylene implements a number of
patterns of greater than 100 in a manner that is known to one
skilled in the art and makes it possible to obtain solid
polymers.
[0009] The primary drawback of the catalytic systems that are based
on titanium or zirconium that involve the alkoxy or phenoxy ligands
and lead to the formation of oligomers from ethylene is the
formation of polymers in addition to the oligomers, which can also
be the cause of a quick deactivation of the catalyst. The
monitoring of the distribution of these oligomers is a very
significant parameter for the industrial future of this type of
catalytic system. In the majority of the systems, this distribution
monitoring is associated with the use of additives (organic, etc.),
which very often complicates the catalytic composition.
[0010] One objective of the invention is to provide a new catalytic
composition for the oligomerization of olefins.
[0011] Another objective of the invention is to provide a process
for oligomerization of olefins that implements said catalytic
composition.
[0012] Another objective of the invention is, in a preferred
embodiment, to provide a process for oligomerization of olefins
that employs a catalytic composition that makes possible a
monitoring of the distribution of the oligomers that are obtained.
The process for oligomerization of olefins according to the
invention makes it possible to obtain a shorter oligomer
distribution, in a very preferred manner, of C2 to C14. One
advantage of the invention is therefore to provide a selective
process for oligomerization of olefins over a range of
oligomers.
[0013] A process for oligomerization of olefins into compounds or
into a mixture of compounds of general formula CpH2p with
4.ltoreq.p.ltoreq.80 that employs a catalytic composition
comprising at least one organometallic complex of an element of
group IV that is selected from among titanium, zirconium or hafnium
has now been found, whereby said organometallic complex contains at
least one alkoxy-type ligand that is functionalized by a heteroatom
that is selected from among nitrogen, oxygen, phosphorus or sulfur
or by an aromatic group, and has the following for a general
formula:
[M(OR).sub.nY.sub.(4-n)]
[0014] in which: [0015] M is an element from group IV that is
selected from among titanium, zirconium, and hafnium, [0016] Y is
an atom of chlorine or bromine, a hydrocarbyl radical that
comprises 1 to 30 carbon atoms, or a radical that is selected from
the group that is formed by the alkoxies R'O--, the amidos R'2N--,
or the carboxylates R'COO--, where R' is a hydrocarbyl radical that
comprises 1 to 30 carbon atoms, [0017] n can assume the integer
values of 1 to 4, [0018] The ligand --OR is an organic compound
that is selected from the family of alkoxy ligands whose general
structure is as follows:
[0018] O--(CR.sup.10R.sup.11).sub.n--X-L
[0019] in which: [0020] The functional group L is a group that
comprises a heteroatom or an aromatic group, whereby said group
that comprises a heteroatom is selected from among the groups
--NR.sup.1R.sup.2, --OR.sup.3, --PR.sup.4R.sup.5, and --SR.sup.6,
[0021] The group X represents a hydrocarbon group
(CR.sup.7R.sup.8), an oxygen atom, or a group that comprises a
nitrogen atom --NR.sup.9, [0022] The groups R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9,
R.sup.10, and R.sup.11 represent a hydrogen atom or a hydrocarbon
chain that may or may not be cyclic, comprising 1 to 30 carbon
atoms, [0023] n can assume the integer values of 0 to 30, and
preferably 0 to 10.
[0024] Within the scope of the invention, the term "alkoxy" is
defined as being a group that corresponds to the general formula
--OR, in which the group R is an alkyl or substituted alkyl group.
This definition of the term "alkoxy" does not include the groups of
aryloxy or phenoxy type. In the catalytic composition according to
the invention, the alkoxy-type ligand as defined above is
functionalized by a heteroatom that is selected from among
nitrogen, oxygen, phosphorus, sulfur, arsenic and antimony or by an
aromatic group, and it corresponds to the claimed formulation.
[0025] Preferably, M is an element of group IV that is selected
from among titanium and zirconium.
[0026] Preferably, Y is a radical that is selected from the group
that is formed by the alkoxies R'O-- where R' is a hydrocarbyl
radical, preferably non-functionalized, comprising 1 to 30 carbon
atoms. In an also preferred manner, Y is a chlorine atom.
[0027] Preferably, the group (CR.sup.10R.sup.11).sub.n is selected
from among the following groups: --CH.sub.2--,
--(CH.sub.2).sub.2--, --(CH.sub.2).sub.3--, --(CH.sub.2).sub.4--,
--(CH.sub.2).sub.5--, --C(CH.sub.3).sub.2--,
--C(CH.sub.3).sub.2--CH.sub.2--, --C(CH.sub.3).sub.2--CH.sub.2--.
CH.sub.2--, --C(CF.sub.3).sub.2--, --C(CF.sub.3).sub.2--CH.sub.2--
and --C(CF.sub.3).sub.2--CH.sub.2--CH.sub.2--.
[0028] Preferably, said functional group L is selected from among
the following groups: methoxy (--OMe), butoxy (--OBu),
dimethylamino (--NMe.sub.2), pyrrolidino (C.sub.4H.sub.8N),
pyridino (--C.sub.5H.sub.4N), phosphino (--PR.sub.2), in which R is
an alkyl or aryl group that may or may not be substituted, thiofene
(--C.sub.4H.sub.3S), tetrahydrofuran (--C.sub.4H.sub.7O), furan
(--C.sub.4H.sub.3O), and phenyl (--C.sub.6H.sub.5), whereby said
groups may or may not be substituted. Said group L is preferably
the phosphino group (--PR.sub.2), in which R is an alkyl or aryl
group that may or may not be substituted.
[0029] Preferably, X represents a hydrocarbon group
(CR.sup.7R.sup.8). In a very preferred manner, X is a hydrocarbon
group (CR.sup.7R.sup.8) that is selected from among the groups
--CH.sub.2-- and --C(CH.sub.3).sub.2.
[0030] The catalytic composition that is used in the
oligomerization process according to the invention can
advantageously also contain a hydrocarbyl aluminum compound, called
an activating agent, selected from the group that is formed by the
tris(hydrocarbyl)aluminum compounds, the chlorinated or brominated
hydrocarbyl aluminum compounds, and the aluminoxanes.
[0031] The tris(hydrocarbyl)aluminum compounds, and the chlorinated
or brominated hydrocarbyl aluminum compounds preferably correspond
to the general formula AlR''.sub.xZ.sub.3-x in which R'' represents
a monovalent hydrocarbon radical that contains, for example, up to
12 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl or
cycloalkyl, Z represents a halogen atom that is selected from
among, for example, chlorine and bromine, whereby Z is preferably a
chlorine atom, and x assumes a value of 1 to 3. As examples of such
compounds of formula AlR''.sub.xZ.sub.3-x, it is possible to
mention ethyl aluminum sesquichloride (Et.sub.3Al.sub.2Cl.sub.3),
dichloroethyl aluminum (EtAlCl.sub.2), dichloroisobutyl aluminum
(iBuAlCl.sub.2), chlorodiethyl aluminum (Et.sub.2AlCl), and
triethyl aluminum (AlEt.sub.3). Among the aluminoxanes that can be
used according to the invention, it is possible to cite methyl
aluminoxane and modified methyl aluminoxane (MMAO). These
activating agents can be used alone or in a mixture.
[0032] According to the nature of the organometallic complex
[M(OR).sub.nY.sub.(4-n)], the activating agent can also be selected
from the group of tris(aryl)borane-type Lewis acids, such as
tris(perfluorophenyl)borane,
tris(3,5-bis(trifluoromethyl)phenyl)borane,
tris(2,3,4,6-tetrafluorophenyl)borane,
tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl)borane and
derivatives thereof. As an activator, it is also possible to use an
(aryl)borate combined with a triphenylcarbenium cation or with a
trisubstituted ammonium cation, such as triphenylcarbenium
tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium
tetrakis(perfluorophenyl)borate, N,N-diethylanilinium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or
triphenylcarbenium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
[0033] Without being tied by any theory, the functional group L
that is characterized by the presence of a heteroatom that is
selected from among nitrogen, oxygen, phosphorus and sulfur or by
the presence of an aromatic group is able to interact with the
metal center M by forming a connection of, for example, the dative
type that thus promotes the formation of the active complex in
catalysis and contributes to its stability.
[0034] Without being limiting, the examples below illustrate the
ligands "O--(CR.sup.10R.sup.11).sub.n--X-L" according to the
invention.
[0035] The ligands are shown below in their protonated form.
##STR00001## ##STR00002## ##STR00003##
Process for the Preparation of the Organometallic Complex
[0036] The process for the preparation of the organometallic
complex of an element of group IV that is selected from among
titanium, zirconium or hafnium of the catalytic composition that is
used in the process according to the invention is done according to
the methods that are known in the literature that relate to the
synthesis of the organometallic complexes comprising at least one
alkoxy ligand. Any process for preparation of this compound may be
suitable, such as, for example, the reaction of the alkoxy-type
ligand that is functionalized by a heteroatom that is selected from
among nitrogen, oxygen, phosphorus or sulfur or by an aromatic
group, with a salt of an element of group IV that is selected from
among titanium, zirconium or hafnium in an organic solvent, such
as, for example, an ether, an alcohol, an alkane such as, for
example, pentane, an aromatic solvent such as, for example,
toluene, or a chlorinated solvent such as, for example,
dichloromethane.
[0037] According to a preferred embodiment of said process for
preparation, the organometallic complex is prepared in situ in the
solvent that is used for the oligomerization reaction. In this
case, the mixing order of the salt of the element of group IV that
is selected from among titanium, zirconium or hafnium, and the
ligand is not critical. However, in a preferred manner, a solution
of a compound of the element of group IV that is selected from
among titanium, zirconium or hafnium that is soluble in an organic
medium is first prepared, and next the alkoxy-type ligand that is
functionalized by a heteroatom that is selected from among
nitrogen, oxygen, phosphorus or sulfur or by an aromatic group is
added.
[0038] According to another preferred embodiment of said process
for preparation, said organometallic complex is isolated before
solubilization in the solvent of the oligomerization reaction.
Process for Preparation of the Catalytic Composition that is Used
in the Process According to the Invention.
[0039] In the case where the catalytic composition that is used in
the oligomerization process according to the invention also
comprises an activating agent, the two components of said catalytic
composition, i.e., the organometallic complex and the activating
agent, are advantageously brought into contact, in any order, in a
solvent that is selected from the group that is formed by the
aliphatic and cycloaliphatic hydrocarbons, such as hexane,
cyclohexane, heptane, butane or isobutane, whereby the unsaturated
hydrocarbons such as the monoolefins or diolefins comprise, for
example, 4 to 20 carbon atoms, the aromatic hydrocarbons such as
benzene, toluene, ortho-xylene, mesitylene, ethylbenzene and the
chlorinated hydrocarbons, such as chlorobenzene or dichloromethane,
pure or in a mixture. Advantageously, the aliphatic hydrocarbons
such as n-heptane and the aromatic hydrocarbons such as
ortho-xylene are used.
[0040] According to another preferred embodiment of the process for
preparation of said catalytic composition and when an activating
agent is used, the activating agent is added in a solution that
contains the organometallic complex of the element of group IV that
is selected from among titanium, zirconium, or hafnium.
[0041] The concentration of the element M of group IV that is
selected from among titanium, zirconium or hafnium in the catalytic
solution is advantageously between 1.10.sup.-4 to 1 mol/L,
preferably from 1.10.sup.-3 to 0.5 mol/L.
[0042] The molar ratio between the optional activating agent and
the organometallic complex of the element M of group IV that is
selected from among titanium, zirconium or hafnium is
advantageously between 1/1 and 1,800/1, preferably from 2/1 to
800/1, and in a preferred manner between 2/1 and 500/1.
[0043] The temperature at which the components of the catalytic
system are mixed is advantageously between -10 and +180.degree. C.,
preferably between 0 and +150.degree. C., for example at a
temperature that is close to ambient temperature (15 to 30.degree.
C.). The mixing can be carried out under an atmosphere of ethylene
or inert gas.
[0044] Oligomerization Reaction.
[0045] The process according to the invention is a process for
oligomerization of olefins for producing compounds or a mixture of
compounds of general formula C.sub.pH.sub.2p with
4.ltoreq.p.ltoreq.80, preferably with 4.ltoreq.p.ltoreq.50, in a
preferred manner with 4.ltoreq.p.ltoreq.26, and in a more preferred
manner with 4.ltoreq.p.ltoreq.14, employing the catalytic
composition that is described above.
[0046] The feedstock that is used in the process for
oligomerization according to the invention consists of C2 to C12
alpha-olefins, and preferably the feedstock is selected from among
ethylene, propylene, or butene, and in a very preferred manner, the
feedstock is ethylene.
[0047] According to a preferred embodiment, in the case where the
element M of group IV is titanium, the process according to the
invention is a process for dimerization of ethylene, and in an even
more preferred manner, a process for selective dimerization of
ethylene into butene-1.
[0048] Preferably, titanium is used as a metal, triethyl aluminum
is used as an activating agent, and a molar ratio of activating
agent to organometallic complex of between 1 and 5 is used for the
dimerization of ethylene.
[0049] According to another preferred embodiment, in the case where
the element M of group IV is zirconium, the process according to
the invention is a process for oligomerization of the ethylene that
makes it possible to obtain a distribution of variable compounds,
i.e., compounds or a mixture of compounds of general formula
C.sub.pH.sub.2p with 4.ltoreq.p.ltoreq.30.
[0050] Preferably, zirconium is used as a metal, ethyl aluminum
sesquichloride is used as an activating agent, and a molar ratio of
activating agent to organometallic complex of between 6 and 30 is
used for the oligomerization of ethylene.
[0051] The oligomerization process of the olefins is advantageously
carried out under a total pressure of between 0.5 and 15 MPa,
preferably 1 to 10 MPa, and at a temperature of between 20 to
180.degree. C., preferably between 40 and 140.degree. C.
[0052] According to a preferred embodiment, the catalytic
oligomerization reaction is implemented intermittently. A selected
volume of the catalytic solution that is constituted as described
above is introduced into a reactor that is equipped with the usual
stirring devices, heating devices and cooling devices, and then it
is pressurized by ethylene to the desired pressure, and the
temperature is adjusted to the desired value. The oligomerization
reactor is kept at constant pressure by introducing ethylene until
the total volume of liquid that is produced represents, for
example, 2 to 50 times the volume of the catalytic solution
originally introduced. The catalyst is then destroyed by any
conventional means known to one skilled in the art, and then it is
drawn off, and the products of the reaction and the solvent are
separated.
[0053] According to another preferred embodiment, the catalytic
oligomerization reaction is implemented continuously. The catalytic
solution is injected at the same time as ethylene into a reactor
that is stirred by standard mechanical means that are known to one
skilled in the art or by an outside recirculation, and it is kept
at the desired temperature. It is also possible to inject the
components of the catalyst separately into the reaction medium.
Ethylene is introduced by an intake valve that is controlled at the
pressure that keeps the former constant. The reaction mixture is
drawn off by means of a valve that is controlled at the liquid
level so as to keep the former constant. The catalyst is
continuously destroyed by any conventional means that is known to
one skilled in the art, and then the products that are obtained
from the reaction as well as the solvent are separated, for example
by distillation. The ethylene that has not been transformed can be
recycled in the reactor. The catalyst residues that are included in
a heavy fraction can be incinerated.
[0054] Products that are Obtained:
[0055] The oligomerization process according to the invention makes
possible the production of compounds or a mixture of oligomer
compounds of general formula C.sub.pH.sub.2p with
4.ltoreq.p.ltoreq.80, preferably with 4.ltoreq.p.ltoreq.50, in a
preferred manner with 4.ltoreq.p.ltoreq.26, and in a very preferred
manner with 4.ltoreq.p.ltoreq.14. The compounds or mixture of
oligomer compounds that are thus obtained are generally liquid
oligomer compounds.
[0056] These compounds or mixture of compounds find a use, for the
lower oligomers (C4, C6, C8, C10), as comonomers with ethylene in
the manufacturing of linear low-density polyethylene or as a
starting product for the manufacturing of lubricating synthesis
oils, and for the olefins that have a chain length of C10 to C26 in
the manufacturing of plasticizers and detergents.
[0057] The Following Examples Illustrate the Invention.
EXAMPLE 1
Synthesis of the Complex [(L7).sub.2Ti(OiPr).sub.2]
[0058] 3.6 g (35 mmol) of ligand L7, 10 ml of dry cyclohexane, as
well as 5 g (17.5 mmol) of [Ti(OiPr).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes and then stirred, still under
argon, for one night. The evaporation of the solvent leads to the
complex [(L7).sub.2Ti(OiPr).sub.2] in the form of an orange oil.
The yield is almost quantitative. The structure of the complex is
confirmed by .sup.1Hand .sup.13C NMR analyses.
EXAMPLE 2
Synthesis of the Complex [(L8).sub.2Ti(OiPr).sub.2]
[0059] 3.4 g (35 mmol) of ligand L8, 10 ml of dry cyclohexane, as
well as 5.0 g (17.5 mmol) of [Ti(OiPr).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes and then stirred, still under
argon, for one night. The evaporation of the solvent leads to the
complex [(L8).sub.2Ti(OiPr).sub.2] in the form of a dark orange
oil. The yield is almost quantitative. The structure of the complex
is confirmed by .sup.1H and .sup.13C NMR analyses.
EXAMPLE 3
Synthesis of the Complex [(L9).sub.2Ti(OiPr).sub.2]
[0060] 3.8 g (35 mmol) of ligand L9, 10 ml of dry cyclohexane, as
well as 5.0 g (17.5 mmol) of [Ti(OiPr).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes and then stirred, still under
argon, for one night. The evaporation of the solvent leads to the
complex [(L9).sub.2Ti(OiPr).sub.2] in the form of a colorless oil.
The yield is almost quantitative. The structure of the complex is
confirmed by .sup.1H and .sup.13C NMR analyses.
EXAMPLE 4
Synthesis of the Complex [(L11).sub.2Ti(OiPr).sub.2]
[0061] 4.3 g (35 mmol) of ligand L11, 10 ml of dry cyclohexane, as
well as 5.0 g (17.5 mmol) of [Ti(OiPr).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes, and then stirred, still
under argon, for one night. The evaporation of the solvent leads to
the complex [(L11).sub.2Ti(OiPr).sub.2] in the form of an orange
oil. The yield is almost quantitative. The structure of the complex
is confirmed by .sup.1H and .sup.13C NMR analyses.
EXAMPLE 5
Synthesis of the Complex [(L12).sub.2Ti(OiPr).sub.2]
[0062] 4.0 g (35 mmol) of ligand L12, 10 ml of dry cyclohexane, as
well as 5.0 g (17.5 mmol) of [Ti(OiPr).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes and then stirred, still under
argon, for one night. The evaporation of the solvent leads to the
complex [(L12).sub.2Ti(OiPr).sub.2] in the form of a yellow liquid.
The yield is almost quantitative. The structure of the complex is
confirmed by .sup.1H and .sup.13C NMR analyses.
EXAMPLE 6
Synthesis of the Complex [(L14).sub.2Ti(OiPr).sub.2]
[0063] 3.2 g (14 mmol) of ligand L14, 10 ml of dry cyclohexane, as
well as 2.0 g (7 mmol) of [Ti(OiPr).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes and then stirred, still under
argon, for one night. The evaporation of the solvent leads to the
complex [(L14).sub.2Ti(OiPr).sub.2] in the form of a yellow viscous
liquid. The yield is almost quantitative. The structure of the
complex is confirmed by .sup.1H, .sup.13C and .sup.31P NMR
analyses.
EXAMPLE 7
Synthesis of the Complex [(L16).sub.2Ti(OiPr).sub.2]
[0064] 3.4 g (14 mmol) of ligand L16, 10 ml of dry cyclohexane, as
well as 2.0 g (7 mmol) of [Ti(OiPr).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes and then stirred, still under
argon, for one night. The evaporation of the solvent leads to the
complex [(L16).sub.2Ti(OiPr).sub.2] in the form of a yellow viscous
liquid. The yield is almost quantitative. The structure of the
complex is confirmed by .sup.1H, .sup.13C, and .sup.31P NMR
analyses.
EXAMPLE 8
Synthesis of the Complex [(L16).sub.2Ti(OnBu).sub.2]
[0065] 2.9 g (12 mmol) of ligand L16, 10 ml of dry cyclohexane, as
well as 2.0 g (6 mmol) of [Ti(OnBu).sub.4] are introduced into a
Schlenk flask under argon at ambient temperature. This mixture is
next brought to reflux for 30 minutes and then stirred, still under
argon, for one night. The evaporation of the solvent leads to the
complex [(L16).sub.2Ti(OnBu).sub.2] in the form of a yellow viscous
liquid. The yield is almost quantitative. The structure of the
complex is confirmed by .sup.1H, .sup.13C, and .sup.31P NMR
analyses and by elementary analysis.
EXAMPLES 9-16 (ACCORDING TO THE INVENTION)
Selective Dimerization of C.sub.2H.sub.4
[0066] 0.15 mmol of the complex [(L).sub.nTi(OiPr).sub.4-n] (or
[(L).sub.nTi(OnBu).sub.4-n]), previously solubilized in cyclohexane
as described in the invention, is introduced in order under argon
atmosphere into a stainless steel autoclave with a useful volume of
35 ml, equipped with electric heating and a cooling system by a
compressed air vortex, making it possible to regulate the
temperature. Next, 0.45 mmol of triethyl aluminum in solution is
introduced into cyclohexane, or an Al/Ti molar ratio=3. The total
quantity of cyclohexane is 6 ml. Then, ethylene is introduced into
the autoclave in such a way as to maintain a constant pressure of 2
MPa. After a reaction time "t," the introduction of ethylene is
stopped, and the reactor cools to ambient temperature. The
autoclave is next depressurized, and the catalytic system is
neutralized by injection of 1 ml of water. A gaseous fraction and a
liquid fraction that are analyzed by chromatography are collected.
If necessary, a small quantity of polyethylene is also
recovered.
[0067] Table 1 below repeats in a detailed manner all of the
results that are obtained:
TABLE-US-00001 TABLE 1 Results of the Tests According to the
Invention Nature of the Time Productivity Distribution (% by
Weight) No. Complex (hour) (g/gTi/h) C4 (.alpha.) C6 (.alpha.) PE 9
[(L7).sub.2Ti(OiPr).sub.2] 1 600 95 (99+) 3 (15) 2 10
[(L9).sub.2Ti(OiPr).sub.2] 1 700 91 (99) 7.5 (6) 0.5 11
[(L11).sub.2Ti(OiPr).sub.2] 1 1400 94 (99+) 5.5 (8) 0.5 12
[(L8).sub.2Ti(OiPr).sub.2] 1 800 94.5 (99+) 4.5 (9) 1 13
[(L12).sub.2Ti(OiPr).sub.2] 1 500 95 (99+) 4 (11) 1 14
[(L14).sub.2Ti(OiPr).sub.2] 0.43 3400 94 (99+) 6 (12) <0.5 15
[(L16).sub.2Ti(OiPr).sub.2] 0.22 6600 92 (99+) 8 (12) <0.5 16
[(L16).sub.2Ti(OnBu).sub.2] 0.15 9700 93 (99+) 7 (9) <0.5
[0068] In this table, the productivity is defined as being the
ethylene mass (C.sub.2H.sub.4) that is consumed per gram of
titanium that is introduced initially and per hour.
[0069] The C4 distribution is the quantity of olefins having a
carbon atom number that is equal to 4 in the total
distribution.
[0070] (.alpha.1) represents the selectivity of linear butene-1
product in the C4 fraction.
[0071] Likewise, the C6 distribution is the quantity of olefins
having a carbon atom number that is equal to 6 in the total
distribution.
[0072] (.alpha.2) represents the selectivity of linear hexene-1
product in the C6 fraction.
[0073] The selectivity of linear butene-1 product in the C4
fraction and the linear hexene-1 product in the C6 fraction is
measured by gas phase chromatography according to a method that is
known to one skilled in the art.
EXAMPLES 17-20 (FOR COMPARISON)
Selective Dimerization of C.sub.2H.sub.4 by [Ti(OiPr).sub.4] in the
Presence of Organic Additives that are not in Accordance with the
Invention
[0074] Examples 17-20 of Table 2 were produced under the same
conditions as those described in Table 1 (the reaction time is
equal to 1 hour). These examples illustrate the negative effect of
the organic additives that have heteroatoms but that are not in
accordance with the invention (and therefore the advantage of the
process according to the invention) on the productivity of
[Ti(OiPr).sub.4] in selective dimerization of the ethylene into
butene-1.
TABLE-US-00002 TABLE 2 Results of the Comparative Tests Nature
Nature of the of the "Additive/Ti" Productivity Distribution (% by
Weight) No. Complex Additive Molar Ratio (g/gTi/h) C4 (.alpha.) C6
(.alpha.) PE 17 [Ti(OiPr).sub.4] THF 2 300 97 (99.sup.+).sup. 3
(15) <0.5 18 [Ti(OiPr).sub.4] Pyridine 2 <100 99
(99.sup.+).sup. <0.5 <0.5 19 [Ti(OiPr).sub.4] MeOBu 2 700 95
(99+) <5 <0.5 20 [Ti(OiPr).sub.4] PPh.sub.3 2 1300 96 (99+)
3.5 (13) 0.5
EXAMPLE 21
Synthesis of the Complex [(L1).sub.2Zr(OiPr).sub.2]
[0075] 0.22 g (2 mmol) of ligand L1, 10 ml of dry cyclohexane, as
well as 0.39 g (2 mmol) of [Zr(OiPr).sub.4(iPrOH)] are introduced
into a Schlenk flask under argon at ambient temperature. This
mixture is stirred, still under argon, for one night at ambient
temperature. The evaporation of the solvent leads to the complex
[(L1).sub.2Zr(OiPr).sub.2] in the form of a white solid. The yield
is almost quantitative. The structure of the complex is confirmed
by .sup.1H and .sup.13C NMR analyses.
EXAMPLE 22
Synthesis of the Complex [(L11).sub.2Zr(OiPr).sub.2]
[0076] 0.5 g (1.9 mmol) of Zr(OiPr).sub.4 as well as 10 ml of dry
toluene are introduced into a Schlenk flask under argon at ambient
temperature. Next, 0.46 g (3.8 mmol) of ligand L11 is added. This
mixture is stirred, still under argon, for one night at ambient
temperature. The evaporation of the solvent leads to the complex
[(L11).sub.2Zr (OiPr).sub.2] in the form of a white viscous oil.
The yield is almost quantitative.
EXAMPLE 23 (ACCORDING TO THE INVENTION)
Oligomerization of C.sub.2H.sub.4 by the Complex
[(L1).sub.2Zr(OiPr).sub.2]
[0077] 0.05 mmol of the complex [(L1).sub.2Zr(OiPr).sub.2],
previously solubilized in a toluene/cyclohexane (1/1) mixture as
described in the invention, is introduced in order, under argon
atmosphere, into a stainless steel autoclave with a useful volume
of 35 ml, equipped with electric heating and a cooling system by
compressed air vortex, making it possible to regulate the
temperature. Next, 0.59 mmol of aluminum sesquichloride in solution
is introduced into the cyclohexane, or an Al/Zr molar ratio=12. The
total quantity of solvent is 6 ml. Then, ethylene is introduced
into the autoclave in such a way as to maintain a constant pressure
of 4 MPa and a temperature of 80.degree. C. After one hour of
reaction, the introduction of ethylene is stopped, and the reactor
is cooled to ambient temperature. The autoclave is next
depressurized, and the catalytic system is neutralized. A liquid
fraction is collected, and said fraction is analyzed by
chromatography. The quantity of polymer that is formed is less than
10 mg.
TABLE-US-00003 Distribution (% by Weight) Productivity C4 C6 C8 C10
(g/gZr/h) (.alpha.) (.alpha.) (.alpha.) (.alpha.) C12 C14 C16 C18
C20+ PE 562 45 27 14 7 3 2 1 <0.5 <0.5 <0.5 (97) (98) (96)
(92)
EXAMPLE 24 (ACCORDING TO THE INVENTION)
Oligomerization of C.sub.2H.sub.4 by the Complex
[(L11).sub.2Zr(OiPr).sub.2]
[0078] The protocol that is used is identical to the one that is
described in Example 23 except that 0.05 mmol of
[(L11).sub.2Zr(OiPr).sub.2] is used. After 45 minutes of reaction,
the results are as follows:
TABLE-US-00004 Productivity Distribution (% by Weight) (g/gZr/h) C4
C6 C8 C10 C12 C14 C16 C18 C20+ PE 3066 24 21 17 12 9 6 4 3 4
<0.5
[0079] Without further elaboration, it is believed that one skilled
in the art can, using the preceding description, utilize the
present invention to its fullest extent. The preceding preferred
specific embodiments are, therefore, to be construed as merely
illustrative, and not imitative of the remainder of the disclosure
in any way whatsoever.
[0080] In the foregoing and in the examples, all temperatures are
set forth uncorrected in degrees Celsius and, all parts and
percentages are by weight, unless otherwise indicated.
[0081] The entire disclosures of all applications, patents and
publications, cited herein and of corresponding French application
Ser. No. 10/02090, filed May 18, 2010, are incorporated by
reference herein.
[0082] The preceding examples can be repeated with similar success
by substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in the
preceding examples.
[0083] From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this invention
and, without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
* * * * *