U.S. patent application number 12/859333 was filed with the patent office on 2010-12-09 for ligands and catalyst systems thereof for the catalytic oligomerization of olefinic monomers.
Invention is credited to Quoc An On, Eric Johannes Maria DE BOER, Johan Paul Smit, Harry Van Der Heijden, Arie Van Zon.
Application Number | 20100311929 12/859333 |
Document ID | / |
Family ID | 38016821 |
Filed Date | 2010-12-09 |
United States Patent
Application |
20100311929 |
Kind Code |
A1 |
DE BOER; Eric Johannes Maria ;
et al. |
December 9, 2010 |
LIGANDS AND CATALYST SYSTEMS THEREOF FOR THE CATALYTIC
OLIGOMERIZATION OF OLEFINIC MONOMERS
Abstract
The present invention relates to a ligand and its use in a
catalyst for the oligomerization of olefinic monomers, the ligand
having the general formula (IV); (R8)(R2)P--N(R3)--P(R4) (IV).
Inventors: |
DE BOER; Eric Johannes Maria;
(Amsterdam, NL) ; Van Der Heijden; Harry;
(Amsterdam, NL) ; An On; Quoc; (Amsterdam, NL)
; Smit; Johan Paul; (Amsterdam, NL) ; Van Zon;
Arie; (Amsterdam, NL) |
Correspondence
Address: |
SHELL OIL COMPANY
P O BOX 2463
HOUSTON
TX
772522463
US
|
Family ID: |
38016821 |
Appl. No.: |
12/859333 |
Filed: |
August 19, 2010 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11961638 |
Dec 20, 2007 |
7803886 |
|
|
12859333 |
|
|
|
|
Current U.S.
Class: |
526/145 ;
502/167; 568/12 |
Current CPC
Class: |
B01J 31/0265 20130101;
C07F 9/657154 20130101; B01J 2531/64 20130101; B01J 2231/14
20130101; B01J 2531/66 20130101; C07C 2/34 20130101; B01J 2531/62
20130101; B01J 31/189 20130101; C07F 11/005 20130101; B01J 2231/20
20130101; C08F 110/02 20130101; C07F 9/5355 20130101; C07F 9/6571
20130101 |
Class at
Publication: |
526/145 ; 568/12;
502/167 |
International
Class: |
C08F 4/78 20060101
C08F004/78; C07F 9/06 20060101 C07F009/06; B01J 31/18 20060101
B01J031/18 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 22, 2006 |
EP |
06256571.8 |
Claims
1. A ligand having the general formula (IV);
(R.sup.8)(R.sup.2)P--N(R.sup.3)--P(R.sup.4) (IV) wherein: the
R.sup.1 group is selected from a hydrocarbyl, substituted
hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl
group; the R.sup.8 group is selected from an aromatic or
heteroaromatic group which comprise at least one polar substituent
group, and optionally one or more non-polar substituent groups; the
R.sup.3 group is selected from hydrogen, a hydrocarbyl group, a
substituted hydrocarbyl group, a heterohydrocarbyl group, a
substituted heterohydrocarbyl group, a silyl group or derivative
thereof; the R.sup.4 group is an optionally substituted
alkylenedioxy, alkylenedimercapto or alkylenediamino structure
which is bound to the phosphorus atom through the two oxygen,
sulphur or nitrogen atoms of the alkylenedioxy, alkylenedimercapto
or alkylenediamino structure or an optionally substituted
arylenedioxy, arylenedimercapto or arylenediamino structure which
is bound to the phosphorus atom through the two oxygen, sulphur or
nitrogen atoms of the arylenedioxy, arylenedimercapto or
arylenediamino structure.
2. A catalyst system comprising: a) a source of chromium,
molybdenum or tungsten; b) the ligand of claim 1; and c) a
cocatalyst.
3. A process for the oligomerisation of olefinic monomers, wherein
the process comprises contacting at least one olefinic monomer with
the catalyst system of claim 1.
4. A process for the preparation of the ligand of claim 1
comprising reacting: i) a compound having the general formula (V);
(R.sup.1)(R.sup.8)P--N(R.sup.3)--R.sup.5 (V) wherein: the R.sup.5
group is selected from hydrogen or a P(R.sup.6)(R.sup.7)-- group;
the R.sup.6 and the R.sup.7 groups are independently selected from
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and
substituted heterohydrocarbyl groups; and ii) a compound of the
formula X--P(R.sup.4), wherein X is a halide, and if the R.sup.5
group is hydrogen, a HX-acceptor, preferably at a temperature in
the range of from -30 to 200.degree. C.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of U.S. application Ser.
No. 11/961,638 filed Dec. 20, 2007, which is incorporated herein by
reference.
FIELD OF THE INVENTION
[0002] The present invention relates to ligands and catalysts
systems thereof which are useful in the oligomerization of olefinic
monomers.
BACKGROUND OF THE INVENTION
[0003] The efficient catalytic trimerization or tetramerization of
olefinic monomers, such as the trimerization and tetramerization of
ethylene to 1-hexene and 1-octene, is an area of great interest for
the production of olefinic trimers and tetramers of varying degrees
of commercial value. In particular, 1-hexene is a valuable
comonomer for linear low-density polyethylene (LLDPE) and 1-octene
is valuable as a chemical intermediate in the production of
plasticizer alcohols, fatty acids, detergent alcohol and
lubrication oil additives as well as a valuable comonomer in the
production of polymers such as polyethylene. 1-Hexene and 1-octene
can be produced by a conventional transition metal oligomerization
process, although the trimerization and tetramerization routes are
preferred.
[0004] Several different catalytic systems have been disclosed in
the art for the trimerization of ethylene to 1-hexene. A number of
these catalysts are based on chromium.
[0005] U.S. Pat. No. 5,198,563 (Phillips) discloses chromium-based
catalysts containing monodentate amine ligands useful for
trimerizing olefins.
[0006] U.S. Pat. No. 5,968,866 (Phillips) discloses an ethylene
oligomerization/trimerization process which uses a catalyst
comprising a chromium complex which contains a coordinating
asymmetric tridentate phosphane, arsane or stibane ligand and an
aluminoxane to produce alpha-olefins which are enriched in
1-hexene.
[0007] U.S. Pat. No. 5,523,507 (Phillips) discloses a catalyst
based on a chromium source, a 2,5-dimethylpyrrole ligand and an
alkyl aluminium activator for use in the trimerization of ethylene
to 1-hexene.
[0008] Chem. Commun., 2002, 8, 858-859 (BP), discloses chromium
complexes of ligands of the type Ar.sub.2PN(Me)PAr.sub.2
(Ar=ortho-methoxy-substituted aryl group) as catalysts for the
trimerization of ethylene.
[0009] U.S. Pat. No. 7,141,633 (BP) discloses a catalyst for the
trimerization of olefins comprising a source of chromium,
molybdenum or tungsten, a ligand containing at least one
phosphorus, arsenic or antimony atom bound to at least one
hydrocarbyl or heterohydrocarbyl group having a polar substituent,
but excluding the case where all such polar substituents are
phosphane, arsane or stibane groups, and optionally an activator.
The ligand used in most of the examples is
(2-methoxyphenyl).sub.2PN(Me)P(2-methoxyphenyl).sub.2.
[0010] Although the catalysts disclosed in the BP documents
mentioned above have good selectivity for 1-hexene within the
C.sub.6 fraction, a relatively high level of products other than
the commercially desirable 1-hexene and 1-octene is typically
observed.
[0011] U.S. Pat. No. 7,273,959 (Shell) discloses a trimerization
catalyst composition and a process for the trimerization of
olefinic monomers using said catalyst composition.
[0012] Catalytic systems for the tetramerization of ethylene to
1-octene have recently been described. A number of these catalysts
are based on chromium.
[0013] U.S. Published Patent Applications Nos. 2006/0128910,
2006/0173226, 2006/0211903, and 2006/0229480 (Sasol) disclose
catalyst compositions and processes for the tetramerization of
olefins. The catalyst compositions disclosed comprise a transition
metal and a heteroatomic ligand having the general formula
(R).sub.nA-B--C(R).sub.m where A and C are independently selected
from a group which comprises phosphorus, arsenic, antimony, oxygen,
bismuth, sulphur, selenium, and nitrogen, and B is a linking group
between A and C, and R is independently selected from any homo or
heterohydrocarbyl group of which at least one R group is
substituted with a polar substituent and n and m are determined by
the respective valence and oxidation state of A and/or C. The other
catalyst compositions disclosed comprise a transition metal and a
heteroatomic ligand having the general formula
(R').sub.nA-B--C(R').sub.m where A, B, C, n and m are as defined
above, and R' is independently selected from any homo or
heterohydrocarbyl group.
[0014] U.S. Published Patent Application No. 2006/0128910 (Sasol)
discloses the tandem tetramerization and polymerisation of
ethylene. Specifically, it discloses a process for polymerising
olefins to produce branched polyolefins in the presence of a
distinct polymerization catalyst and a distinct tetramerization
catalyst, wherein the tetramerization catalyst produces 1-octene in
a selectivity greater than 30% and the 1-octene produced is at
least partially incorporated into the polyolefin chain.
[0015] Although the tetramerization catalysts disclosed in the
Sasol documents mentioned above have good selectivity for 1-octene
within the C.sub.8 fraction, however, only about 70 to 80% wt. of
the C.sub.6 composition is 1-hexene, with the remaining C.sub.6
by-product comprising compounds such as methylcyclopentane and
methylenecyclopentane. The presence of these other C.sub.6
compositions, which have very little commercial use or value, is
highly undesirable from both an economic point of view as well as
from a product separation point of view.
[0016] Heteroatom Chemistry, volume 2, page 477 discloses the
preparation of (phenyl).sub.2P--N(isopropyl)-P=catechol and
catechol=P--N(isopropyl)-P=catechol. However there is no disclosure
in this document of the use of these compounds in catalyst systems
for the trimerization and tetramerization of olefins.
[0017] It has now surprisingly been found that the catalyst systems
derived from the ligands of the present invention are valuable in
providing high levels of both hexene and octene in a process for
the simultaneous trimerization and tetramerization of ethylene,
with a high selectivity for both 1-hexene and 1-octene within the
C6 and C8 fractions, respectively. In addition, the catalyst
systems of the present invention have improved activity and allow
the trimerization/tetramerization reaction to proceed at
industrially attractive process conditions (e.g. elevated
temperature and pressure) without fast decay of the catalyst.
SUMMARY OF THE INVENTION
[0018] According to a first aspect of the present invention there
is provided a ligand having the general formula (I);
P(R.sup.4)--P(R.sup.1)(R.sup.2).dbd.N(R.sup.3) (I)
wherein: the R.sup.1 group is selected from a hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl and substituted
heterohydrocarbyl group; the R.sup.2 group is selected from
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and
substituted heterohydrocarbyl groups; the R.sup.3 is selected from
hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a
heterohydrocarbyl group, a substituted heterohydrocarbyl group, a
silyl group or derivative thereof; the R.sup.4 group is an
optionally substituted alkylenedioxy, alkylenedimercapto or
alkylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
alkylenedioxy, alkylenedimercapto or alkylenediamino structure or
an optionally substituted arylenedioxy, arylenedimercapto or
arylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
arylenedioxy, arylenedimercapto or arylenediamino structure.
[0019] According to a second aspect of the present invention there
is provided a ligand having the general formula (II);
P(R.sup.1)(R.sup.2)--P(R.sup.4).dbd.N(R.sup.3) (II)
wherein: the R.sup.1 group is selected from a hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl and substituted
heterohydrocarbyl group; the R.sup.2 group is selected from a
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and
substituted heterohydrocarbyl group; the R.sup.3 group is selected
from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl
group, a heterohydrocarbyl group, a substituted heterohydrocarbyl
group, a silyl group or derivative thereof; the R.sup.4 group is an
optionally substituted alkylenedioxy, alkylenedimercapto or
alkylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
alkylenedioxy, alkylenedimercapto or alkylenediamino structure or
an optionally substituted arylenedioxy, arylenedimercapto or
arylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
arylenedioxy, arylenedimercapto or arylenediamino structure.
[0020] According to a further aspect of the present invention there
is provided a process for the preparation of a ligand of formula
(I) or (II) comprising reacting:
[0021] i) a compound having the general formula (III);
(R.sup.1)(R.sup.2)P--N(R.sup.3)--R.sup.5 (III)
wherein: the R.sup.1 group is selected from hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl and substituted
heterohydrocarbyl groups; the R.sup.2 group is selected from
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and
substituted heterohydrocarbyl groups; the R.sup.3 group is selected
from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl
group, a heterohydrocarbyl group, a substituted heterohydrocarbyl
group, a silyl group or derivative thereof; the R.sup.5 group is
selected from hydrogen and a P(R.sup.6)(R.sup.7)-- group; the
R.sup.6 and the R.sup.7 groups are independently selected from
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and
substituted heterohydrocarbyl groups; and
[0022] ii) a compound of the formula X--P(R.sup.4), wherein X is a
halide and the R.sup.4 group is a group which comprises an
optionally substituted alkylenedioxy, alkylenedimercapto or
alkylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
alkylenedioxy, alkylenedimercapto or alkylenediamino structure or
an optionally substituted arylenedioxy, arylenedimercapto or
arylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
arylenedioxy, arylenedimercapto or arylenediamino structure,
and if the R.sup.5 group is hydrogen, a HX-acceptor, preferably at
a temperature in the range of from -30 to 200.degree. C.
[0023] According to yet a further aspect of the present invention
there is provided a ligand system comprising the product formed by
reacting
[0024] i) a compound having the general formula (III);
(R.sup.1)(R.sup.2)P--N(R.sup.3)--R.sup.5 (III)
wherein: the R.sup.1 group is selected from hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl and substituted
heterohydrocarbyl groups; the R.sup.2 group is selected from
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and
substituted heterohydrocarbyl groups; the R.sup.3 group is selected
from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl
group, a heterohydrocarbyl group, a substituted heterohydrocarbyl
group, a silyl group or derivative thereof; the R.sup.5 group is
selected from hydrogen and a P(R.sup.6)(R.sup.7)-- group; the
R.sup.6 and the R.sup.7 groups are independently selected from
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and
substituted heterohydrocarbyl groups; and
[0025] ii) a compound of the formula X--P(R.sup.4), wherein X is a
halide and the R.sup.4 group is a group which comprises an
optionally substituted alkylenedioxy, alkylenedimercapto or
alkylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
alkylenedioxy, alkylenedimercapto or alkylenediamino structure or
an optionally substituted arylenedioxy, arylenedimercapto or
arylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
arylenedioxy, arylenedimercapto or arylenediamino structure,
and if the R.sup.5 group is hydrogen, a HX-acceptor, preferably at
a temperature in the range of from -30 to 200.degree. C.
[0026] According to a further aspect of the present invention there
is provided a ligand having the general formula (IV);
(R.sup.1)(R.sup.8)P--N(R.sup.3)--P(R.sup.4) (IV)
wherein: the R.sup.1 group is selected from a hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl and substituted
heterohydrocarbyl group; the R.sup.8 group is selected from an
aromatic or heteroaromatic group which comprise at least one polar
substituent group, and optionally one or more non-polar substituent
groups; the R.sup.3 group is selected from hydrogen, a hydrocarbyl
group, a substituted hydrocarbyl group, a heterohydrocarbyl group,
a substituted heterohydrocarbyl group, a silyl group or derivative
thereof; the R.sup.4 group is an optionally substituted
alkylenedioxy, alkylenedimercapto or alkylenediamino structure
which is bound to the phosphorus atom through the two oxygen,
sulphur or nitrogen atoms of the alkylenedioxy, alkylenedimercapto
or alkylenediamino structure or an optionally substituted
arylenedioxy, arylenedimercapto or arylenediamino structure which
is bound to the phosphorus atom through the two oxygen, sulphur or
nitrogen atoms of the arylenedioxy, arylenedimercapto or
arylenediamino structure.
[0027] According to a further aspect of the present invention there
is provided a process for the preparation of a ligand of formula
(IV) comprising reacting:
[0028] i) a compound having the general formula (V);
(R.sup.1)(R.sup.8)P--N(R.sup.3)--R.sup.5 (V)
wherein: the R.sup.1 group is selected from hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl and substituted
heterohydrocarbyl groups; the R.sup.8 group is selected from an
aromatic or heteroaromatic group which comprise at least one polar
substituent group, and optionally one or more non-polar substituent
groups; the R.sup.3 is selected from hydrogen, a hydrocarbyl group,
a substituted hydrocarbyl group, a heterohydrocarbyl group, a
substituted heterohydrocarbyl group, a silyl group or derivative
thereof; the R.sup.5 group is selected from hydrogen or a
P(R.sup.6)(R.sup.7)-- group; the R.sup.6 and the R.sup.7 groups are
independently selected from hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl and substituted heterohydrocarbyl groups; and
[0029] ii) a compound of the formula X--P(R.sup.4), wherein X is a
halide and the R.sup.4 group is a group which comprises an
optionally substituted alkylenedioxy, alkylenedimercapto or
alkylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
alkylenedioxy, alkylenedimercapto or alkylenediamino structure or
an optionally substituted arylenedioxy, arylenedimercapto or
arylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
arylenedioxy, arylenedimercapto or arylenediamino structure,
and if the R.sup.5 group is hydrogen, a HX-acceptor, preferably at
a temperature in the range of from -30 to 200.degree. C.
[0030] According to the present invention there is further provided
a ligand having the general formula (VI);
(R.sup.9)(R.sup.10)P--N(R.sup.3)--P(R.sup.4) (VI)
wherein: the R.sup.9 and R.sup.10 groups are independently selected
from optionally substituted alkyl or heteroalkyl groups; the
R.sup.3 group is selected from hydrogen, a hydrocarbyl group, a
substituted hydrocarbyl group, a heterohydrocarbyl group, a
substituted heterohydrocarbyl group, a silyl group or derivative
thereof; the R.sup.4 group is an optionally substituted
alkylenedioxy, alkylenedimercapto or alkylenediamino structure
which is bound to the phosphorus atom through the two oxygen,
sulphur or nitrogen atoms of the alkylenedioxy, alkylenedimercapto
or alkylenediamino structure or an optionally substituted
aylenedioxy, arylenedimercapto or arylenediamino structure which is
bound to the phosphorus atom through the two oxygen, sulphur or
nitrogen atoms of the arylenedioxy, arylenedimercapto or
arylenediamino structure.
[0031] According to yet a further aspect of the present invention
there is provided a process for the preparation of a ligand of
general formula (VI) as described above comprising reacting:
[0032] i) a compound having the general formula (VII);
(R.sup.9)(R.sup.10)P--N(R.sup.3)--R.sup.5 (VII)
wherein: the R.sup.9 and R.sup.10 groups are independently selected
from optionally substituted alkyl or heteroalkyl groups; the
R.sup.3 group is selected from hydrogen, a hydrocarbyl group, a
substituted hydrocarbyl group, a heterohydrocarbyl group, a
substituted heterohydrocarbyl group, a silyl group or derivative
thereof; the R.sup.5 group is selected from hydrogen or a
P(R.sup.6)(R.sup.7)-- group; the R.sup.6 and the R.sup.7 groups are
independently selected from hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl and substituted heterohydrocarbyl groups; and
[0033] ii) a compound of the formula X--P(R.sup.4), wherein X is a
halide and the R.sup.4 group is a group which comprises an
optionally substituted alkylenedioxy, alkylenedimercapto or
alkylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
alkylenedioxy, alkylenedimercapto or alkylenediamino structure or
an optionally substituted arylenedioxy, arylenedimercapto or
arylenediamino structure which is bound to the phosphorus atom
through the two oxygen, sulphur or nitrogen atoms of the
arylenedioxy, arylenedimercapto or arylenediamino structure,
and if the R.sup.5 group is hydrogen, an HX-acceptor, preferably at
a temperature in the range of from -30 to 200.degree. C.
[0034] According to a further aspect of the present invention there
is provided a catalyst system comprising the product formed by
combining:
[0035] a) a source of chromium, molybdenum or tungsten;
[0036] b) one or more ligands as described herein and;
[0037] c) a cocatalyst.
[0038] According to a further aspect of the present invention there
is provided a catalyst system comprising the product formed by
combining:
[0039] a) a source of chromium, molybdenum or tungsten;
[0040] b) a ligand system as described herein and;
[0041] c) a cocatalyst.
[0042] According to yet a further aspect of the present invention
there is provided a process for the oligomerisation of olefinic
monomers, wherein the process comprises contacting at least one
olefinic monomer with a catalyst system described herein.
DETAILED DESCRIPTION OF THE INVENTION
[0043] As used herein, the term "trimerization" means the catalytic
trimerization of an olefinic monomer to give a product composition
enriched in the compound derived from the reaction of three of said
olefinic monomers. The term trimerization includes the cases
wherein all the olefinic monomers in the feed stream are identical
as well as the cases wherein the feed stream contains two or more
different olefinic monomers.
[0044] In particular, the term "trimerization" when used in
relation to the trimerization of ethylene means the trimerization
of ethylene to form a C.sub.6 alkene, especially 1-hexene.
[0045] The term "trimerization selectivity" when used in relation
to the trimerization of ethylene to 1-hexene means the amount of
C.sub.6 fraction formed within the product composition.
[0046] The term "1-hexene selectivity" when used in relation to the
trimerization of ethylene to 1-hexene means the amount of 1-hexene
formed within the C.sub.6 fraction of the product composition. The
overall yield of 1-hexene in the trimerization of ethylene is the
product of the "trimerization selectivity" multiplied by the
"1-hexene selectivity".
[0047] The term "tetramerization" means the catalytic
tetramerization of an olefinic monomer to give a product
composition enriched in the compound derived from the reaction of
four of said olefinic monomers. The term tetramerization includes
the cases wherein all the olefinic monomers in the feed stream are
identical as well as the cases wherein the feed stream contains two
or more different olefinic monomers.
[0048] In particularly, the term "tetramerization" when used in
relation to the tetramerization of ethylene means the
tetramerization of ethylene to form a C.sub.8 alkene, especially
1-octene.
[0049] The term "tetramerization selectivity" when used in relation
to the tetramerization of ethylene to 1-octene means the amount of
C.sub.8 fraction formed within the product composition.
[0050] The term "1-octene selectivity" when used in relation to the
tetramerization of ethylene to 1-octene means the amount of
1-octene formed within the C.sub.8 fraction of the product
composition. The overall yield of 1-octene in the tetramerization
of ethylene is the product of the "tetramerization selectivity"
multiplied by the "1-octene selectivity".
[0051] One aspect of the present invention relates to ligands
having the general formulae (I), (II), (IV) and (VI):
P(R.sup.4)--P(R.sup.1)R.sup.2.dbd.N(R.sup.3) (I)
P(R.sup.1)(R.sup.2)--P(R.sup.4).dbd.N(R.sup.3) (II)
(R.sup.1)(R.sup.8)P--N(R.sup.3)--P(R.sup.4) (IV)
(R.sup.9)(R.sup.10)P--N(R.sup.3)--P(R.sup.4) (VI)
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.8, R.sup.9 and
R.sup.10 are as defined above.
[0052] While not wishing to be limited by theory, it is thought
that in the presence of an activated metal component (a), e.g.
activated chromium, an equilibrium exists between ligands of the
P--P.dbd.N type and ligands of the P--N--P type. For example:
P(R.sup.4)--P(R.sup.1)(R.sup.2).dbd.N(R.sup.3)P(R.sup.1)(R.sup.2)--P(R.s-
up.4).dbd.N(R.sup.3)(R.sup.1)(R.sup.2)P--N(R.sup.3)--P(R.sup.4)
[0053] The term "hydrocarbyl" as used herein in relation to
R.sup.1-R.sup.10 the R groups refers to a group only containing
carbon and hydrogen atoms. The hydrocarbyl group may be a saturated
or unsaturated, linear, branched or cyclic. If the hydrocarbyl is
cyclic, the cyclic group may be an aromatic or non-aromatic group.
Unless otherwise stated, the preferred hydrocarbyl groups for use
herein are those containing from 1 to 20 carbon atoms.
[0054] The term "substituted hydrocarbyl" as used herein in
relation to the R.sup.1-R.sup.10 groups refers to hydrocarbyl
groups which are substituted with one or more substituents defined
hereinbelow.
[0055] The term "heterohydrocarbyl" as used herein refers to a
hydrocarbyl group wherein one or more of the carbon atoms is
replaced by a heteroatom, such as Si, S, N or O. Included within
this definition are heteraromatic rings, i.e. wherein one or more
carbon atom within the ring structure of an aromatic ring is
replaced by a heteroatom.
[0056] The term "substituted heterohydrocarbyl" as used herein
refers to heterohydrocarbyl groups which are substituted with one
or more substituents, defined hereinbelow.
[0057] The term "aromatic" as used herein, refers to a monocyclic
or polycyclic aromatic, ring having from 5 to 14 ring atoms.
Examples of polycyclic aromatic groups include biphenyl,
binaphthyl, naphthyl and anthracenyl. Unless otherwise stated, the
preferred aromatic groups are monocyclic or polycyclic aromatic
rings having from 5 to 10 ring atoms. More preferred aromatic
groups are monocyclic aromatic rings containing 6 carbon atoms. A
most preferred aromatic group is a phenyl group.
[0058] The term "heteroaromatic" as used herein, refers to a
monocyclic or polycyclic, heteroaromatic ring having from 5 to 14
ring atoms, containing from 1 to 3 heteroatoms selected from N, O
and S in the ring, with the remaining ring atoms being carbon.
Preferably, the heteroaromatic groups are monocyclic heteroaromatic
rings, more preferably monocyclic heteroaromatic groups having from
5 to 10 ring atoms, most preferably from 5 to 6 carbon atoms.
[0059] The term "substituted aromatic" as used herein means that
the aromatic group may be substituted with one or more substituents
defined hereinbelow.
[0060] The term "substituted heteroaromatic" as used herein means
that the aromatic group may be substituted with one or more
substituents defined hereinbelow.
[0061] Suitable substituent groups for use in the present invention
can contain carbon atoms and/or heteroatoms. The substituents may
be either polar or non-polar.
[0062] Polar is defined by IUPAC as an entity with a permanent
electric dipole moment. Therefore, as used herein, the term "polar
substituent" means a substituent group which incorporates a
permanent electric dipole moment.
[0063] IUPAC defines non-polar as an entity without a permanent
electric dipole moment. Therefore, as used herein, the term
"non-polar substituent" means a substituent group which does not
incorporate a permanent electric dipole moment.
[0064] Suitable substituents include hydrocarbyl and
heterohydrocarbyl groups, which may be straight-chain or branched,
saturated or unsaturated, aromatic or non-aromatic. Non-limiting
examples of suitable aromatic substituents include monocyclic and
polycyclic aromatic and heteroaromatic groups, preferably aromatic
groups having from 5 to 10 atoms in the ring, examples of such
groups include phenyl and C.sub.1-C.sub.4 alkyl substituted phenyl
groups. Non-limiting examples of suitable non-aromatic hydrocarbyl
substituents include linear or branched alkyl or cycloalkyl groups,
preferably having from 1 to 10 carbon atoms, more preferably 1 to 4
carbon atoms. Non-limiting examples of suitable non-aromatic
heterohydrocarbyl substituents include linear or branched alkoxy,
alkoxyalkyl, alkylsulphonyl, alkylthioalkyl, alkylamino, alkylsilyl
and heterocyclic groups.
[0065] Other suitable substituent groups include halides such as
chloride, bromide and iodide, thiol, --OH, A.sup.1-O--, --S--Al,
--CO--Al, --NA.sup.1A.sup.2, --CO--NA.sup.1A.sup.2 in which A.sup.1
and A.sup.2, independently, are non-aromatic hydrocarbyl or
heterohydrocarbyl groups, preferably having from 1 to 10 carbon
atoms, more preferably 1 to 4 carbon atoms, e.g. methyl, ethyl,
propyl and isopropyl.
[0066] Preferred substituent groups are hydrocarbyl groups,
heterohydrocarbyl groups, and halides, in particularly hydrocarbyl
groups.
[0067] The R.sup.1, R.sup.2, R.sup.6 and R.sup.7 groups are
independently selected from hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl and substituted heterohydrocarbyl groups.
[0068] Examples of suitable R.sup.1, R.sup.2, R.sup.6 and R.sup.7
groups include optionally substituted benzyl, phenyl, tolyl, xylyl,
mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy,
tolyloxy, dimethylamino, diethylamino, methylethylamino,
thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl,
dimethylhydrazyl, methyl, ethyl, ethenyl, propyl, butyl, propenyl,
propynyl, cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl
groups.
[0069] The R.sup.1, R.sup.2, R.sup.6 and R.sup.7 groups are
preferably independently selected from optionally substituted
aromatic and optionally substituted heteroaromatic groups, more
preferably optionally substituted aromatic groups, especially
optionally substituted phenyl.
[0070] In one embodiment of the present invention, the R.sup.1 and
R.sup.2 groups are independently selected from an aromatic or
heteroaromatic group, especially phenyl, which comprises at least
one polar substituent group, and optionally one or more non-polar
substituents.
[0071] In another embodiment of the present invention, the R.sup.1
and R.sup.2 groups are independently selected from an unsubstituted
aromatic or heteroaromatic group, preferably an unsubstituted
aromatic group, especially phenyl.
[0072] In yet another embodiment, R.sup.1 is selected from an
aromatic or heteroaromatic group, especially phenyl, which
comprises at least one polar substituent group, and optionally one
or more non-polar substituents, and R.sup.2 is selected from an
unsubstituted aromatic or heteroaromatic group, especially
phenyl.
[0073] Suitable non-polar substituent groups include hydrocarbyl
substituent groups which do not contain heteroatoms.
[0074] Examples of suitable non-polar substituents include methyl,
ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl,
hexyl, cyclopentyl, 2-methylcyclohexyl, cyclohexyl,
cyclopentadienyl, phenyl, bi-phenyl, naphthyl, tolyl, xylyl,
mesityl, ethenyl, propenyl and benzyl groups, or the like.
[0075] Preferred non-polar substituent groups include alkyl groups,
in particularly C.sub.1-C.sub.4 alkyl groups such as methyl, ethyl,
propyl, isopropyl, butyl, and isobutyl groups.
[0076] Suitable polar substituents for use herein include, but are
not necessarily limited to, optionally branched C.sub.1-C.sub.20
alkoxy groups, (e.g. connected to the R1 and R2 groups through an
oxygen bridging atom); optionally substituted C.sub.5-C.sub.14
aryloxy groups, (e.g. connected to the R1 and R2 groups through an
oxygen bridging atom); optionally branched C.sub.1-C.sub.20
alkoxy(C.sub.1-C.sub.20)alkyl groups, (e.g. a C.sub.1-C.sub.20
hydrocarbyl group bearing a C.sub.1-C.sub.20 alkoxy group); halides
such as chloride, bromide and iodide; hydroxyl; amino;
(di-)C.sub.1-C.sub.6 alkylamino; nitro; C.sub.1-C.sub.6
alkylsulphonyl; C.sub.1-C.sub.6 alkylthio(C.sub.1-C.sub.6)alkyl
groups; sulphate; heterocyclic groups, especially with at least one
N and/or O ring atom; and tosyl groups.
[0077] Specific examples of suitable polar substituents include
methoxy, ethoxy, isopropoxy, phenoxy, pentafluorophenoxy,
trimethylsiloxy, dimethylamino, methylsulphonyl, tosyl,
methoxymethyl, methylthiomethyl, 1,3-oxazolyl, hydroxyl, amino,
methoxymethyl, phosphino, arsino, stibino, sulphate, nitro and the
like.
[0078] Preferably, the polar substituents on the R.sup.1 and
R.sup.2 groups are independently selected from optionally branched
C.sub.1-C.sub.20 alkoxy groups, optionally substituted
C.sub.5-C.sub.14 aryloxy groups, and optionally branched
C.sub.1-C.sub.20 alkyl(C.sub.1-C.sub.20)alkoxy groups. More
preferably, the polar substituents are independently selected from
optionally branched C.sub.1-C.sub.20 alkoxy groups, especially
optionally branched C.sub.1-C.sub.6 alkoxy groups such as, for
example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
tert-butoxy, pentoxy, isopentoxy, hexoxy or isohexoxy, of which
methoxy, ethoxy and isopropoxy are particularly preferred polar
substituent groups.
[0079] In one embodiment, the R.sup.1 and/or R.sup.2 groups
independently bears a polar substituent on at least one of the
ortho-positions. Said R.sup.1 and/or R.sup.2 group can also be
optionally substituted by either a polar or non-polar group at any
other position on the aromatic or heteroaromatic group.
[0080] For the avoidance of doubt, the phrase "bears a polar
substituent on at least one of the ortho-positions" means, for
example, that the R.sup.1 and/or R.sup.2 group is substituted with
a polar substituent on one or both of its ortho positions.
[0081] By the term "ortho-position" when used in relation to
substituents on the R.sup.1 and R.sup.2 groups, it is meant that
the substituent is in the ortho position relative to the atom
bonded to the phosphorus atom.
[0082] The R.sup.3 group is selected from hydrogen, a hydrocarbyl
group, a substituted hydrocarbyl group, a heterohydrocarbyl group,
a substituted heterohydrocarbyl group, a silyl group or derivative
thereof. Typically, R.sup.3 is selected from hydrogen or the groups
consisting of alkyl, substituted alkyl, aryl, substituted aryl,
aryloxy, substituted aryloxy, alkenyl, substituted alkenyl,
cycloalkyl, substituted cycloalkyl, alkoxycarbonyl, carbonyloxy,
alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups or
derivatives thereof, and alkyl or aryl groups substituted with any
of these substituents or halogen or a nitro group.
[0083] Preferably, the R.sup.3 group is selected from a hydrocarbyl
group, a substituted hydrocarbyl group, a heterohydrocarbyl group,
a substituted heterohydrocarbyl group, a silyl group or derivative
thereof. More preferably R.sup.3 is an alkyl, substituted alkyl
(including heterocyclic substituted alkyl with at least one
heteroatom, such as N or O, and alkyl groups substituted with a
heteroatom or heteroatomic group), cycloalkyl, substituted
cycloalkyl, substituted cyclic aryl, substituted aryl, aryloxy or
substituted aryloxy group.
[0084] Examples of suitable R.sup.3 groups include C.sub.1-C.sub.15
alkyl groups, substituted C.sub.1-C.sub.15 alkyl groups,
C.sub.1-C.sub.15 alkenyl groups, substituted C.sub.1-C.sub.15
alkenyl groups, C.sub.3-C.sub.15 cycloalkyl groups, substituted
C.sub.3-C.sub.15 cycloalkyl groups, C.sub.5-C.sub.15 aromatic
groups, substituted C.sub.5-C.sub.15 aromatic groups,
C.sub.1-C.sub.15 alkoxy groups and substituted C.sub.1-C.sub.15
alkoxy groups. Most preferred R.sup.3 groups are the
C.sub.1-C.sub.15 alkyl groups, which include both linear and
branched alkyl groups; suitable examples include methyl, ethyl,
propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, alkyl
branched pentyl groups, hexyl, alkyl branched hexyl groups, heptyl,
alkyl branched heptyl groups, octyl and alkyl branched octyl
groups.
[0085] Examples of suitable --N(R.sup.3)-- groups include
--N(methyl)-, --N(ethyl)-, --N(propyl)-, --N(isopropyl)-,
--N(butyl)-, --N(t-butyl)-, --N(pentyl)-, --N(hexyl)-,
--N(2-ethylhexyl)-, --N(cyclohexyl)-, --N(1-cyclohexylethyl)-,
--N(2-methylcyclohexyl)-, --N(benzyl)-, --N(phenyl)-,
--N(2-octyl)-, --N(4-methoxyphenyl)-, --N(4-tert-butylphenyl)-,
--N((CH.sub.2).sub.3--N-morpholine)-, --N(Si(CH.sub.3).sub.3)--,
--N(CH.sub.2CH.sub.2CH.sub.2Si(OMe).sub.3))-, --N(decyl)- and
--N(allyl)-.
[0086] In the compound of formula X--P(R.sup.4), the halide group,
X, is typically selected from fluoride, chloride, bromide or
iodide, preferably, fluoride, chloride or bromide, especially
bromide or chloride.
[0087] The R.sup.4 group is an optionally substituted
alkylenedioxy, alkylenedimercapto or alkylenediamino structure
which is bound to the phosphorus atom through the two oxygen,
sulphur or nitrogen atoms of the alkylenedioxy, alkylenedimercapto
or alkylenediamino structure or an optionally substituted
arylenedioxy, arylenedimercapto or arylenediamino structure which
is bound to the phosphorus atom through the two oxygen, sulphur or
nitrogen atoms of the arylenedioxy, arylenedimercapto or
arylenediamino structure.
[0088] Suitable examples of arylenedioxy groups include, but are
not limited to, 1,2-phenylenedioxy, 1,2-dihydroxynaphthalene,
2,3-dihydroxynaphthalene, 1,2-dihydroxyanthracene,
1,2-dihydroxyphenanthrene, 2,3-dihydroxyphenanthrene,
3,4-dihydroxyphenanthrene, 9,10-dihydroxyphenanthrene,
1,8-dihydroxynaphthalene, 2,2'-dihydroxybiphenyl, and
2,2'-dihydroxy-1,1'-binaphthyl. The dimercapto and optionally
substituted diamino analogues of these compounds are examples of
suitable arylenedimercapto and arylenediamino groups,
respectively.
[0089] Suitable alkylenedioxy groups include
2,3-dimethyl-2,3-butylenedioxy (=tetramethylethylenedioxy) and
1,3-propylenedioxy. The dimercapto and optionally substituted
diamino analogues of these compounds are examples of suitable
alkylenedimercapto and alkylenediamino groups, respectively.
[0090] In preferred embodiments, R.sup.4 is an optionally
substituted alkylenedioxy or arylenedioxy group. 1,2-alkylenedioxy
or 1,2-arylenedioxy groups are most preferred, especially
1,2-arylenedioxy groups.
[0091] In a particularly preferred embodiment the R.sup.4 group is
an optionally substituted 1,2-arylenedioxy group having the
following structure, which is bound to the phosphorus atom through
the two ortho positioned oxygen atoms of the ortho-arylenedioxy
structure, i.e.
##STR00001##
[0092] wherein the R.sup.11 to R.sup.14 groups on the phenyl ring
are independently selected from hydrogen, hydrocarbyl groups,
substituted hydrocarbyl groups, inert functional groups or any two
of the R.sup.11 to R.sup.14 groups may be linked together to form a
cyclic hydrocarbyl or heterohydrocarbyl structure.
[0093] Preferably, the R.sup.11 to R.sup.14 groups are
independently selected from hydrogen, halogen, hydrocarbyl,
heterohydrocarbyl, or two of the R.sup.11 to R.sup.14 groups are
linked together to form a cyclic hydrocarbyl or heterohydrocarbyl
structure.
[0094] Examples of suitable R.sup.11 to R.sup.14 groups include
hydrogen, fluorine, chlorine, bromine, iodine, C.sub.1-C.sub.15
alkyl groups, substituted C.sub.1-C.sub.15 alkyl groups,
C.sub.1-C.sub.15 alkenyl groups, substituted C.sub.1-C.sub.15
alkenyl groups, C.sub.3-C.sub.15 cycloalkyl groups, substituted
C.sub.3-C.sub.15 cycloalkyl groups, C.sub.5-C.sub.15 aromatic
groups, substituted C.sub.5-C.sub.15 aromatic groups,
C.sub.1-C.sub.15 alkoxy groups, substituted C.sub.1-C.sub.15 alkoxy
groups, alcohol groups, amino groups and thiol groups.
Alternatively, two of the R.sup.11 to R.sup.14 groups are linked
together to form a cyclic hydrocarbyl or heterohydrocarbyl
structure, examples of such structures include optionally
substituted phenyl, biphenyl, naphthyl, binaphthyl, anthracenyl,
phenanthryl, thiophenyl, pyridyl, cyclopentyl, cyclohexyl,
ferrocenyl and tetrahydrofuranyl groups.
[0095] In one specific preferred embodiment, the R.sup.11 to
R.sup.14 groups are hydrogen, i.e. ortho-phenylenedioxy.
[0096] In the ligand of formula (IV):
(R.sup.1)(R.sup.8)--P--N(R.sup.3)--P(R.sup.4) (IV)
the R.sup.1 group is selected from a hydrocarbyl, substituted
hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl,
as defined hereinabove; and the R.sup.8 group is selected from an
aromatic or heteroaromatic group which comprises at least one polar
substituent group, and optionally one or more non-polar substituent
groups.
[0097] In the case of ligand (IV), it is preferable that the
R.sup.1 group is selected from an optionally substituted aromatic
or optionally substituted heteroaromatic group, such as an
optionally substituted phenyl, more preferably an optionally
substituted aromatic or optionally substituted heteroaromatic group
which comprises at least one polar substituent group, and
optionally one or more non-polar substituent groups, such as a
phenyl group substituted with at least one polar substituent.
[0098] In the case of ligand (IV), it is particularly preferred
that R.sup.1 and R.sup.8 are both phenyl groups substituted with a
polar group on at least one of the ortho positions.
[0099] In the case of ligand (VI):
(R.sup.9)(R.sup.10)P--N(R.sup.3)--P(R.sup.4)
R.sup.9 and R.sup.10 are independently selected from optionally
substituted alkyl or heteroalkyl groups. Suitable alkyl groups
include bulky alkyl groups have 4 or more carbon atoms, preferably
alkyl groups having 4 to 8 carbon atoms. Suitable heteroalkyl
groups include those bulky alkyl groups listed above wherein one or
more of the carbon atoms is substituted with one or more
heteroatoms such as Si, S, N or O. In preferred embodiments,
R.sup.9 and R.sup.10 are both independently selected from an
optionally substituted alkyl, preferably a C.sub.4-C.sub.8 alkyl,
especially tert-butyl.
[0100] The ligands of general formulae (I) and (II) are prepared
herein by a process which comprises reacting:
[0101] i) a compound having the general formula (III):
(R.sup.1)(R.sup.2)P--N(R.sup.3)--R.sup.5 (III)
wherein R.sup.1, R.sup.2, R.sup.3 are as defined above for formulae
(I) and (II) and R.sup.5 is selected from hydrogen and a
P(R.sup.6)(R.sup.7)-- group; wherein R.sup.6 and R.sup.7 are
independently selected from hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl and substituted heterohydrocarbyl groups; and
[0102] ii) a compound of the formula X--P(R.sup.4), wherein X is a
halide and the R.sup.4 groups is as defined above for ligands of
general formulae (I) and (II); preferably at a temperature in the
range of from -30 to 200.degree. C.
[0103] Importantly, if the R.sup.5 group is hydrogen, an HX
acceptor compound must also be used. Suitable HX-acceptors for use
herein include neopentyl lithium, n-butyl lithium, sec-butyl
lithium, lithium hydride, sodium hydride, potassium hydride,
triethylamine, trimethylamine, tripropylamine and the like.
[0104] In the case where R.sup.5 is P(R.sup.6)(R.sup.7), it should
be noted that the ligand composition formed also comprises
X--P(R.sup.6)(R.sup.7) as by-product. This by-product does not
interfere to any significant degree with an oligomerization
reaction and therefore need not be removed from the resulting
ligand composition prior to formation of a catalyst
composition.
[0105] In preferred embodiments, R.sup.6 and R.sup.7 are selected
from an aromatic or heteroaromatic group, preferably an aromatic
group comprising at least one polar substituent group.
[0106] The product of the reaction of compound (III) with
X--P(R.sup.4) may comprise a mixture of ligands in equilibrium with
each other, for example, a mixture of ligands (I) and (II) with
their P--N--P analogue (R.sup.1)(R.sup.2)P--N(R.sup.3)--P(R.sup.4).
Indeed, in the examples section below, the preparation of ligand F
gives a 4:1 mixture of P--P.dbd.N and P--N--P structures. This
mixture of ligands can be used as such in a catalyst composition,
without first separating out the individual ligands. Hence
according to another aspect of the present invention there is
provided a ligand system comprising the product formed by reacting
(i) a compound having the general formula (III) as defined
hereinabove with a compound of formula X--P(R.sup.4) as defined
hereinabove.
[0107] The ligand of general formula (IV) can be prepared by a
process comprising reacting:
[0108] (i) a compound having the general formula (V)
(R.sup.1)(R.sup.8)P--N(R.sup.3)--R.sup.5 (V)
wherein R.sup.1, R.sup.8, R.sup.3 and R.sup.5 are as defined
hereinabove; and
[0109] (ii) a compound of formula X--P(R.sup.4) wherein X and
R.sup.4 are defined hereinabove; and if the R.sup.5 group is H, an
HX-acceptor, preferably at a temperature of from -30.degree. C. to
200.degree. C.
[0110] The ligand of formula (VI) can be prepared by a process
comprising reacting:
[0111] (i) a compound having the general formula (VII)
(R.sup.9)(R.sup.10)P--N(R.sup.3)--R.sup.5 (VII)
wherein R.sup.9, R.sup.10, R.sup.3 and R.sup.5 are as defined
hereinabove; and
[0112] (ii) a compound of formula X--P(R.sup.4) wherein X and
R.sup.4 are defined hereinabove,
and if the R.sup.5 group is H, an HX-acceptor, preferably at a
temperature of from -30.degree. C. to 200.degree. C.
[0113] The ligands and ligand systems of the present invention are
useful in catalyst compositions for the oligomerization of olefins.
The catalyst compositions of the present invention comprise: [0114]
(a) a source of chromium, molybdenum or tungsten; [0115] (b) one or
more ligands or ligand systems as described herein; and [0116] (c)
a cocatalyst.
[0117] The source of chromium, molybdenum or tungsten, component
(a), for the catalyst system of the present invention can include
simple inorganic and organic salts of chromium, molybdenum or
tungsten. Examples of simple inorganic and organic salts are
halides, acetylacetonates, carboxylates, oxides, nitrates, sulfates
and the like. Further sources of chromium, molybdenum or tungsten
can also include co-ordination and organometallic complexes, for
example chromium trichloride tris-tetrahydrofuran complex,
(benzene)tricarbonylchromium, chromium hexacarbonyl, and the like.
Preferably, the source of chromium, molybdenum or tungsten,
component (a), for the catalyst system is selected from simple
inorganic and organic salts of chromium, molybdenum or
tungsten.
[0118] In one embodiment of the present invention, the source of
chromium, molybdenum or tungsten, component (a), for the catalyst
system is a simple inorganic or organic salt of chromium,
molybdenum or tungsten, which is soluble in a solvent such as those
disclosed in U.S. Pat. No. 7,141,633 which is herein incorporated
by reference.
[0119] The source of chromium, molybdenum or tungsten can also
include a mixture of any combination of simple inorganic salts,
simple organic salts, co-ordination complexes and organometallic
complexes.
[0120] In a preferred embodiment herein, component (a) is a source
of chromium, particularly chromium (III).
[0121] Preferred sources of chromium for use herein are simple
inorganic and organic salts of chromium and co-ordination or
organometallic complexes of chromium. More preferred sources of
chromium for use herein are the simple inorganic and organic salts
of chromium, such as salts of carboxylic acids, preferably salts of
alkanoic acids containing 1 to 30 carbon atoms, salts of
aliphatic-.beta.-diketones and salts of .beta.-ketoesters (e.g.
chromium (III) 2-ethylhexanoate, chromium (III) octanoate and
chromium (III) acetylacetonate), and halide salts of chromium, such
as chromium trichloride, chromium trichloride tris-tetrahydrofuran
complex, chromium tribromide, chromium trifluoride, and chromium
tri-iodide. Specific examples of the preferred source of chromium
for use herein is chromium (III) acetylacetonate, also called
chromium tris(2,4-pentanedionate), Cr(acac).sub.3, chromium
trichloride, CrCl.sub.3, and chromium trichloride
tris-tetrahydrofuran complex, CrCl.sub.3(THF).sub.3.
[0122] The cocatalyst, may in principle be any compound or mixture
of compounds that generates an active catalyst system with the
source of chromium, molybdenum or tungsten, component (a), and the
ligand, component (b).
[0123] Compounds which are suitable for use as a cocatalyst include
organoaluminium compounds, organoboron compounds, organic salts,
such as methyllithium and methylmagnesium bromide and the like.
[0124] Particularly preferred cocatalysts are organoaluminium
compounds. Suitable organoaluminium compounds for use herein are
those having the formula AlR.sup.15.sub.3, wherein each R.sup.15
group is independently selected from C.sub.1-C.sub.30 alkyl
(preferably C.sub.1-C.sub.12 alkyl), oxygen containing moieties and
halides, and compounds such as LiAlH.sub.4 and the like.
Non-limiting examples of suitable organoaluminium compounds include
trimethylaluminium (TMA), triethylaluminium (TEA),
tri-isobutylaluminium (TIBA), tri-n-octylaluminium, methylaluminium
dichloride, ethylaluminium dichloride, dimethylaluminium chloride,
diethylaluminium chloride and aluminoxanes (also called
alumoxanes). Mixtures of organoaluminium compounds are also
suitable for use herein.
[0125] In a preferred embodiment herein, the cocatalyst is an
aluminoxane cocatalyst. These aluminoxane cocatalysts may comprise
any aluminoxane compound or a mixture of aluminoxane compounds.
Aluminoxanes may be prepared by the controlled addition of water to
an alkylaluminium compound, such as those mentioned above, or are
available commercially. In this context it should be noted that the
term "aluminoxane" as used within this specification includes
commercially available aluminoxanes, which are derived from the
corresponding trialkylaluminium by addition of water and which may
contain from 2 to 15% wt., typically about 5% wt., but optionally
about 10% wt., of aluminium.
[0126] Other suitable co-catalysts include those disclosed in U.S.
Pat. No. 7,141,633, U.S. Published Patent Applications Nos.
2006/0128910, 2006/0173226, 2006/0211903, and 2006/0229480, which
are incorporated herein in their entirety by reference.
[0127] The components of the catalyst system may be added together
simultaneously or sequentially in any order so as to provide an
active catalyst. The three catalyst components of the catalyst
system, (a), (b) and (c), may be contacted in the presence of any
suitable solvent. Suitable solvents are known to those skilled in
the art, suitable solvents may include any inert solvent that does
not react with the co-catalyst component, such as saturated
aliphatic, unsaturated aliphatic, aromatic, halogenated
hydrocarbons and ionic liquids. Typical solvents include, but are
not limited to, benzene, toluene, xylene, ethylbenzene, cumene,
propane, butane, pentane, heptane, decane, dodecane, tetradecane,
methylcyclohexane, methylcyclopentane, cyclohexane, 1-hexene,
1-octene and the like. Other examples of suitable solvents are
those disclosed in U.S. Pat. No. 7,141,633, such as hydrocarbon
solvents and polar solvents such as diethyl ether, tetrahydrofuran,
dichloromethane, chloroform, chlorobenzene and the like.
[0128] The ligand, component (b), can either be formed prior to the
formation of the catalyst, can be formed simultaneously with the
formation of the catalyst or a catalyst precursor comprising
catalyst components (a) and (b), or can be formed in-situ under an
olefinic monomer, e.g. an ethylene, atmosphere. If the ligand is
formed prior to the formation of the catalyst, this is typically
performed by reacting the compound having the general formula
(III), (V) or (VII) and the compound of the formula X--P(R.sup.4)
in a solvent, such as those mentioned above, at a temperature in
the range of from -30 to 200.degree. C. Depending on R.sup.5.dbd.H
or R.sup.5.dbd.P(R.sup.6)(R.sup.7) temperature is either below 0
and 100.degree. C., respectively. The reaction of the compound
having the general formula (III), (V) or (VII) and the compound of
the formula X--P(R.sup.4) can be performed under an inert
atmosphere.
[0129] Because the by-product formed in the reaction of the
compound having the general formula (III), (V) and (VII) and the
compound of the formula X--P(R.sup.4) does not interfere with the
catalytic activity of the catalyst composition, it is not necessary
to isolate the ligand having the formula (I), (II), (IV) and/or
(VI). Since the catalytic activity of the catalyst composition is
independent of the presence of the by-product compound, the
optional isolation of the ligand having the formula (I), (II), (IV)
or (VI) by any method known in the art, and using said isolated
ligand in the catalyst composition are also included herein. It is,
however, observed that the absence of co-produced
(R.sup.6)(R.sup.7)P--X e.g. (o-anisyl).sub.2P--Cl, as in the case
of the isolated ligands, leads to higher activity of the catalyst
system as evidenced by the higher Turnover Frequencies (TOF's). The
methods of preparation described hereinabove in which the R.sup.5
group in the compounds of formula (III), (V) or (VII) is hydrogen,
advantageously does not produce (R.sup.6)(R.sup.7)P--X as
byproduct.
[0130] In one embodiment of the present invention, the catalyst
system is formed by adding the co-catalyst component, (c), to a
catalyst precursor composition comprising components (a) and
(b).
[0131] The catalyst system of the present invention may be prepared
either in the presence (i.e. "in-situ") or absence of the olefinic
monomer. The three catalyst components of the catalyst system, (a),
(b) and (c), may be combined fully in the absence of the olefinic
monomer, or the olefinic monomer may be included prior to
contacting the components of the catalyst system, simultaneously
with the components of the catalyst system or at any point in the
process of contacting the components of the catalyst.
[0132] The three components of the catalyst system, (a), (b) and
(c), if component (b) has been preformed, may be combined at a
temperature in the range of from -100 to 200.degree. C., preferably
0 to 150.degree. C., more preferably 20 to 100.degree. C., and, if
(b) has not been preformed, may be combined at a temperature in the
range of from 30 to 200.degree. C., preferably 50 to 150.degree.
C., more preferably 70 to 150.degree. C.
[0133] The catalyst system of the process of the present invention
may be unsupported or supported on a support material. Examples of
suitable support materials can be found in U.S. Pat. No. 7,141,633
and U.S. Published Patent Applications Nos. 2006/0128910,
2006/0173226, 2006/0211903, and 2006/0229480, which are
incorporated herein in their entirety by reference.
[0134] The quantity of cocatalyst in the catalyst system the
present invention is typically enough to provide a ratio in the
range from 0.1 to 20,000, preferably from 1 to 2000, more
preferably 1 to 1000, most preferably 1 to 500, aluminium or boron
atoms per atom of chromium, molybdenum or tungsten.
[0135] The amount of chromium, molybdenum or tungsten, and the
amount of the ligand, can be present in the catalyst composition in
a molar ratio in the range from 10000:1 to 1:10000, preferably from
100:1 to 1:100, more preferably from 10:1 to 1:10. Most preferably,
the chromium, molybdenum or tungsten, and the ligand are present in
a molar ratio in the range from 3:1 to 1:3. Generally the amount of
chromium, molybdenum or tungsten, and the amount of ligand are
approximately equal or double, i.e. a molar ratio in the range from
1.5:1 to 1:3.
[0136] The olefinic monomers suitable for use in the trimerization
and tetramerization process of the present invention can be any
olefinic monomers, which can be converted into a trimer or
tetramer. Suitable olefinic monomers include, but are not
necessarily limited to, ethylene, propylene, optionally branched
C.sub.4-C.sub.24, preferably C.sub.4-C.sub.20 .alpha.-olefins,
optionally branched C.sub.4-C.sub.24, preferably C.sub.4-C.sub.20
internal olefins, optionally branched C.sub.4-C.sub.24, preferably
C.sub.4-C.sub.20 vinylidene olefins, optionally branched
C.sub.4-C.sub.24, preferably C.sub.4-C.sub.20 cyclic olefins and
optionally branched C.sub.4-C.sub.24, preferably C.sub.4-C.sub.20
dienes, as well as optionally branched C.sub.4-C.sub.24, preferably
C.sub.4-C.sub.20 functionalized olefins. Examples of suitable
olefinic monomers include, but are not necessarily limited to,
linear .alpha.-olefins, such as ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,
1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and
1-eicosene; branched .alpha.-olefins such as 4-methylpent-1-ene and
1-ethyl-1-hexene; linear and branched internal-olefins such as
2-butene; styrene; cyclohexene; norbornene and the like.
[0137] Mixtures of olefinic monomers can also be used in the
process of the present invention.
[0138] Preferred olefinic monomers for use in the trimerization and
tetramerization process of the present invention are propylene and
ethylene. Especially preferred is ethylene.
[0139] The catalyst system and process of the present invention are
particularly useful for the oligomerization of ethylene with a high
selectivity towards 1-hexene and 1-octene.
[0140] The oligomerization reaction can be performed in solution
phase, slurry phase, gas phase or bulk phase.
[0141] When the oligomerization is performed in solution or slurry
phase, a diluent or solvent, which is substantially inert under the
oligomerization conditions may be employed. Suitable diluents or
solvents are aliphatic and aromatic hydrocarbons, halogenated
hydrocarbons and olefins which are substantially inert under
oligomerization conditions may be employed, such as those disclosed
in U.S. Pat. No. 7,141,633 and U.S. Published Patent Applications
Nos. 2006/0128910, 2006/0173226, 2006/0211903, and 2006/0229480,
which are incorporated herein in their entirety by reference.
[0142] The oligomerization process of the present invention may be
performed in any one of a number of suitable reactors, which are
well known to one skilled in the art. Typically the oligomerization
process of the present invention is carried out in a batch,
semi-batch or continuous mode.
[0143] The oligomerization process of the present invention may be
carried out under the following range of reaction conditions.
Typically, the temperature will be in the range from about
0.degree. C. to about 150.degree. C., preferably from about
30.degree. C. to about 150.degree. C., and more preferably from
about 70.degree. C. to about 150.degree. C. The pressure range
under which the process of the present invention may be performed
is typically in the range of from below atmospheric pressure to
about 100 barg. Preferably, the pressure will be in the range from
about 0.1 to about 80 barg, more preferably from about 0.5 to about
70 barg, especially in the range of from about 1 to about 60 barg.
Temperatures and pressures outside those stated above may also be
employed, however, the reaction product slate will either have an
excess of heavy and/or solid by-products or an insignificant amount
of the trimer or tetramer.
[0144] By varying the temperature and pressure it is possible for
ratio of trimers and tetramers produced in the process of the
present invention to be varied. A trend observed indicates that the
amount of trimers produced in the process of the present invention
increases with increasing temperature. Another trend which has been
observed indicates that the amount of tetramers produced in the
process of the present invention increases with increasing
pressure.
[0145] Therefore, by varying the reaction conditions of the process
of the present invention, the amount of trimers and tetramers in
the oligomerization product composition may be varied. This may be
useful for a continuous or semi-continuous oligomerization process
which produces a high proportion of trimers and tetramers, wherein
the product composition can be changed (e.g. from producing a
higher proportion of trimers to a higher proportion of tetramers,
or vice-versa,) by changing the reactor conditions without having
to interrupt the olefinic monomer feed or the oligomerization
product flow. In particular, this may be especially useful for a
continuous or semi-continuous process for the oligomerization of
ethylene, wherein the product composition can be changed (e.g. from
producing a higher proportion of 1-hexene to a higher proportion of
1-octene, or vice-versa) by changing the reactor conditions without
having to interrupt the olefinic monomer feed or the
oligomerization product flow.
[0146] In one embodiment of the present invention, there is a
process for the oligomerization of olefinic monomers, wherein the
process comprises contacting at least one olefinic monomer under
oligomerization reaction conditions with a catalyst system of the
process of the present invention, wherein the process is a
continuous or semi-continuous process and the reaction conditions
are varied during the process. Variation of the reaction conditions
can be performed to make continual adjustments to a process to
ensure a consistent product composition or can be performed to a
process to change the product composition produced. A preferred
version of this embodiment is a process for the oligomerization of
ethylene, wherein the process comprises contacting ethylene with a
catalyst system of the process of the present invention, wherein
the process is a continuous or semi-continuous process and the
reaction conditions are varied during the process.
[0147] Separation of the products, reactant and catalyst can be
performed by any technique known to one skilled in the art, such as
distillation, filtration, centrifugation, liquid/liquid separation,
extraction, and the like.
[0148] Further details regarding reactors, solvents, separation
techniques, and the like, can be found in U.S. Patent No. 7,141,633
which is herein incorporated by reference.
[0149] The use of the process of the present invention for the
catalytic oligomerization of olefinic monomers provides a simple
method for producing trimers and tetramers of the olefinic monomer.
In particular, the use of the process of the present invention for
the catalytic oligomerization of ethylene provides a simplified
method for producing 1-hexene and 1-octene, with very high
selectivity for 1-hexene and 1-octene over all the other products
formed in the C.sub.6 and C.sub.8 fractions respectively.
[0150] The overall yield of 1-hexene and 1-octene in the process
for the trimerization and tetramerization of ethylene of the
present invention depends upon the reaction conditions
employed.
[0151] Typically, the trimerization and tetramerization selectivity
(i.e. the amount of trimers and tetramers of the olefinic monomers
in the overall product composition) of the process of the present
invention is at least 60% wt, preferably at least 70% wt, more
preferably at least 80% wt, of the overall product composition. The
trimerization and tetramerization selectivity for the trimerization
and tetramerization of ethylene (i.e. the amount of C.sub.6 and
C.sub.8 fraction in the overall product composition) using the
process of the present invention is at least 60% wt, preferably at
least 70% wt, more preferably at least 80% wt, of the overall
product composition.
[0152] The amount of 1-hexene produced by the trimerization and
tetramerization of ethylene using the process of the present
invention is typically in the range of from 10% wt to 90% wt,
preferably from 11% wt to 85% wt, more preferably from 12% wt to
80% wt, of the overall product composition. The amount of 1-octene
produced by the trimerization and tetramerization of ethylene using
the process of the present invention is typically in the range of
from 10% wt to 90% wt, preferably from 11% wt to 85% wt, more
preferably from 12% wt to 80% wt, of the overall product
composition.
[0153] The 1-hexene selectivity (i.e. the amount of 1-hexene
present in the C.sub.6 fraction of the product composition) in the
trimerization and tetramerization of ethylene using the process of
the present invention is preferably at least 85% wt, more
preferably at least 90% wt, most preferably at least 92% wt of the
C.sub.6 fraction of the product composition.
[0154] The 1-octene selectivity (i.e. the amount of 1-octene
present in the C.sub.8 fraction of the product composition) in the
trimerization and tetramerization of ethylene using the process of
the present invention is preferably at least 85% wt, more
preferably at least 90% wt, most preferably at least 92% wt, of the
C.sub.8 fraction product composition.
[0155] The amount of C.sub.10 produced in the trimerization and
tetramerization of ethylene using the process of the present
invention is typically at most about 10% wt.
[0156] The amount of solids produced in the trimerization and
tetramerization of ethylene using the process of the present
invention is typically at most about 5% wt. Lower levels of solid
olefin waxes and polyethylene produced in the trimerization and
tetramerization of ethylene are desirable in commercial operations
as this can reduce the amount of fouling of the reactor equipment,
reduce the amount of waste by-products and reduce the amount of
operational "downtime" due to maintenance and cleaning of the
reactor equipment.
[0157] In one embodiment of the present invention, the olefinic
product composition of the oligomerization of ethylene using the
process of the present invention typically comprises a combined
total content of 1-hexene and 1-octene in the range of from 60 to
98% wt of the overall product composition, preferably from 70 to
98% wt and more preferably from 80 to 100% wt, wherein the 1-hexene
content is typically at least 10% wt of the overall product
composition, the 1-hexene selectivity is typically at least 90% wt
of the C.sub.6 fraction of the product composition, the 1-octene
content is typically at least 10% wt of the overall product
composition, the 1-octene selectivity is typically at least 90% wt
of the C.sub.8 fraction of the product composition, and the amount
of solids produced is at most about 5% wt of the overall product
composition.
[0158] In another embodiment of the present invention, the olefinic
product composition of the trimerization and tetramerization of
ethylene using the process of the present invention comprises a
total content of compounds other than 1-hexene and 1-octene of at
most 40% wt of the overall product composition, preferably at most
30% wt and more preferably at most 20% wt, wherein the 1-hexene
content is typically at least 10% wt of the overall product
composition, the 1-hexene selectivity is typically at least 90% wt
of the C.sub.6 fraction of the product composition, the 1-octene
content is typically at least 10% wt of the overall product
composition, the 1-octene selectivity is typically at least 90% wt
of the C.sub.8 fraction of the product composition, and the amount
of solids produced is at most about 5% wt of the overall product
composition.
[0159] The process of the present invention is illustrated by the
following non-limiting examples.
EXAMPLES
General Procedures and Characterisation
[0160] All chemicals used in preparations were purchased from
Aldrich and used without further purification unless mentioned
otherwise.
[0161] All the operations with the catalyst systems were carried
out under nitrogen atmosphere. All solvents used were dried using
standard procedures. Anhydrous toluene (99.8% purity) was dried
over 4 .ANG. molecular sieves (final water content of about 3
ppm).
[0162] Ethylene (99.5% purity) was purified over a column
containing 4 .ANG. molecular sieves and BTS catalyst (BASF) in
order to reduce water and oxygen content to <1 ppm.
[0163] The oligomers obtained were characterised by Gas
Chromatography (GC), in order to evaluate oligomer distribution
using a HP 5890 series II apparatus and the following
chromatographic conditions:
[0164] Column: HP-1 (cross-linked methyl siloxane), film
thickness=0.25 .mu.m, internal diameter=0.25 mm, length 60 m (by
Hewlett Packard); injection temperature: 325.degree. C.; detection
temperature: 325.degree. C.; initial temperature: 40.degree. C. for
10 minutes; temperature programme rate: 10.0.degree. C./minute;
final temperature: 325.degree. C. for 41.5 minutes; internal
standard: n-hexylbenzene. The yields of the C.sub.4-C.sub.30
olefins were obtained from the GC analysis.
[0165] The amount of "solids", mainly consisting of heavy wax and
polyethylene, has been determined by weighing, after its isolation
from the reactor wall and appendages, followed by washing with
toluene on a glass filter (P3) and by vacuum drying.
[0166] The amount of "total product" is the sum of the amount of
largely olefinic product derived from GC analysis and the amount of
solids.
[0167] The NMR data was obtained at room temperature with a Varian
300 MHz or 400 MHz apparatus.
Catalyst Compositions
[0168] A number of catalyst systems containing ligand compositions
A, A', B', C'', C', C*, D'', D', E, F, G'', H'', K'', L, M'', N'',
Q, T', U and V and a chromium source were prepared and used in the
oligomerisation reactions described below.
Chromium Source
[0169] Chromium tris-(2,4-pentanedionate), also called chromium
tris(acetylacetonate), was used as the chromium source
throughout.
Ligand Composition A
[0170] The reaction product of (2-methoxyphenyl).sub.2PNH(methyl)
and (o-phenylenedioxy)PCl (ligand composition A) was prepared as
follows.
[0171] Under a nitrogen atmosphere 1.015 g (3.62 mmol)
(2-methoxyphenyl).sub.2PCl (available from Aldrich) was added to 10
ml methylamine (2M in THF) in 50 ml pentane. The resulting mixture
was stirred overnight at room temperature. The precipitate was
removed by centrifugation. The solvents were removed from the
resulting solution under vacuum. Washing with pentane yielded 0.85
g (3.09 mmol; (84%)) (2-methoxyphenyl).sub.2PNH(methyl) as a white
solid. .sup.31P-NMR (in C.sub.6D.sub.6) .delta. 31.6.
[0172] Under a nitrogen atmosphere, 133 mg (1.70 mmol) of neopentyl
lithium was slowly added to 428 mg (1.55 mmol) of
(2-methoxyphenyl).sub.2PNH(methyl) in 60 ml dry toluene. To the
resulting mixture 280 mg (1.60 mmol) (o-phenylenedioxy)PCl
(available from Aldrich) in 5 ml toluene was slowly added. The
mixture was stirred for 2 hours at room temperature. To the mixture
25 ml pentane was added. The precipitate was removed by
centrifugation. The solvent was removed under vacuum. The resulting
sticky material was washed with pentane (twice) and a white solid
was isolated. According to .sup.31P-NMR the product consisted at
least predominantly of a P--P.dbd.N(methyl) structure with on one P
atom the o-phenylenedioxy group and on the other P atom two
2-methoxyphenyl groups (either
(o-phenylenedioxy)P(2-methoxyphenyl).sub.2PN(methyl) or
(2-methoxyphenyl).sub.2P(o-phenylenedioxy)PN(methyl)). .sup.31P-NMR
(in C.sub.6D.sub.6) signals at .delta. 153.1 and 35.3 (J.sub.PP=359
Hz).
Ligand Composition A'
[0173] The reaction product of
(2-methoxyphenyl).sub.2PN(methyl)P(2-methoxyphenyl).sub.2 and
(o-phenylenedioxy)PCl (ligand composition A') was prepared as
follows.
[0174] Under a nitrogen atmosphere, 87 mg (o-phenylenedioxy)PCl
(available from Aldrich) was added to 260 mg
(2-methoxyphenyl).sub.2PN(methyl)P(2-methoxyphenyl).sub.2 (Ligand
composition K'') in 2 ml dry toluene. The resulting mixture was
heated to 110.degree. C. overnight.
[0175] The solvent was removed from the solution by heating under
vacuum. Part of the resulting mixture was dissolved in pentane, the
pentane solution was isolated and subsequently the solvent was
removed and the residue was dried under vacuum. According to
.sup.31P-NMR spectroscopy, the product was an approximately 1 to 1
(mol/mol) mixture of (2-methoxyphenyl).sub.2PCl and a
P--P.dbd.N(methyl) structure with on one P atom the
o-phenylenedioxy group and on the other P atom two 2-methoxyphenyl
groups (either (o-phenylenedioxy)P(2-methoxyphenyl).sub.2PN(methyl)
or (2-methoxyphenyl).sub.2P(o-phenylenedioxy)PN(methyl)).
.sup.31P-NMR (in CO.sub.6) .delta. 153.1 and 35.3 (J.sub.pp=359
Hz).
[0176] This mixture was used as such in the catalyst for ethylene
oligomerization experiments without further purification.
Ligand Composition B'
[0177] The reaction product of
(2-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)(2-methoxyphenyl) and
(o-phenylenedioxy)PCl (ligand composition B') was prepared as
follows.
[0178] The
(2-methoxyphenyl)(phenyl)PN(CH.sub.3)P(2-methoxyphenyl)(phenyl)
ligand was prepared by first forming a suspension of 0.42 g lithium
(60 mmol) in 80 ml of tetrahydrofuran (THF), to which was added
9.66 g of (2-methoxyphenyl).sub.2P(phenyl) (30 mmol) at 0.degree.
C. under an argon atmosphere. The mixture was stirred for 4 hours,
after which time a 5 ml aliquot of methanol was added. 60 ml of
toluene was added to the mixture, after which the solution was
extracted with two 40 ml portions of water. The extracted toluene
solution was then concentrated to a volume of approximately 20 ml,
which resulted in formation of a suspension. The concentrated
toluene solution was, filtered, and 4.6 g of C.sub.2Cl.sub.6 was
added to the toluene filtrate, which was then stirred for 2 hours
at 90.degree. C. The HCl gas, which evolved from the reaction, was
"trapped" in an alkali bath. The mixture was then cooled to room
temperature and purged with nitrogen to remove all of the remaining
HCl present in the solution.
[0179] At room temperature, a 5 ml aliquot of triethylamine was
added to the concentrated toluene solution and left for a few
minutes, after which 6 ml of 2 M H.sub.2NMe (12 mmol) was added a
few drops at a time. The suspension was filtered and washed with 20
ml of toluene. The toluene filtrate and the toluene wash fraction
were combined. The combined toluene fractions were evaporated to
dryness and 30 ml of methanol was added. The methanol solution was
left overnight at -35.degree. C. wherein a white
(2-methoxyphenyl)(phenyl)PN(CH.sub.3)P(2-methoxyphenyl)(phenyl)
precipitate was formed in the solution. The precipitated ligand was
then isolated.
[0180] The precipitated ligand consisted of two isomers, a racemic
isomer (the RR and/or the SS enantiomers of the ligand) and a meso
isomer (the RS enantiomer of the ligand). The proportions of these
two isomers were determined by .sup.31P NMR with peaks at 63.18 and
64.8 ppm corresponding to the two different isomers respectively.
These two samples consisted of mixtures of both the racemic and the
meso isomers having weight ratios of 57/43 and 92/8 respectively.
Only the sample of
(2-methoxyphenyl)(phenyl)PN(CH.sub.3)P(2-methoxyphenyl)(phenyl)
with the racemic and the meso isomers in a weight ratio of 57/43
was used.
[0181] Under a nitrogen atmosphere, 14 mg (o-phenylenedioxy)PCl was
added to 37 mg
(2-methoxyphenyl)(phenyl)PN(methyl)P(phenyl)(2-methoxyphenyl) in
1.0 ml dry CO.sub.6. The resulting mixture was heated overnight in
an oil bath at 90.degree. C.
[0182] Based on the .sup.31P-NMR spectrum, the main products were
an approximate 1 to 1 (mol/mol) mixture of
(2-methoxyphenyl)(phenyl)PCl and a P--P.dbd.N(methyl) structure
with on one P atom the o-phenylenedioxy group and on the other P
atom one 2-methoxyphenyl group and one phenyl group (either
(o-phenylenedioxy)P(2-methoxyphenyl)(phenyl)PN(methyl) or
(2-methoxyphenyl)(phenyl)P(o-phenylenedioxy)PN(methyl)).
.sup.31P-NMR (in C.sub.6D.sub.6) .delta. 151.7 and 43.0
(J.sub.pp=353 Hz).
[0183] This mixture was used as such in the catalyst for ethylene
oligomerization experiments without further purification.
Ligand Composition C'', Ligand Composition C' and Ligand
composition C*
[0184] The reaction product of
(2-methoxyphenyl).sub.2PNH(isopropyl) and (o-phenylenedioxy)PCl
(ligand composition C'') was prepared as follows.
[0185] Under a nitrogen atmosphere, 3 ml triethylamine was added to
1.5 ml isopropylamine (17.6 mmol) in 5 ml dry toluene. To the
resulting mixture, 2.2 g (7.84 mmol) (2-methoxyphenyl).sub.2PCl in
20 ml toluene was slowly added and allowed to stir overnight at
room temperature. The precipitate was removed by centrifugation.
The solvents were removed from the resulting solution in vacuo.
Washing with pentane yielded (2-methoxyphenyl).sub.2PNH(isopropyl)
as a white solid. .sup.31P-NMR in C.sub.6D.sub.6) .delta. 21.8.
[0186] Under a nitrogen atmosphere, 60 mg (0.77 mmol) of neopentyl
lithium was slowly added to 226 mg of
(2-methoxyphenyl).sub.2PNH(isopropyl) in 20 ml dry toluene. To the
resulting mixture 130 mg (0.75 mmol) (o-phenylenedioxy)PCl in 1 ml
toluene was slowly added. The mixture was stirred for 2 hours at
room temperature. The precipitate was removed by centrifugation.
The solvent was removed in vacuo. After washing with methanol a
product, which according to .sup.31P-NMR had at least predominantly
the P--N(isopropyl)-P structure, i.e.
(2-methoxyphenyl).sub.2PN(isopropyl)P(o-phenylenedioxy), was
isolated as a white solid. .sup.31P-NMR (in C.sub.6D.sub.6) .delta.
156.9 and 11.6 (J.sub.PP=.about.20 Hz).
[0187] According to .sup.31P-NMR spectroscopy the same P--N--P
product as present in ligand composition C'',
(2-methoxyphenyl).sub.2PN(isopropyl)P(o-phenylenedioxy), was formed
almost quantitatively upon reaction of (o-phenylenedioxy)PCl with
ligand composition N'',
(2-methoxyphenyl).sub.2PN(isopropyl)P(Phenyl).sub.2 overnight in
C.sub.6D.sub.6 at 80.degree. C. with concomitant formation of an
equivalent amount of (phenyl).sub.2PCl (designated ligand
composition C'). .sup.31P-NMR (in C.sub.6D.sub.6) .delta. 157 and
12.
[0188] According to .sup.31P-NMR spectroscopy the same P--N--P
product as present in ligand composition C'',
(2-methoxyphenyl).sub.2PN(isopropyl)P(o-phenylenedioxy), was formed
almost quantitatively upon reaction of (o-phenylenedioxy)PCl with
P--P.dbd.N ligand composition L,
(2-methoxyphenyl).sub.2P--P(2-methoxyphenyl).sub.2.dbd.N(isopropyl)
during <0.5 hour in C.sub.6D.sub.6 at 20.degree. C. with
concomitant formation of an equivalent amount of
(2-methoxyphenyl).sub.2P--Cl (designated ligand composition C*).
.sup.31P-NMR (in C.sub.6D.sub.6) 157 and 12.
Ligand Composition D'' and Ligand Composition D'(Comparative)
[0189] The (phenyl).sub.2PN(isopropyl)P(o-phenylenedioxy) ligand
composition was prepared according to the method reported in
Heteroatom Chem. Vol. 2, 477 (1991).
[0190] Under a nitrogen atmosphere, 12 ml triethylamine was added
to 3.39 g isopropylamine in 10 ml dry toluene. To the resulting
mixture, 5.15 ml (phenyl).sub.2PCl (available from Aldrich) was
slowly added and allowed to stir overnight at room temperature. The
precipitate was removed by filtration. The solvents were removed
from the resulting solution in vacuo. To the evaporation residue,
pentane was added. The solvent was then removed in vacuo from the
pentane solution, yielding (phenyl).sub.2PNH(isopropyl) as a
colourless oil, which crystallized on standing at room temperature.
.sup.31P-NMR (in C.sub.6D.sub.6) .delta. 35.8.
[0191] Under a nitrogen atmosphere, 1.7 ml triethyl amine was added
to 2.00 g of (phenyl).sub.2PNH(isopropyl) in 10 ml dry toluene. The
resulting mixture was cooled to approximately 0.degree. C. and
1.435 g of (o-phenylenedioxy)PCl (available from Aldrich) was
slowly added. The mixture was then stirred overnight at room
temperature (approximately 20.degree. C.).
[0192] The precipitate which formed in the solution was removed by
centrifugation. The resulting solution was concentrated under
vacuum and was subsequently filtered over silica gel.
[0193] The solvent was removed under vacuum, which yielded a white
solid of (phenyl).sub.2PN(isopropyl)P(o-phenylenedioxy).
.sup.31P-NMR (in C.sub.6D.sub.6) .delta. 157.4 and 30.0
(J.sub.PP=17 Hz).
[0194] According to .sup.31P-NMR spectroscopy the same P--N--P
product as present in ligand composition D'',
(phenyl).sub.2PN(isopropyl)P(o-phenylenedioxy), was formed in about
10% yield upon reaction of (o-phenylenedioxy)PCl with ligand
composition M'', (phenyl).sub.2PN(isopropyl)P(phenyl).sub.2
overnight in C.sub.6D.sub.6 at 90.degree. C. with concomitant
formation of (phenyl).sub.2PCl (designated ligand composition D').
The remainder of the reaction mixture were predominantly starting
components. .sup.31P-NMR (in C.sub.6D.sub.6) .delta. 157 and
30.
Ligand Composition E
[0195] The reaction product of (phenyl).sub.2PNH(methyl) and
(o-phenylenedioxy)PCl (ligand composition E) was prepared as
follows.
[0196] Under a nitrogen atmosphere, 400 mg triethylamine was added
to 2 ml methylamine (2 M in THF) in 5 ml dry toluene. The resulting
solution was cooled to -15.degree. C. and 440 mg (phenyl).sub.2PCl
in 5 ml toluene was slowly added and allowed to stir overnight at
room temperature. To the resulting mixture pentane was added. The
precipitate was removed by centrifugation. The solvents were
removed under vacuum. The resulting sticky product was extracted
with cold pentane. After removing the pentane under vacuum
(phenyl).sub.2PNH(methyl) was isolated as an oil. .sup.31P-NMR (in
C.sub.6D.sub.6) .delta. 45.7.
[0197] To 55 mg (phenyl).sub.2PNH(methyl) in 1 ml C.sub.6D.sub.6
was added 50 mg triethylamine and 44 mg (o-phenylenedioxy)PCl.
After standing overnight 2 ml of pentane was added. The precipitate
was removed by centrifugation. The solvents were removed under
vacuum. The product was isolated as an oil. According to
.sup.31P-NMR the product consisted at least predominantly of a
P--P.dbd.N(methyl) structure with on one P atom the
o-phenylenedioxy group and on the other P atom two phenyl groups
(either (o-phenylenedioxy)P(phenyl).sub.2PN(methyl) or
(phenyl).sub.2P(o-phenylenedioxy)PN(methyl)). .sup.31P-NMR (in
C.sub.6D.sub.6) .delta. 151.9 and 49.1 (J.sub.PP=351 Hz).
Ligand Composition F
[0198] The reaction product of (tert-butyl).sub.2PNH(methyl) and
(o-phenylenedioxy)PCl (ligand composition F) was prepared as
follows.
[0199] Under a nitrogen atmosphere, 3 ml triethylamine was added to
6 ml methylamine (2 M in THF) in 20 ml dry toluene. To the
resulting solution, 1.6 g (tert-butyl).sub.2PCl (available from
Aldrich) was slowly added and allowed to stir overnight at room
temperature. To the resulting mixture pentane was added. The
precipitate was removed by centrifugation. The solvents were
removed under vacuum. The resulting oil was crystallized from
pentane (-20.degree. C.). Yielding white crystals of
(tert-butyl).sub.2PNH(methyl). .sup.31P-NMR (in C.sub.6D.sub.6)
.delta. 82.8. This product has been described as an oil in
Phosphorus, Sulfur and Silicon, 1990, vol. 54, p. 55-61.
[0200] Under a nitrogen atmosphere, 95 mg triethylamine was added
to 83 mg (tert-butyl).sub.2PNH(methyl) in 3 ml dry toluene. To the
resulting solution, 83 mg (o-phenylenedioxy)PCl was slowly added
and allowed to stir overnight at room temperature. To the resulting
mixture pentane was added. The precipitate was removed by
centrifugation. The solvents were removed under vacuum. The
resulting white solid was washed with cold pentane. The
.sup.31P-NMR spectrum in C.sub.6D.sub.6 showed 2 products one with
a set of doublets at .delta. 151.2 and 84.7 (J.sub.PP=375) and one
with a set of doublets at .delta. 153.8 and 115.8 (J.sub.PP=42 Hz)
in a 4 to 1 (mol/mol) ratio. Most probably the product consisted of
a 4 to 1 (mol/mol) mixture of isomers having a P--P.dbd.N(methyl)
structure with on one P atom the o-phenylenedioxy group and on the
other P atom two tert-butyl groups (either
(o-phenylenedioxy)P(tert-butyl).sub.2PN(methyl) or
(tert-butyl).sub.2P(o-phenylenedioxy)PN(methyl)) and a
P--N(methyl)-P structure,
(tert-butyl).sub.2P--N(methyl)-P(o-phenylenedioxy).
Ligand Composition G''
[0201] The reaction product of
(2-methoxyphenyl).sub.2PNH(pentafluorophenyl) and
(o-phenylenedioxy)PCl (ligand composition G'') was prepared as
follows.
[0202] Under a nitrogen atmosphere, 0.5 g (6.3 mmol) of
neopentyllithium (available from Aldrich) was slowly added to 1.15
g (6.3 mmol) pentafluoroaniline (available from Aldrich) in 25 ml
dry toluene and stirred for 0.5 hour at room temperature. To the
resulting mixture 1.76 g (6.3 mmol) (2-methoxyphenyl).sub.2PCl in
15 ml toluene was slowly added and allowed to stir for 1 hour at
room temperature. The precipitate was removed by centrifugation.
The solution was concentrated to about 5 ml. Pentane was added
(about 20 ml), the precipitate was collected. Washing with pentane
yielded (2-methoxyphenyl).sub.2PNH(C.sub.6F.sub.5) as a white
solid. .sup.31P-NMR (in C.sub.6D.sub.6) .delta. 38.4 (t)
(J.sub.PF=60 Hz). .sup.19F-NMR (in C.sub.6D.sub.6) .delta. 156 (o);
-165.2 (m); -170.3 (p).
[0203] Under a nitrogen atmosphere, 128 mg (1.64 mmol) of
neopentyllithium was slowly added to 700 mg (1.64 mmol)
(2-methoxyphenyl).sub.2PNH(C.sub.6F.sub.5) in 25 ml dry toluene and
stirred for 1 hour at room temperature. To the resulting mixture
286 mg (1.64 mmol) (o-phenylenedioxy)PCl in 10 ml toluene was
slowly added and allowed to stir for 1 hour at room temperature.
The precipitate was removed by centrifugation. The solvent was
removed in vacuo. Pentane was added (about 10 ml) yielding a clear
solution. From this solution
(2-methoxyphenyl).sub.2PN(C.sub.6F.sub.5)(o-phenylenedioxy)
precipitated in several fractions. .sup.31P-NMR (in C.sub.6D.sub.6)
.delta. 138.4 and 51.3 (J.sub.pp=16 Hz). .sup.19F-NMR (in
C.sub.6D.sub.6) .delta. -143 (o); -164.1 (m); -157.1 (p).
Ligand Composition H'' (Comparative)
[0204] The (o-phenylenedioxy)PN(methyl)P(o-phenylenedioxy) ligand
composition was prepared by analogy to the method reported for the
preparation of (o-phenylenedioxy)PN(isopropyl)P(o-phenylenedioxy)
in Heteroatom Chem. Vol. 2, 477 (1991).
[0205] Under a nitrogen atmosphere 1 ml methylamine (2 M in THF)
was added to 5 ml dry toluene. This solution was cooled to
-20.degree. C. At this temperature slowly 150 mg
(o-phenylenedioxy)PCl in 1 ml toluene was slowly added. After
several days 87 mg Et.sub.3N in 5 ml pentane was added. The
precipitate was removed by centrifugation. The solvents were
removed under vacuum. Yielding (o-phenylenedioxy)PNH(methyl)
contaminated with a small amount of toluene. .sup.31P-NMR (in
C.sub.6D.sub.6) .delta. 143.9.
[0206] To 30 mg (o-phenylenedioxy)PNH(methyl) in 1 ml
C.sub.6D.sub.6 was added 30 mg triethylamine and 30 mg
(o-phenylenedioxy)PCl. An instantaneous reaction was observed by
.sup.31P-NMR. Finally 2 ml of pentane was added. The precipitate
was removed by centrifugation. The solvents were removed under
vacuum. The final product was isolated as a white solid.
.sup.31P-NMR (in C.sub.6D.sub.6) .delta. 142.0.
Ligand Composition K'' (Comparative)
[0207] The
(2-methoxyphenyl).sub.2PN(CH.sub.3)P(2-methoxyphenyl).sub.2 ligand
was prepared by first forming a solution of 1.59 g (5 mmol)
(2-methoxyphenyl).sub.2PNEt.sub.2 in 20 ml diethyl ether. To this
solution 10 ml of a 1 M HCl solution in diethyl ether (10 mmol HCl)
was added under an inert atmosphere at room temperature. The
suspension thus formed was stirred overnight. The diethyl ether was
removed from the product under vacuum and 20 ml of dry toluene was
added. The resulting solution was filtered and the toluene was
removed from the filtrate under vacuum, to yield a white solid
(2-methoxyphenyl).sub.2PCl product.
[0208] A solution of 0.51 g (5 mmol) of triethylamine in 20 ml of
dry dichloromethane was added to the (2-methoxyphenyl).sub.2PCl
product. To the resulting mixture, 1.25 ml of a 2 M H.sub.2NMe
solution in THF (2.5 mmol) was added and allowed to stir overnight.
The solvents were removed from the resulting solution in vacuo and
20 ml of dry toluene was added. The mixture was then filtered.
[0209] The toluene was removed from the filtrate under vacuum, and
10 ml of methanol was added to the residue to produce a suspension,
which was filtered once more, to leave the solid white
(2-methoxyphenyl).sub.2PN(CH.sub.3)P(2-methoxyphenyl).sub.2 product
which was isolated.
Ligand Composition L (Comparative)
[0210] The reaction product of
(2-methoxyphenyl).sub.2PNH(isopropyl) and
(2-methoxyphenyl).sub.2PCl (ligand composition L) was prepared as
follows.
[0211] Under a nitrogen atmosphere, 3 ml triethylamine was added to
1.5 ml isopropylamine (17.6 mmol) in 5 ml dry toluene. To the
resulting mixture, 2.2 g (7.84 mmol) (2-methoxyphenyl).sub.2PCl in
20 ml toluene was slowly added and allowed to stir overnight at
room temperature. The precipitate was removed by centrifugation.
The solvents were removed from the resulting solution in vacuo.
[0212] Washing with pentane yielded
(2-methoxyphenyl).sub.2PNH(isopropyl) as a white solid.
.sup.31P-NMR (in C.sub.6D.sub.6) .delta. 21.8.
[0213] Under a nitrogen atmosphere, 80 mg (1.0 mmol) of neopentyl
lithium was slowly added to 300 mg (0.99 mmol) of
(2-methoxyphenyl).sub.2PNH(isopropyl) in 30 ml dry toluene. To the
resulting mixture 277 mg (0.99 mmol) (2-methoxyphenyl).sub.2PCl was
slowly added. The mixture was stirred overnight at room
temperature. The precipitate was removed by centrifugation. The
solvent was removed in vacuo. The residue was washed with pentane.
The product has according to .sup.31P-NMR at least predominantly
the P--P.dbd.N(isopropyl) structure, i.e.
(2-methoxyphenyl).sub.2P(2-methoxyphenyl).sub.2PN(isopropyl), and
was used without further purification. .sup.31P-NMR (in
C.sub.6D.sub.6) .delta. 0.0 and -35.4 (J.sub.pp=258 Hz).
Ligand Composition M'' (Comparative)
[0214] The (phenyl).sub.2PN(isopropyl)P(phenyl).sub.2 ligand was
prepared by the following method. At 0.degree. C., under a nitrogen
atmosphere, 15 ml triethylamine was added to 6.3 g
(phenyl).sub.2PCl in 80 ml of dry dichloromethane. To the resulting
mixture, 0.844 g isopropylamine was added and allowed to stir
overnight at room temperature. The solvents were removed from the
resulting solution in-vacuo and 50 ml of dry toluene was added. The
mixture was then filtered over a small layer of silica. The toluene
was removed from the filtrate under vacuum,
(phenyl).sub.2PN(isopropyl)P(phenyl).sub.2 product was isolated as
a white solid. Crystallization from ethanol yielded
(phenyl).sub.2PN(isopropyl)P(phenyl).sub.2 as white crystals.
Ligand Component N'' [Used in the In Situ Preparation of Ligand
Composition C']
[0215] The (phenyl).sub.2PN(isopropyl)P(2-methoxyphenyl).sub.2
ligand was prepared by the following method.
[0216] Under a nitrogen atmosphere, 12 ml triethylamine was added
to 3.39 g isopropylamine in 10 ml dry toluene. To the resulting
mixture, 5.15 ml (phenyl).sub.2PCl was slowly added and allowed to
stir overnight at room temperature. The precipitate was removed by
filtration. The solvents were removed from the resulting solution
in vacuo. To the evaporation residue pentane was added and
subsequently the solvent was removed in vacuo from the pentane
solution, yielding (phenyl).sub.2PNH(isopropyl) as a colourless
oil, which crystallized on standing at room, temperature.
[0217] Under a nitrogen atmosphere, 3 ml triethyl amine was added
to 0.9 g of the isolated (phenyl).sub.2PNH(isopropyl) in 5 ml of
dry dichloromethane. To the resulting mixture, 1.1 g
(2-methoxyphenyl).sub.2PCl was added and allowed to stir for a week
at room temperature. To the resulting reaction mixture 5-10 ml of
dry toluene was added. The precipitate was removed by
centrifugation. The solvents were removed from the resulting
solution in vacuo. The resulting mixture was first washed with
pentane and thereupon stirred with methanol yielding a white solid.
The white solid was washed with pentane and dried in vacuo. Yield
0.7 g of (phenyl).sub.2PN(isopropyl)P(2-methoxyphenyl).sub.2.
.sup.31P-NMR (in C.sub.6D.sub.6) broad signals .delta. 55.9 and
24.8.
Ligand Component Q [Used in the In Situ Preparation of Ligand
Composition T']
[0218] The racemic phosphorus derivative of
rac-2,2'dihydroxy-1,1'-binaphthyl,
(Rac-1,1'-binaphthyl-2,2'-dioxy)PCl, also called
(rac-1,1'-binaphthalene-2,2'-dioxy)PCl,
rac-1,1'-binaphthyl-2,2'phosphorochloridite or
(rac-O,O-binaphtholato)PCl was prepared from phosphorus trichloride
and rac-2,2'-dihydroxy-1,1'-binaphthyl (purchased from Aldrich)
according to the method reported by N. Greene and T. P. Kee,
Synthetic Communications 23 (1993) 1651. The product showed in
.sup.31P-NMR (in C.sub.6D.sub.6) a signal at .delta. 179.5
(.delta..sub.P 178.8 (s) according to the above-mentioned
literature).
Ligand Composition T'
[0219] The reaction product of
(2-methoxyphenyl).sub.2PN(methyl)P(2-methoxyphenyl).sub.2 and
(rac-1,1'-binaphthyl-2,2'-dioxy)PCl (ligand composition T') was
prepared as follows.
[0220] In a NMR-tube under a nitrogen atmosphere 14 mg (40 mmol)
(rac-1,1'-binaphthyl-2,2'-dioxy)PCl was added to 22 mg (36 mmol)
(2-methoxyphenyl).sub.2PN(methyl)P(2-methoxyphenyl).sub.2 in 1 ml
dry d8-toluene. This mixture was heated in an oil bath of
110.degree. C. for 40 hours. According to .sup.31P-NMR
spectroscopy, the product was an approximately 1 to 1 (mol/mol)
mixture of (2-methoxyphenyl).sub.2PCl and predominantly a
P--P.dbd.N(methyl) structure with on one P atom the
rac-1,1'-binaphthyl-2,2'-dioxy group and on the other P atom two
2-methoxyphenyl groups (either
(rac-1,1'-binaphthyl-2,2'-dioxy)P(2-methoxyphenyl).sub.2PN(methyl)
or
(2-methoxyphenyl).sub.2P(rac-1,1'-binaphthyl-2,2'-dioxy)PN(methyl))
(see Scheme 1). .sup.31P-NMR (in C.sub.7D.sub.8) .delta. 151.3 and
35.1 (J.sub.pp=385 Hz). This mixture was used as such in the
catalyst for ethylene oligomerization experiments without further
purification.
##STR00002##
Ligand Component U
[0221] The preparation of
N-methylnaphto[1,8-de][1,3,2]dioxaphosphinine-2-amine (see Scheme
2).
##STR00003##
[0222] Under a nitrogen atmosphere, 0.4 ml triethylamine was added
to 1.5 ml methylamine (2 M in THF) in 20 ml dry toluene. To the
resulting solution was cooled to 5.degree. C. and 250 mg
2-chloronaphtho[1,8-de][1,3,2]dioxaphosphinine (available from
Hansa Fine Chemicals GmbH, Bremen, Germany) was slowly added. After
stirring overnight at room temperature 20 ml hexane was added. The
precipitate was removed by centrifugation. The solvents were
removed under vacuum. The product
N-methylnaphtho[1,8-de][1,3,2]dioxaphosphinine-2-amine was isolated
as an oil and used as such. .sup.31P-NMR C.sub.6D.sub.6 .delta.
121.2.
Ligand Composition V
[0223] The reaction product of
N-methylnaphtho[1,8-de][1,3,2]dioxaphosphinine-2-amine and
(2-methoxyphenyl).sub.2PCl (ligand composition V, see Scheme 3) was
prepared as follows.
##STR00004##
[0224] Under a nitrogen atmosphere, 350 mg triethylamine was added
to 150 mg N-methylnaphtho[1,8-de][1,3,2]dioxaphosphinine-2-amine 20
ml dry toluene. To the resulting solution, 230 mg
(2-methoxyphenyl).sub.2PCl was slowly added and allowed to stir
overnight at room temperature. To the resulting mixture hexane was
added. The precipitate was removed by centrifugation. The solvents
were removed under vacuum. The product was crystallized from a
hexane/toluene mixture (-20.degree. C.) and isolated as a white
solid. .sup.31P-NMR C.sub.6D.sub.6 .delta. 130.6 and 36.3
(J.sub.PP=370 Hz).
Co-Catalyst
[0225] The co-catalyst used in the experiments below was selected
from:
[0226] Methyl aluminoxane (MAO) in toluene, [Al]=5.20% wt, supplied
by Crompton GmbH, Bergkamen, Germany;
Examples 1-31
Catalyst System Preparation for Simultaneous Trimerization and
Tetramerization in a Batch Autoclave
[0227] In a Braun MB 200-G dry box the chromium
tris(acetylacetonate) (typically about 30 .mu.mol) and the ligand
component, as indicated in Table 1, were placed in a glass bottle.
Dry toluene (typically 4 g) was added to the glass bottle to obtain
a catalyst precursor solution. Finally, the bottle was sealed by a
septum cap.
[0228] The solution or part of the solution was used in the
oligomerisation reaction of ethylene.
Oligomerisation Reactions of Ethylene in a 1.0-Litre Batch
Autoclave
[0229] Oligomerisation experiments were performed in a 1.0-litre
steel autoclave equipped with jacket cooling with a heating/cooling
bath (ex. Julabo, model ATS-2) and a turbine/gas stirrer and
baffles.
[0230] The reactor was scavenged by introducing 250 ml toluene, MAO
(0.6 g solution) and subsequent stirring at 70.degree. C. under
nitrogen pressure of 0.4-0.5 MPa for 30 min. The reactor contents
were discharged via a tap in the base of the autoclave. The reactor
was evacuated to about 0.4 kPa and loaded with approximately 250 ml
toluene, heated to 40.degree. C. and pressurised with ethylene to
15 barg.
[0231] Whilst stirring, an MAO-solution (typically an intake of
3.12 g, 6 mmol Al, to attain an Al/Cr atomic ratio of 200) was
added to the reactor with the aid of toluene (the total volume
injected was about 25 ml: the MAO-solution diluted with toluene to
8 ml was injected and the injector system was rinsed twice with 8
ml toluene) and the stirring at 800 rpm was continued for 30
minutes.
[0232] The Cr-catalyst precursor, prepared as described above, was
introduced into the stirred reactor using an injection system with
the aid of toluene (the total volume injected was about 25 ml: the
catalyst solution diluted with toluene to 8 ml was injected and the
injector system was rinsed twice with 8 ml toluene). The initial
loading of the reactor was about 300 ml of largely toluene.
[0233] The addition of the catalyst system resulted, after an
initial induction period of about 5 minutes, in an exotherm
(generally 5-10.degree. C.), which typically reached a maximum
within 1 minute and was followed by establishment of the
temperature and pressure indicated in Table 1.
[0234] After consuming the desired volume of ethylene, the reaction
was stopped by rapid cooling to room temperature (about 5 minutes),
followed by venting of the ethylene, and decanting the product
mixture into a collection bottle using a tap in the base of the
autoclave. Exposure of the mixture to air resulted in rapid
deactivation of the catalyst.
[0235] After addition of n-hexylbenzene, (0.5-3.5 g) as an internal
standard, to the crude product, the amount of the C.sub.4-C.sub.30
olefins and purity of C.sub.6, C.sub.8 and C.sub.10 olefins was
determined by gas chromatography. The experimental data is reported
in Table 1.
[0236] In the case of experiments under 30, 40 or 50 barg of
ethylene pressure, a similarly equipped 0.5-litre steel autoclave
has been used, loaded (in the same manner as the above-described
procedure for the 1.0-litre autoclave) with half the amounts of the
components used in the corresponding 1.0-litre experiments to
maintain the same Al/Cr atomic ratio (of about 200) and final alpha
olefin concentration as much as practicable.
[0237] The experimental data is provided in Table 1 below.
TABLE-US-00001 TABLE 1 The performamce of
R.sup.a.sub.2P--P(R.sup.c).sub.2.dbd.N--R.sup.b,
R.sup.b--N.dbd.P(R.sup.a).sub.2PR.sup.c.sub.2 and/or
R.sup.a.sub.2P--N(R.sup.b)--PR.sup.c.sub.2 ligands in Cr- catalyzed
ethylene oligomerization Ex- ample Cr (.mu.mol) Ligand ( mol lig )
_ ( mol Cr ) ##EQU00001## Co- Catalyst Temp- erature (Initial Temp)
(.degree. C.) Pressure (barg) Time (min) TOF (TON).sup..dagger-dbl.
C.sub.6 (% wt) 1-C.sub.6* (% wt) 1 32 A MAO 70 15 30 130 53.6 97.7
(1.1) (40) (65) 2 15 A MAO 70 30 72 246 49.6 97.7 (1.1) (40) (295)
3 14 A MAO 85 30 35 415 51.1 97.4 (1.1) (40) (242) 4 15 A MAO 85 30
40 343 50.6 97.4 (2.3) (40) (229) 5 3 A MAO 100 50 60 594 50.1 97.6
(1.1) (40) (594) 6 3 A MAO 100 50 90 365 52.4 97.4 (2.3) (40) (547)
7 30 A' MAO 70 15 60 76 45.1 97.2 (1.1) (40) # # (76) 8 15 A' MAO
70 30 38 139 33.4 96.7 (1.2) (70) (88) 9 20 A' MAO 85 30 43 69 45.3
97.1 (1.2) (70) (49) 10 30 B' MAO 70 15 225 20 57.2 94.1 (1.1) (70)
# # (76) 11 15 B' MAO 70 30 94 48 45.5 92.0 (1.1) (70) (75) 12 15
C'' MAO 70 30 19 317 50.8 98.6 (1.1) (70) (100) 13 15 C'' MAO 85 30
80 185 59.8 98.2 (2.4) (40) (246) 14 3 C'' MAO 100 50 80 643 64.9
98.1 (2.4) (40) (858) 15 15 D'' MAO 70 30 30 7 29.6 71.6 # (1.3)
(40) (4) 16 15 E MAO 70 30 30 9 10.6 66.4 (1.1) (40) (4) 17 30 F
MAO 70 15 85 78 38.8 98.8 (1.1) (40) (111) 18 15 F MAO 70 30 37 270
44.7 99.0 (1.1) (40) (167) 19 16 F MAO 85 30 35 269 33.6 98.7 (2.3)
(40) (157) 20 3 F MAO 100 50 60 181 40.8 98.8 (2.3) (40) (181) 21
15 G'' MAO 70 30 35 5 58.9 97.8 (1.3) (70) (3) 22 17 G'' MAO 120 50
85 5 16.0 95.8 (2.4) (40) (8) 23 15 H'' MAO 70 30 75 2 26.4 93.6 #
(0.9) (40) (3) 24 15 K'' MAO 70 30 36 705 85.0 97.5 # (1.1) (40)
(423) 25 16 L MAO 70 30 20 5 82.5 100.0 # (1.5) (70) (2) 26 15 M''
MAO 40 30 33 203 17.4 68.5 # (1.1) (40) (113) 27 15 M'' MAO 80 30
30 26 20.3 92.8 # (1.1) (80) (13) 28 15 T' MAO 70 30 32 148 42.5
97.6 (1.1) (70) (79) 29 15 T' MAO 85 30 37 137 49.2 97.3 (1.1) (85)
(84) 30 15 T' MAO 85 40 30 183 44.0 97.1 (1.1) (85) (92) 31 15 V
MAO 70 30 21 174 32.5 96.5 (1.2) (70) (61) 1-C.sub.6 + 1-C.sub.8 on
Total Total C.sub.8 1-C.sub.8** C.sub.10.sup..dagger.
C.sub.12-C.sub.14.sup..dagger. Solids Product Product Example (%
wt) (% wt) (% wt) (% wt) (% wt) (g) (% wt) 1 35.9 98.4 3.4 4.6 0.05
54.6 87.7 2 38.2 98.5 4.1 4.6 0.02 124 .3 86.1 3 37.2 98.3 3.6 4.4
1.5 95.8 86.4 4 38.5 98.3 3.4 4.4 1.0 96.1 87.2 5 32.2 98.3 2.9 2.4
10.3 49.8 80.5 6 38.5 98.3 2.6 2.8 1.4 45.7 88.9 7 44.6 98.5 2.4
4.4 0.05 64.8 87.8 8 52.7 98.5 2.0 4.4 1. 3 37.2 84.1 9 43.1 98.2
2.1 3.4 1.7 28.1 86.3 10 31.7 97.2 4.3 4.3 0.08 62.8 84.6 11 43.6
96.8 3.5 4.6 0.5 31.5 84.1 12 34.2 98.8 8.1 6.8 0.07 43.5 83.8 13
22.6 98.4 10.3 5.7 0.6 103.1 81.0 14 21.1 98.3 8.6 3.9 1.0 71.6
84.3 15 60.8 97.1 2.1 2.2 2.7 1.5 80.2 16 21.6 92.6 5.5 7.5 43.4
1.8 27.0 .dagger..dagger. 17 25.7 99.2 5.4 5.5 19.3 93.4 63.9 18
39.0 99.5 5.2 6.0 3.7 69.8 83.0 19 24.9 99.2 3.7 4.7 25.0 70.0 57.9
20 26.8 99.3 3.0 3.5 19.7 15.2 66.9 21 12.4 95.5 4.5 4.5 18.6 1.2
69.4 22 4.7 91.8 2.1 2.9 65.1 3.6 19.6 23 24.6 96.1 10.9 14.3 7.7
1.3 48.3 # .dagger..dagger. 24 4.1 99.8 10.0 0.9 0.02 177.6 87.0 #
25 3.6 93.0 3.0 3.1 7.2 0.7 85.8 # 26 70.2 98.8 1.8 4.4 0.5 47.2
81.3 # .dagger..dagger. 27 25.9 94.4 2.3 3.7 47.4 5.5 43.3 #
.dagger..dagger. 28 48.3 98.6 1.9 3.1 0.06 33.9 89.1 29 43.8 98.4
2.1 2.8 0.06 35.2 90.9 30 47.8 98.5 1.9 2.9 0.05 38.7 89.8 31 53.8
98.6 1.8 3.4 3.5 25.4 84.4
[0238] The following equilibria are assumed in the presence of
activated chromium:
R.sup.a.sub.2P--P(R.sup.c).sub.2.dbd.N--R.sup.bR.sup.a.sub.2P--N(R.sup.b-
)--PR.sup.c.sub.2R.sup.b--N.dbd.P(R.sup.a).sub.2--PR.sup.c.sub.2
TABLE-US-00002 A R.sup.a.sub.2 = o-phenylenedioxy, R.sup.b =
methyl, R.sup.c = o-methoxyphenyl (A: ligand predominantly in
either of the P--P.dbd.N forms). A' R.sup.a.sub.2 =
o-phenylenedioxy, R.sup.b = methyl, R.sup.c = o-methoxyphenyl (A':
in-situ prepared ligand A; containing about 1 mol/mol
(o-methoxyphenyl).sub.2P--Cl). B' R.sup.a.sub.2 = o-phenylenedioxy,
R.sup.b = methyl, R.sup.c.sub.2 = o- methylphenyl + phenyl (B':
in-situ prepared ligand B, predominantly in either of the
P--P.dbd.N forms; containing about 1 mol/mol (o-
methoxyphenyl)(phenyl)P--Cl). C'' R.sup.a.sub.2 = o-phenylenedioxy,
R.sup.b = isopropyl, R.sup.c = o- methoxyphenyl (C'': ligand
predominantly in the P--N--P form). D'' R.sup.a.sub.2 =
o-phenylenedioxy, R.sup.b = isopropyl, R.sup.c = phenyl (D'':
ligand predominantly in the P--N--P form). E R.sup.a.sub.2 =
o-phenylenedioxy, R.sup.b = methyl, R.sup.c = phenyl (E: ligand
predominantly in either of the P--P.dbd.N forms). F R.sup.a.sub.2 =
o-phenylenedioxy, R.sup.b = methyl, R.sup.c = tert-butyl (F: ligand
predominantly in either of the P--P.dbd.N forms). G'' R.sup.a.sub.2
= o-phenylenedioxy, R.sup.b = pentafluorophenyl, R.sup.c = o-
methoxyphenyl (G'': ligand predominantly in the P--N--P form). H''
R.sup.a.sub.2 = o-phenylenedioxy, R.sup.b = methyl, R.sup.c.sub.2 =
o- phenylenedioxy (H'': ligand predominantly in the P--N--P form).
K'' R.sup.a = o-methoxyphenyl, R.sup.b = methyl, R.sup.c =
o-methoxyphenyl (K'': ligand predominantly in the P--N--P form). L
R.sup.a = o-methoxyphenyl, R.sup.b = isopropyl, R.sup.c =
o-methoxyphenyl (L: ligand predominantly in either of the
P--P.dbd.N forms). M'' R.sup.a = phenyl, R.sup.b = isopropyl,
R.sup.c = phenyl (M'': ligand predominantly in the P--N--P form).
T' R.sup.a.sub.2 = rac-1,1'-binaphthyl-2,2'-dioxy, R.sup.b =
methyl, R.sup.c = o- methoxyphenyl (T': in-situ prepared T,
predominantly in either of the P--P.dbd.N forms; containing about 1
mol/mol (o-methoxyphenyl).sub.2P--Cl). V R.sup.a.sub.2 =
1,8-naphthalenedioxy, R.sup.b = methyl, R.sup.c = o- methoxyphenyl
(V: ligand predominantly in either of the P--P.dbd.N forms). #
Comparative example. ## During 30 minutes at 40.degree. C.
.dagger-dbl. Turnover frequency (TOF) in hourly kmol converted
ethylene/mol catalyst (kmol/mol * h); turnover number (TON) in kmol
converted ethylene/mol catalyst (kmol/mol). * Percentage (%) of
1-hexene by weight of the C.sub.6 portion of the product
composition. ** Percentage (%) of 1-octene by weight of the C.sub.8
portion of the product composition. .dagger. Predominantly branched
and/or internal olefins, unless indicated differently.
.dagger..dagger. Equal or larger than 50% of 1-decene by weight of
the C.sub.10 portion of the product composition. C.sub.6
Hydrocarbons containing 6 carbon atoms; 1-C.sub.6 is 1- hexene.
C.sub.8 Hydrocarbons containing 8 carbon atoms; 1-C.sub.8 is 1-
octene. C.sub.10 Hydrocarbons containing 10 carbon atoms.
C.sub.12-C.sub.14 Hydrocarbons containing 12 and/or 14 carbon
atoms. Solids: The amount of wax and polyethylene isolated by
filtration. Total The amount of C.sub.4-C.sub.100 olefins, derived
from product: GC analysis, including the amount of solids.
[0239] For economic narrow-cut alpha-olefin production, e.g. the
production of a mixture of 1-hexene and 1-octene in a combined
overall yield of >80%, preferably in a weight ratio of 20/80 to
80/20, each in >92% selectivity (on total C6 or total C8) in a
single plant to enhance the economy of scale a special kind of
catalyst is required. At industrially interesting pressures and
temperatures of at least 30 barg and 70.degree. C. the comparative
catalyst K'' and analogous catalyst L predominantly produce
1-hexene and hardly 1-octene. Under these conditions the
comparative catalyst M'' produces a mixture of hexenes and octenes
of low 1-hexene content, but also a large amount of solids at a low
TOF. Only at 40.degree. C. comparative catalyst M'' produces a
mixture of hexenes and octenes of low 1-hexene content at a high
TOF.
[0240] Surprisingly only the "o-phenylenedioxy-phosphorus"
containing catalysts A, A', C'', the
rac-1,1'-binaphthyl-2,2'-dioxy-phosphorus containing catalyst T'
and the 1,8-naphthalenedioxy-phosphorus containing catalyst V and
to a less extent B' and F, but remarkably to far less extent, if
any, D'', E, G'', and H'', produce mainly 1-hexene and 1-octene in
high activities (TOF's) at temperatures of 70.degree. C. and 30
barg. Even at 70-100.degree. C. and 30-50 barg catalysts A, A', C''
and T' provide for the selective production of both highly pure
1-hexene and 1-octene in the desired weight ratios with only minor
amounts of solids (wax and polyethylene) co-produced. Hence, what
is particularly preferred for efficient narrow-cut production of
highly pure 1-hexene and 1-octene at industrially interesting rates
and temperatures and pressures is a Cr-complex with a PNP structure
or its PPN isomers with a methyl or isopropyl group on N, one
cyclic alkylenedioxy or arylenedioxy group, preferably
one-optionally mono-tetra alkylated-o-phenylenedioxy (catechol) or
one-optionally mono-dodeca alkylated-racemic or optically pure
1,1'-binaphthyl-2,2'-dioxy group on one P and at least one
o-methoxyphenyl and one phenyl, but preferably two o-methoxyphenyl
groups on the other P. If, instead two tert-butyl (also sterically
demanding, but electronically different) groups are present on the
latter P, generally besides 1-hexene and 1-octene a relatively
large (>3.7% wt) amount of solids, mainly wax, is
co-produced.
[0241] It should be noted that the differences in hexenes/octenes
ratios between experiments with ligand A and in-situ prepared
ligand A (ligand A') are probably due to the differences in
start-up temperature. The activities obtained with the in-situ
prepared ligand A' are however invariably lower than those obtained
with ligand A, which is ascribed to the presence of
(o-methoxyphenyl).sub.2P--Cl.
* * * * *