Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR THE PREPARATION OF COPOLYMERS OF CARBON
MONOXIDE AND OLEFINICALLY UNSATURATED COMPOUNDS
The present invention relates to a process for the
preparation of copolymers of carbon monoxide and one or
more olefinically unsaturated compounds, to copolymers
prepared by such a process, and to the use of such
copolymers.
Copolymers of interest in relation to the present
invention are described, for example, in EP-A-121965,
EP-A-248483, EP-A-743336 and W096/13549, and also
described therein are catalyst compositions useful for
the preparation of the copolymers, and uses to which the
copolymers may be put. The catalyst compositions are
based on a Group VIII metal and a dentate ligand which
can be indicated by the general formula
R2M1 Y M2R2 (I)
In this formula M1 and M2 independently represent a
phosphorus, nitrogen, arsenic or antimony-atom, each
group R may be selected from a wide variety of organic
groups, for example optionally substituted alkyl,
aralkyl, cycloalkyl or, preferably, aryl groups and Y
represents a bivalent bridging group.
The present invention provides a copolymerization
process comprising the step of copolymerizing carbon
monoxide and an olefinically unsaturated compound in the
presence of a catalyst composition based on a Group VIII
metal and a dentate ligand having the general formula
R1R2M1 Y M2R3R4 CI)
where M1 and M2 independently represent one of
phosphorous, nitrogen, arsenic and antimony, R1
represents an aryl group having a substituent of the
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general formula -S(O)n-X, in which n represents 0, 1 or 2
and X represents a hydroxy group, which aryl group is
optionally further substituted; R2, R3 and R4
independently represent an optionally substituted alkyl
group or optionally substituted aryl group, on the
understanding that at least one of R1, R2, R3 and R4
represents an aryl group having a substituent or a
further substituent selected from hydroxy, alkoxy and
alkoxyalkoxy; and Y represents a bridging group; or an
ester or salt derivative of such a ligand.
Generally, unless stated otherwise in this speci-
fication, any aryl substituent or aryl moiety of a group
may comprise up to 20 ring carbon atoms, preferably up to
10 ring carbon atoms (excluding substituents). A
preferred optionally substituted aryl group is an
optionally substituted phenyl group.
Generally, unless otherwise stated in this speci-
fication, any substituted aryl group of a compound of
formula I may suitably be substituted by 1-3 substi-
tuent(s). Generally, unless otherwise stated, any said
further substituent of an aryl group may be any one of
the group comprising halogen, especially fluorine,
chlorine and bromine atoms, and nitro, cyano, hydroxy,
alkyl, haloalkyl, haloalkoxy, alkoxyalkyl, aryloxy,
alkoxy, alkoxyalkoxy, amino, mono- and di-alkylamino,
aminoalkyl, mono- and di-alkylaminoalkyl, amido, mono-
and di-alkylamido groups, alkylthio, alkylsulphonyl,
dialkylamidosulphonyl and alkylsulphonate groups. It is
preferred for any of the aryl groups mentioned above,
that it has at least one such further substituent
selected from hydroxy, alkoxyalkoxy and, especially,
alkoxy.
Generally unless otherwise stated in this
specification, any alkyl group or alkyl moiety of a group
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may be linear, branched or cyclic and may suitably
contain 1 to 24, preferably 1 to 12, most preferably 1 to
6, and especially 1 to 4, carbon atoms, suitable examples
being methyl, ethyl and propyl.
Preferably, n is 2. Thus, preferred ligands are
sulphonic acids, or esters or salts thereof, more
preferably acids or salts, most preferably salts thereof.
Preferred salts of the ligands of general formula I
are metal salts, for example alkali metal salts.
The sulphonated compounds as used in the method of
the invention may include zwitterionic forms; for example
with some ligands having phosphorus or nitrogen atoms M1
and M2 and a plurality of sulphonyl groups both
phosphorus or nitrogen atoms may be protonated whilst two
sulphonic acid groups may be deprotonated.
Suitably R1 has a said further substituent,
preferably at the 2- position.
Preferably R1 is further substituted by one or more
groups independently selected from hydroxy, alkoxyalkoxy
and, especially, alkoxy, and preferably by only one such
further group.
Preferably any one of R2, R3 and R4 represents
independently an aryl group having a substituent of the
general formula -S(0)n-X, which aryl group is optionally
further substituted, preferably by one or more groups
independently selected from hydroxy, alkoxyalkoxy and,
especially, alkoxy, and more preferably by only one such
further group.
Preferably an aryl group R2, R3 or R4 has a said
further substituent, preferably at the 2- position.
Preferably, any substituent of general formula
-S(0)n-X is located at a meta position relative to the
linkage to the respective group M1 or M2. Preferably, a
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substituent of general formula -S(0)n-X is located at the
para position relative to a further substituent of the
aryl group. Thus, a preferred group R1, R2, R3 and R4 has
a substituent, preferably an alkoxy group, especially
methoxy, at the 2-position and a substituent of general
formula -S(0)n-X at the 5-position.
Preferably, a group R1, R2, R3 or R4 having a
substituent -S(0)n-X has only one substituent of this
formula.
Preferably, at least one of R1 and R2 and at least
one of R3 and R4 represents an aryl group having a
substituent of general formula -S(O)n-X and at least one
said further substituent. Preferably each of R1, R2, R3
and R4 represents such a group.
The bridging group Y preferably contains, in addition
to hydrogen atoms, 1 to 12 atoms of which: up to 4 may be
hetero atoms; and at least 1 is a bridging atom. By
"bridging atom(s)" is meant atoms) directly linking
between groups M1 and M2. Preferably there are from 2 to
4 bridging atoms. Bridging atoms may be selected from C,
N, 0, Si and S atoms. Preferably R is an organic bridging
group containing at least one bridging atom which is
typically carbon. More preferably R is an organic
bridging group containing from 2 to 4 bridging atoms, at
least two of which are carbon atoms. Examples of such
groups R are -CH2-CH2-, -CH2-CH2-CH2-, -CH2-C(CH3)2-CH2-,
-CH2-C(C2H5)2-CH2-, -CH2-Si(CH3)2-CH2- and
_CH2-CH2_CH2_CH2_.
At least one of M1 or M2 preferably represents a
phosphorus atom. More preferably, both of M1 and M2
represents a phosphorus atom.
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Ligands in accordance with the present invention for
use in a catalyst composition preferably form a complex
with the Group VIII metal. It would appear that the
presence of two complexing sites in one ligand molecule
significantly contributes to the activity of the
catalysts.
Preferred ligands include 1,3-bis[bis(2-methoxy-5-
sulphophenyl)phosphino]propane, 1,3-bis[bis(2-methoxy-5-
sulphophenyl)phosphino]-2,2-dimethylpropane and
1,3-bis[bis(2-methoxy-5-sulphophenyl)phosphino]-2,2-
diethylpropane, and salts thereof. Salts of such ligands,
in particular alkali metal salts and notably sodium
salts, appear to be more effective for polymerization
processes than the free acids. The term "sulpho" is used
herein to denote sulphonic acid groups -S02-OH whilst the
term "sulphonato" denotes salts. The skilled person will
take note of the fact that ligands denoted by
nomenclature may, in fact, exist in zwitterionic forms.
The amount of a said dentate ligand supplied may vary
considerably, but is usually dependent on the amount of
Group VIII metal present in the catalyst composition.
Preferred amounts of a said phosphorus-containing dentate
ligand are in the range of from 0.5 to 1.5 moles per gram
atom of Group VIII metal.
Generally, unless otherwise stated, the Group VIII
metal (in more modern nomenclature a Group 8, 9 or 10
metal) may comprise nickel or cobalt. However, the
Group VIII metal is preferably a noble Group VIII metal,
of which palladium is most preferred.
A Group VIII metal is typically employed as a
cationic species. As the source of Group VIII metal
cations conveniently a Group VIII metal salt is used.
Suitable salts include salts of mineral acids, such as
sulphuric acid, nitric acid, phosphoric acid, perchloric
acid and sulphonic acids, and organic salts, such as
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acetylacetonates. Preferably, a salt of a carboxylic acid
is used, for example a carboxylic acid with up to
8 carbon atoms, such as acetic acid, trifluoroacetic
acid, trichloroacetic acid, propionic acid and citric
acid. Palladium (II) acetate and palladium (II) tri-
fluoroacetate represent particularly preferred sources of
palladium cations. Another suitable source of Group VIII
metal cations is a compound of the Group VIII metal in
its zero-valent state.
Such a Group VIII metal containing catalyst
composition may, as an optional measure, be based on
another additional component which functions during the
copolymerization as a source of anions which are non- or
only weakly co-ordinating with the Group VIII metal under
the conditions of the copolymerization. Typical
additional components are, for example, erotic acids,
Lewis acids, acids obtainable by combining a Lewis acid
and a erotic acid, and an aluminoxane.
The amount of the additional component which
functions during the copolymerization as a source of
anions which are non- or only weakly co-ordinating with
the Group VIII metal, when present, is preferably
selected in the range of 0.1 to 50 equivalents per gram
atom of Group VIII metal, in particular in the range of
from 0.5 to 25 equivalents per gram atom of Group VIII
metal. However, the aluminoxanes may be used in such
quantity that the molar ratio of aluminium to the
Group VIII metal is in the range of from 4000:1 to 10:1,
preferably from 2000:1 to 100:1.
The amount of such a catalyst composition used in the
said copolymerization of the invention may vary between
wide limits. Recommended quantities of catalyst
composition are in the range of 10-8 to 10-2, calculated
as gram atoms of Group VIII metal per mole of
olefinically unsaturated compound to be copolymerized
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with carbon monoxide. Preferred quantities are in the
range of 10-~ to 10-3 on the same basis.
A said copolymerization process employing a catalyst
composition described above may be carried out in the
presence of a liquid diluent, but it may also be carried
out as a gas phase process. If it is carried out in the
presence of a liquid diluent, preferably a liquid diluent
is used in which the copolymer to be prepared forms a
separate, liquid or solid phase, in which case a diluent
may be selected in which the copolymer is insoluble or
virtually insoluble. A solution polymerization may be
carried out in a liquid diluent in which the copolymer to
be prepared is soluble. Examples of liquid diluents are
water, ketones (e. g. acetone), chlorinated hydrocarbons
(e. g. chloroform or dichloromethane), aromatics
(e. g.
toluene, benzene, chlorobenzene), and, preferably, erotic
organic diluents, such as lower alcohols (e. g. methanol
and ethanol) and alkanoic acids, for example acetic acid.
Mixtures of liquid diluents may be used as well, for
example erotic diluents may comprise an aprotic diluent.
Protic organic diluents may contain water.
Generally, unless otherwise stated in this
specification, the term "lower" indicates that the
organic compound to which it refers contains at most
6 carbon atoms.
The diluent may comprise water and an alkanol,
preferably a C1_4 alkanol, in particular ethanol and,
especially, methanol. The ratio of water to alkanol is
preferably in the range of 1:0.1-200, more preferably in
the range of 1:0.3-10, by volume.
The diluent may comprise water and an alkanoic acid,
preferably having from 2 to 5 carbon atoms, preferably
acetic acid. The ratio of water to the alkanoic acid is
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suitably in the range 1:10-10:1, preferably 1:10-3:1,
especially 1:5-2:1, by volume.
The diluent may comprise an alkanol, as defined
above, and an alkanoic acid, as defined above. The ratio
of the alkanol to the alkanoic acid as added is suitably
in the range 1:1 to 20:1, preferably 5:1 to 15:1, by
volume.
The diluent may comprise water, an alkanol, as
defined above, and an alkanoic acid, as defined above,
the relative proportions of these components being within
the definitions given in each of the three preceding
paragraphs.
The diluent may comprise an ester of an alkanol as
defined above and an alkanoic acid, as defined above.
An especially preferred diluent comprises an alkanol,
as defined above, an alkanoic acid, as defined above, and
an ester of an alkanol and an alkanoic acid (preferably
of the same alkanol and alkanoic acid), in water. A
preferred mixture has the following relative proportions,
by volume: alkanol 3-20; water 1-15; alkanoic acid 1;
ester 1-10. An especially preferred mixture has the
following relative proportions by volume: alkanol 5-12;
water 4-10; alkanoic acid 1; ester 2-6. Especially
preferred is 8-9; 5-6; 1; 3-4, as such mixtures represent
under the prevailing conditions equilibrium mixtures of
the ester forming/ester hydrolysis equilibrium.
Suitably the ligand is in salt form, for example in
the form of a metal salt, such as an alkali or earth
alkaline metal salt.
A salt (additional to the ligand when the ligand is
in salt form) for example an alkali metal salt, notably
sodium sulphate (which may be a by-product of a prior
sulphonation reaction) or sodium acetate, may
advantageously be present. A salt may be present in an
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amount of 1-80, preferably 2-30, mol per mol ligand.
Salts of erotic acids may be useful.
Alternatively or additionally a base may
advantageously be present (additional to any base needed
to neutralize a protonated-form ligand). A suitable base
is an alkali metal hydroxide. A base may suitably be
present in an amount of 1-80, preferably 2-30, mol per
mol ligand. A compound which is a salt and which
functions as a base may be employed.
When a said copolymerization process is carried out
as a gas phase process it is preferred to use a catalyst
system supported on a solid carrier, usually in order to
facilitate the introduction of the catalyst composition
into the reactor.
Suitable carrier materials may be inorganic, such as
silica, alumina or charcoal, or organic such as cellulose
or dextrose. Furthermore a polymer material may be used
as carrier, such as polyethene, polypropene or, in
particular, copolymers of carbon monoxide with an
ethylenically unsaturated compound, for example linear
alternating copolymers of carbon monoxide with ethene or
carbon monoxide with ethene and propene or butene-1.
Conveniently the carrier is impregnated with a
solution of the catalyst system in a suitable liquid. It
will be appreciated that the amount of liquid used is
relatively small, so that any excess thereof can easily
be removed before or during the initial stage of the
copolymerization process. On the other hand it has been
observed, that the addition of a minor amount of liquid
during the copolymerization process has a delaying effect
on the deactivation rate of the catalyst, the quantity of
liquid being so small that the gas phase is the
continuous phase during the polymerization. The quantity
of liquid is in particular selected such that it is
20-80o by weight, more in particular 40-60o by weight, of
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the quantity which is sufficient to saturate the gas
phase under the conditions of the polymerization. Polar
liquids are preferred, such as lower alcohols, for
example methanol and ethanol, lower ethers such as
diethylether, tetrahydrofuran or the dimethylether of
diethylene glycol (diglyme) and lower ketones such as
acetone and methylethylketone.
The copolymerization may also be carried out as an
emulsion or solution polymerization reaction.
The presence of a small amount of hydrogen gas may
assist the polymerization reaction.
The performance of such a Group VIII metal catalyst
composition in a said copolymerization process may be
improved by introducing an organic oxidant, such as a
quinone or an aromatic vitro compound. Preferred oxidants
are quinones selected from the group consisting of
benzoquinone, naphthoquinone and anthraquinone. When the
process is carried out as a gas phase process, the
quantity of oxidant is advantageously in the range of
from 1 to 50, preferably in the range of from 1 to
20 mole per gram atom of metal of Group VIII.
A said copolymerization process is usually carried
out at a temperature between 20 and 200 °C, preferably at
a temperature in the range of from 30 to 150 °C, and
usually applying a pressure between 0.2 and 20 MPa,
pressures in the range of from 1 to 10 MPa being
preferred.
The copolymer may be recovered from a said
copolymerization mixture by any suitable conventional
technique. For example solvents) may be evaporated off,
and condensed and recycled if wished. If suitable, the
polymer may be recovered by filtration or centrifugation.
An advantageous method which may sometimes be used with
the preferred solvents of this invention (comprising
water and/or an alkanol and/or an alkanoic acid and/or an
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ester) is to cool the reaction mixture, adding water if
necessary to cause it to separate into two phases. This
typicalJ_y occurs around or above ambient temperature, for
example at 10-50 °C, preferably 20-40 °C. The diluent
rich layer has been found to contain the major amount of
catalyst and may simply be re-used, with some recharging
with additional catalyst, if desired. A lesser amount of
catalyst can sometimes be extracted from the polymer rich
layer, and re-used. The polymer is recovered from the
polymer rich layer.
It has been found that a copolymerization process in
accordance with the present invention offers surprisingly
good rates of reaction. The process exhibits a further
advantage in that catalyst recycling is facilitated, as
mentioned above. Further, a polymerization product having
a better polymer morphology (bulk density) can be
obtained, if the process is carried out as a suspension
copolymerization process.
Olefinically unsaturated compounds which can be used
as monomers in the copolymerization process of the
invention include compounds consisting exclusively of
carbon and hydrogen and compounds which in addition
comprise hetero atoms, such as unsaturated esters.
Unsaturated hydrocarbons are preferred. Examples of
suitable monomers are lower olefins, i.e. olefins
containing from 2 to 6 carbon atoms, such as ethene,
propene and butene-1, cyclic olefins such as
cyclopentene, aromatic compounds such as styrene and
alpha-methylstyrene and vinyl esters, such as vinyl
acetate and vinyl propionate. Of course, a mixture of
olefins may be used.
Generally, the molar ratio of on the one hand carbon
monoxide and on the other hand the olefinically
unsaturated compounds) used as monomer is in the range
of 1:50 to 50:1, preferably 1:5 to 5:1. More preferably
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the molar ratio is in the range of 1:2 to 2:1,
substantially equimolar ratios being preferred most.
Copolymers are preferably prepared in which the units
originating from carbon monoxide on the one hand and the
units originating from the olefinically unsaturated
compounds) on the other hand occur in an alternating or
substantially alternating arrangement. The term
"substantially alternating" will be understood by the
skilled person to means the molar ratio of the units
originating from the carbon monoxide to the units
originating from the olefinically unsaturated compounds)
is above 35:65 in particular above 40:60. When the
copolymers are alternating this ratio is 50:50.
Linear copolymers of carbon monoxide and one or more
olefinically unsaturated compounds) which are alter-
nating or substantially alternating, can be produced in a
wide range of molecular weights.
For high molecular weight copolymers prepared by the
process of the invention, the limiting viscosity number
(LVN), or intrinsic viscosity, of the copolymers is
indicative of the molecular weight thereof. A high LVN
indicates a high molecular weight copolymer and a lower
LVN indicates a lower molecular weight copolymer. The LVN
is calculated from determined viscosity values, measured
for different copolymer concentrations in m-cresol at
60 °C. High molecular weight copolymers have an LVN in
the range of from 0.2 to 10 dl/g, in particular, from 0.4
to 8 dl/g, more particularly from 0.6 to 6 dl/g.
A high molecular weight copolymer is usually a solid
at the temperatures generally used for producing the
copolymer, for example ambient temperature. High
molecular weight copolymers generally have a melting
point above 150 °C, as determined by differential
scanning calorimetry (DSC). They are particularly
suitable as a thermoplastic for fibres, films or sheets,
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or for injection moulding, compression moulding and blow
moulding applications. Such a high molecular weight
copolymer may be used for applications in the car
industry, for the manufacture of packaging materials for
food and drinks and for various uses in the domestic
sphere.
A lower molecular weight copolymer includes a polymer
having a number average molecular weight within the range
200-20,000, preferably in the range 500-10,000, more
preferably in the range 1000-5000, as determined by gel
permeation chromatography, using polystyrene standards.
A lower molecular weight copolymer can be liquid, or
flowable under low pressure or shear, or solid at the
temperatures generally used for processing the copolymer
for example ambient temperature. Such copolymers having a
high ethylene content may tend to be solid.
For copolymers of lower molecular weight the
copolymerization process can generally employ ethene in
admixture with propene or an alpha-C4_6 olefin,
preferably straight chain. Examples of suitable olefins
are 1-hexene, 1-pentene, 1-butene and, especially
1-propene. Suitably the C3-6 olefin is present in an
amount at least 20 mol%, preferably at least 30 molo, of
the total olefin content of the polymer. The balance is
suitably ethene.
In the case of high molecular weight copolymers a
higher proportion of ethene is preferred. For such
copolymers ethene is suitably the only olefinically
unsaturated component or the major one. In high molecular
weight linear, alternating copolymers of carbon monoxide,
ethene and a C3-6 olefin, the molar ratio of the C3-6
olefin to ethene content in the copolymer is typically
above 1:100, preferably in the range from 1:100 to 1:3,
more preferably in the range of from 1:50 to 1:5.
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International patent application No. WO 96/13549
discloses a suitable method of preparation of lower
molecular weight copolymers comprising monomers of carbon
monoxide and an olefinically unsaturated compound, and
examples of use of the resultant copolymers, and is
incorporated herein by reference. The presence of
carbonyl groups in the polymer may facilitate many cross-
linking reactions, and the lower molecular weight
copolymers may be useful in curable resin compositions.
There are several methods of preparing an appropriate
sulphonated ligand for use in a copolymerization reaction
as described above.
A conventional method of sulphonating molecules
involves treatment with fuming sulphuric acid, or oleum.
However, this method of sulphonation is problematic in
that, apart from the general undesirability of working
with oleum, it is difficult to control the selectivity of
the sulphonation process and mixtures of products,
including undesired phosphine oxidation products, may be
obtained.
A further known method of sulphonation involves
mixing the compound to be sulphonated with a mixture of
orthoboric acid and concentrated sulphuric acid, followed
by dropwise addition of S03 in H2S04 at a temperature of
around 0 °C. This method is set out in several patent
specifications including European patent applications
numbers 632 047, 704 450 and 704 451. An advantage
claimed for this method is that the sulphonation is more
selective and that undesired phosphine oxidation products
are minimal.
Preferably, however, the ligands used are made by a
new sulphonation method, which employs mild sulphonation
conditions and does not require orthoboric acid. In a
further aspect, the present invention relates to a
process for sulphonation as defined in claim 15,
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hereinafter. The new sulphonation method is suitably
carried out in the substantial absence of orthoboric
acid, and using, as sulphonating agent, sulphuric acid of
concentration at least 85 %wt or oleum of grade 5 15 owt.
Reference to oleum of grade 5 15o denotes that up to 150
of the total weight of the S03/H2S04 composition is
provided by the S03 component; sulphuric acid of
concentration at least 85o denotes that at least 850 of
the total weight of H2S04/H20 is provided by the H2S04
component. Preferably, the sulphonating agent comprises
sulphuric acid of concentration at least 900, more
preferably at least 920, most preferably at least 940,
and especially at least 950. When the sulphonating agent
comprises oleum this is preferably oleum of grade <_ 100,
most preferably oleum of grade S 50. Preferably, however,
sulphuric acid of concentration at most 980, as opposed
to oleum, is used as the sulphonating agent.
The new sulphonation method is preferably carried out
in the substantial absence of a boron-containing acid.
The phrases "in the substantial absence of" used in
relation to orthoboric acid and a boron-containing acid
are herein defined to mean that the sulphonating agent
generally comprises less than 50 of the boron-containing
acid, preferably less than 20, most preferably less than
0.50, in particular less than O.lo by weight in the
reaction mixture. Preferably there is no boron-containing
acid in the reaction mixture.
Suitably, the new sulphonation method is carried out
at a temperature in the range 0-100 °C, preferably
10-60 °C, especially 20-40 °C. Preferably the method is
carried out without external heating.
The new sulphonation method will generally be carried
out for sufficient time to achieve effective
sulphonation, for the conditions and starting materials
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selected. This may be for at least 3-12 hours, depending
on the conditions and starting materials selected.
Suitably, the new sulphonation method is carried out for
no more than 50 hours, preferably for no more than
24 hours, more preferably for no more than 6 hours.
The new sulphonation method may be carried out in an
inert atmosphere, most preferably of nitrogen. In some
cases this appears to assist in avoiding undesired
products or oxidation at the phosphorus atom(s). In other
cases it appears not to make a difference. Simple trial
and error will enable the skilled person to determine
whether there is advantage in using an inert atmosphere.
Preferably the sulphonating agent is present in
considerable excess over the compound to be sulphonated,
on a molar basis, in the new sulphonation method.
Suitably the ratio of H2SOq (calculated on the basis of
the sulphur content of sulphuric acid or of oleum) to the
compound to be sulphonated is at least 5:1, preferably at
least 10:1, most preferably at least 35:1, on a mol:mol
basis. For practical reasons this ratio is typically at
most 10,000:1, more typically at most 1000:1, on the same
basis.
Suitably the new sulphonation method does not employ
an additional solvent; that is, the sulphuric acid or
oleum serves as sulphonating agent and as solvent.
Using the new sulphonation method mild sulphonation
conditions can be employed to obtain target sulphonated
compounds in good yields within reasonable timescales,
and with low production of undesired side products, such
as phosphine oxides.
A sulphonated compound or a salt thereof, whether
made by the new method or a known method, may be
separated from a sulphonation mixture by conventional
methods, for example employing an alkali metal hydroxide,
as described above. However, the compound is preferably
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separated by a new work-up method which comprises, at the
end of the sulphonation method, whether a known
sulphonation method or the new sulphonation method,
isolating the sulphonated product as a sulphonic acid
from the reaction mixture, the isolating step comprising
contacting the reaction mixture with a precipitating
agent for the sulphonic acid, and separating the
sulphonic acid as a solid from the resulting liquid. In a
further aspect the present invention relates to a process
for preparing a ligand, which process comprises the
steps (a) and (b) as defined in claim 14, hereinafter.
An advantage of the new work-up method is that it
does not need neutralisation of any acid present in the
sulphonation reaction mixture and that it comprises less
steps than the prior art methods.
The precipitating agent is preferably water, but
organic compounds which comprise a hetero atom such as
oxygen, nitrogen or sulphur and which have typically up
to 6 carbon atoms are also suitable, as well as mixtures
thereof and mixtures with water.
In the new work-up method, preferably the reaction
mixture is cooled. In principle the reaction mixture can
be lowered to any temperature at which it does not
freeze.
In some embodiments of the new work-up method contact
with water alone even without lowering of the temperature
causes rapid precipitation of the sulphonic acid which
can be removed by filtration, and washed if desired. In
such embodiments the reaction mixture may be poured into
water at room temperature, then filtered. In other
embodiments when the temperature is to be lowered it may
be advantageous to pour the reaction mixture into water
at room temperature, then to cool the resultant mixture.
In yet other, more preferred, embodiments in which the
temperature is to be lowered, the reaction mixture may be
CA 02372519 2001-11-07
WO 00/68296 - 18 _ PCT/EP00/04216
poured into chilled water, or more preferably, into ice
or ice/water, to effect the contacting with water and the
cooling together.
In some embodiments of the new work-up method the
contact with water and lowering of the temperature, if
carried out, causes slow precipitation of the sulphonated
compound, which can be removed by filtration, and washed
if desired. In some embodiments the contact with water
alone may cause immediate precipitation, but subsequent
cooling may assist in causing further precipitation. In
all such embodiments in which precipitation is not
rapidly completed there is preferably a period for which
the reaction mixture is held at the lowered temperature,
subsequent to the contacting with water. This may be an
extended period, suitably at least 8 hours, preferably at
least 16 hours.
In the new work-up method, when the temperature of
the reaction mixture is lowered, it is preferably lowered
to 10 °C or less; preferably to 5 °C or less. Whilst the
temperature could be lower, for example down to -10 °C,
or -25 °C, or even less, it is convenient to use ice or
ice/water, and so the lowered temperature is preferably
about 0 °C.
Generally, in the new work-up method, the amount of
water with which the sulphonation reaction mixture is
mixed can affect the rate and/or degree of
crystallisation of the sulphonated product. This can be
determined by trial and error. However a ratio of the
reaction mixture to water within the range 1:1 to 1:15,
preferably 1:2 to 1:10, by volume, is generally suitable.
The term "water" used in the definitions of this
specification may be taken to include ice.
The water used to contact the reaction mixture in the
new work-up method is preferably reasonably pure.
Demineralised water is suitable.
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The statements of the preceeding five paragraphs
which relate to the use of water or ice are in an
analogous way applicable to embodiments in which another
precipitating agent or mixture is used instead of water.
The effectiveness of the new work-up method is
surprising. It was not expected that the sulphonated
compounds would be less soluble in water/sulphuric acid
mixtures, than in sulphuric acid alone. Indeed, they
appear to be less soluble in water/sulphuric acid
mixtures, than they are in water alone, and in sulphuric
acid alone.
The new work-up method is, clearly, simple and
convenient. Furthermore experiments have shown it to be
an advantageous method in terms of product yield and/or
purity. The product of the new work-up method is in
acidic form. When water is involved the product has one
or more groups of the general formula
-S03H(H2S04)x(H20)y. x may typically be in the range 0-1,
especially 0-0.5. y may typically be in the range 0-7,
especially 0.5-6. Further, the yield achieved using the
new work-up method has been similar to or exceeded that
achieved by the prior art multi-step work-up method, e.g.
employing sodium hydroxide, assuming like-for-like
sulphonation methods.
The new sulphonation method and/or the new work-up
method can be used to produce and/or isolate compounds of
general formula I having phosphorus atoms M1 and M2, and
wherein in an aryl group which has a substituent of
general formula -S(O)n-X, n represents 2 and R1 has at
least one further substituent independently selected from
hydroxy, alkoxyalkoxy and, especially, alkoxy. The
definitions of preferred ligands given above apply,
within this definition.
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WO 00/68296 _ 2 0 - PCT/EP00/04216
Preferably the catalyst compositions used in the
methods of this invention employ as ligands sulphonated
compounds made by the new sulphonation method, and
isolated by the new work-up method.
The invention is illustrated by the following
examples. In these examples sulphuric acid (95-97 wto),
30o sulphur trioxide solution in sulphuric acid (i.e.
"300 oleum") and solid 98o purity boric acid (H3B03) were
purchased in p.a. grade from Merck or Aldrich and p.a.
grade solvents were used. The sulphonation reactions were
carried out without application of external heat
(although in practice at the addition rates employed the
temperature of some reaction mixtures may rise to
40-50 °C because of exotherms). The water or ice used in
the work-up was demineralised. Product confirmation of
ligands described below was by 1H-, 31p_~ 13C-NMR and
elemental analysis. The position of the sulphonyl groups
was determined by the technique PFG-HMQC (Pulse Field
Gradient Heteronuclear Multiple Quantum Coherence).
EXAMPLE 1
Preparation of 1,3-bis[bis(2-methoxy-5-sodiumsulphonato
phenyl)phosphino]propane (BDOMPP-S)
Orthoboric acid (H3B03, 3.2 g, 51.7 mmol) was added
to sulphuric acid (30 ml) and the mixture was stirred
until a homogeneous solution was obtained. Subsequently,
1,3-bis[bis(2-methoxyphenyl)phosphino]propane (BDOMPP,
7.3 g, 13.7 mmol) was added. The reaction mixture was
cooled to 0 °C and a solution of 300 oleum (150 ml) was
added dropwise, whilst the temperature of the reaction
mixture was maintained between 0 and 5 °C. After addition
was complete, stirring was continued at ambient
temperature for 48 hours. The mixture was then hydrolysed
by addition of ice (400 g). The acidic reaction mixture
was then neutralised by addition of a 25 wto solution of
CA 02372519 2001-11-07
WO 00/68296 - 21 - PCT/EP00/04216
sodium hydroxide in water. The neutralised mixture was
concentrated by evaporation of water at 75 °C and
200 mbar (20 kPa) pressure until a white suspension was
formed. Methanol (750 ml) was then added to the mixture,
which was then stirred for 15 minutes. The residual
precipitate, consisting mainly of sodium sulphate, was
removed by filtration. After removal of the solvent
methanol, by evaporation under a vacuum, the residual
white solid still contained a significant amount of
sodium sulphate. Therefore, a second extraction with
methanol was carried out by first dissolving the impure
white solid in methanol followed by removal of
non-dissolved salt by filtration and subsequent removal
of methanol by evaporation under vacuum.
Elemental analysis of the end product as isolated
gave the following results: carbon 12.89 ow; hydrogen
2.81 ow; phosphorus 2.81 %w; sulphur 15.42 ow; sodium
17.92 ow. The elemental analysis corresponds to a
molecular structure: 1BDOMPP-S, 29.7 H20, 7.6 Na2S04. It
was calculated that a 33.7 wto yield of BDOMPP-S as a
sodium salt was obtained.
EXAMPLE 2
Preparation of a BDOMPP-S based catalyst
Palladium acetate (5.0 mg) and BDOMPP-S (obtained in
accordance with Example 1 above, 65.9 mg) were dissolved
in acetone (5 ml), then water (5 ml) was added. After
1 hour, neat trifluoroacetic acid (10.1 mg) was added.
A clear yellow solution was obtained, which was used
to catalyse the copolymerization reaction described in
Example 3 below.
~vTnrtnr r
Polymerization reaction using BDOMPP-S based catalyst
The polymerization reaction was carried out in a
350 ml magnetically stirred steel batch autoclave. The
CA 02372519 2001-11-07
WO 00/68296 _ 2 2 - PCT/EP00/04216
reactor was charged with 129 ml of a MeOH/H20/HOAc/MeOAc
mixture (45.4:29.5:5.3:19.6, v/v). After purging the
reactor with nitrogen, 60 g of propylene was added
thereto. The reactor was thereafter pressurised with
7 bar (0.7 MPa) of hydrogen gas and 1 bar (0.1 MPa) of
carbon monoxide. The mixture was subsequently heated to
89 °C and 30 bar (3.0 MPa) of a 80/20 v/v CO/ethene
mixture gas was added to the autoclave.
After stabilization of temperature and pressure, all
of the BDOMPP-S based catalyst produced in accordance
with Example 2 above, was injected into the reactor to
start the reaction. The catalyst system was flushed with
10 ml of acetone to ensure quantitative catalyst
injection. The reactor temperature increased to 91 °C.
The pressure was kept constant by continuous addition of
an 80/20 v/v CO/ethene mixture gas.
After 3 hours the reaction was stopped. The flow of
mixture gas was then stopped by blocking the gas supply
then the reactor was cooled rapidly down to room
temperature and then the gases that did not react were
vented until atmospheric pressure was obtained. The
reactor content was subsequently transferred to a
rotavapor, where the solvents were removed under reduced
pressure (60 mbar (6.0 kPa) to 1 mbar (0.1 kPa)) at 70 °C
and the isolated polymer was weighed and analyzed for
molecular weight and ethene content.
Reaction rate data was calculated on the basis of gas
flow uptake and on the basis of average product weight.
The results are summarised in Table 1 below.
EXAMPLE 4 (comparative)
Polymerization reaction usin a BDOMPP based catal st
A catalyst was prepared by dissolving 5.0 mg of
palladium acetate and 12.5 mg of BDOMPP in 10 ml of
acetone. After 1 hour, 10.1 mg of trifluoroacetic acid
was added. The resulting clear yellow liquid was used to
CA 02372519 2001-11-07
WO 00/68296 - 2 3 - PCT/EP00/04216
start the following oligomerisation reaction within
30 minutes of addition of the trifluoroacetic acid.
The catalyst was then used in place of the BDOMPP-S
based catalyst of Example 2 in a repeat of the
polymerization reaction of Example 3. Again, the reaction
rate data was calculated and is set out in Table 1.
The data set out in Table 1 clearly illustrates that
the reaction rate and the product yield is more than
twice as high as a result of use of a catalyst comprising
a sulphonated ligand than the reaction rate or product
yield when the reaction rate is carried out with a
catalyst comprising a corresponding, but non-sulphonated,
ligand.
Table 1
Property BDOMPP BDOMPP-S (Ex.3)
(Ex.4)
Initial ratea 6.1 14.3
(kg.gPd_l.h_1)
End of run ratea 4.2 11.5
(kg.gPd_l.h_1)
Yield (g) 29.7 70.0
Average rateb 4.2 9.9
(kg.gPd_l.h_1)
Mn (Dalton) 2869 3284
Molo ethenec 37 33
a - initial rate and end of run rate calculated on bases
of gas flow and on Pd intake.
b - average rate calculated on base of polymer yield on
Pd intake.
c - molo based on total olefin content of the polymer.
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WO 00/68296 - 2 4 - PCT/EP00/04216
T~VTTAT'1T T C
Recycling the catalyst
The reactor of a 350 ml, magnetically stirred AISI
316 steel batch autoclave was charged with 129 ml of a
MeOH/H20/HOAc/MeOAc mixture (45.5:29.5:5.3:19.6 v/v).
After purging the reactor with nitrogen, 60 g of
propylene was added. The reactor was thereafter
pressurised with hydrogen gas at 7 bar (0.7 MPa) and
carbon monoxide at 1 bar (0.1 MPa) pressure. The mixture
was heated to 89 °C and 30 bar of a 80/20 v/v mixture of
carbon monoxide and ethene was added to the reactor.
Total reactor pressure was 65-67 bar (6.5-6.7 MPa). After
stabilisation of temperature and pressure, the catalyst,
as prepared in accordance with Examples 1 and 2 above,
was injected to start the oligomerisation reaction. The
reactor was flushed with 10 ml of acetone to ensure
quantitative catalyst injection. The reactor temperature
increased to 91 °C. The pressure was kept constant by
continuous addition of a 80/20 v/v mixture of carbon
monoxide and ethene gas.
After three hours the reaction was stopped by steps
taken in the following order: first the flow of the
mixture gas was stopped by blocking the gas supply, then
the reactor was cooled down to room temperature and the
gases that did not react were vented until atmospheric
pressure was obtained. The reactor content was
subsequently transferred to a separation funnel. After
approximately 1 hour the two phases were separated and
weighed. The top layer was used to charge the reactor,
the bottom layer was washed with the equilibrium solvent
mixture MeOH/H20/HOAc/MeOAc (45.5:29.5:5.3:19.6 v/v),
with a volume of V(wash)=V(reactor solvent)
(129 ml) - V(top layer).
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WO 00/68296 _ 2 5 _ PCT/EP00/04216
This mixture of the bottom layer and the wash-solvent
were allowed to settle and were separated after
approximately 1 hour. A second top layer and bottom layer
were formed. Both layers were weighed. The reactor,
already containing the first top layer, was charged with
the second top layer. If needed, the volume was brought
to the initial solvent volume of 129 ml. The new bottom
layer containing polyketone product was transferred to a
rotavapor. The solvents were removed at a reduced
pressure of 1 mbar (0.1 kPa) at 70 °C and the isolated
polymer was analysed for molecular weight and ethene
content.
The solvent mixture in the reactor was used to
perform the same experiment again. However, this time no
catalyst was injected. Two recycles were carried out by
this method. The results of this experiment are labelled
Experiment A in Table 2 below.
A variant of this procedure involves injecting extra
catalyst into the system compensating for the loss of
active catalyst during the recycle experiments. Again two
recycles were performed by this method, 34 owt of fresh
catalyst being added at the start of each such recycle.
The results are labelled Experiment B in Table 2 below.
CA 02372519 2001-11-07
WO 00/68296 PCT/EP00/04216
-26-
w o
U O
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CA 02372519 2001-11-07
WO 00/68296 _ 2 .~ - PCT/EP00/04216
Table 2 shows that without addition of extra fresh
catalyst the product yield declines from 56.4 g of
polymer to 35.8 g of polymer in the second recycle. This
is likely to be caused by a combination of catalyst
deactivation and the loss of active species with the
polyketone polymer via the bottom phase.
Comparison of initial and end of run reaction data
gives an indication of the catalytic decay during each
cycle. It also illustrates the decline in activity
between a specific cycle and the preceding cycle. Based
on the difference in these activity values between the
cycles it was concluded that approximately 660 of the
activity is maintained by recycling the catalyst species.
It was therefore concluded that addition of 340 of fresh
catalyst should counteract that decline.
Table 2 illustrates that by addition of 340 of fresh
catalyst, product yield in the first, second and third
cycle were of a similar order of magnitude. This
illustrates that addition of 34o catalyst between the
first and second cycles and the second and third cycles
was sufficient to counteract the decline in activity of
the recycled catalyst.
~vTnanr ~ G
Investigation of effects of added base or salt
Firstly a protonated ligand was prepared as
follows:
BDOMPP (22.5 g) was added to sulphuric acid (110 ml).
The mixture was stirred for 24 hours at ambient
temperature under a nitrogen atmosphere. The reaction
mixture was then poured into water (1000 ml, room
temperature) and cooled. After storage at 4 °C overnight
a white prec~.pitate was present. The precipitate was
filtered and washed twice with methyl ethyl ketone
(2 x 250 ml). After drying BDOMPP-S in protonated form,
4.1 H20 (32.7 g, 830) was obtained.
CA 02372519 2001-11-07
WO 00/68296 - 2 8 - PCT/EP00/04216
A number of experiments were carried out under
different reaction conditions, and employing as diluent
methanol/water/acetic acid/methyl acetate equilibrium
mixtures, following the procedure set out in Example 3.
The experiments are summarised, and the results given, in
Table 3 below. Experiments were included using ligands of
which the sulpho groups were neutralised in situ with
sodium hydroxide, or in the presence of sodium sulphate
(a constituent of the earlier salt-form examples).
CA 02372519 2001-11-07
WO 00/68296 PCT/EP00/04216
_29_
0
O N ~ ~
k ~ -I~ ACS -i
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CA 02372519 2001-11-07
WO 00/68296 PCT/EP00/04216
-30-
0
0 O N
o
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r1 ~ M N O
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CA 02372519 2001-11-07
WO 00/68296 _ 31 _ PCT/EP00/04216
~vrnrtnr ~
Investigation of solvent effects
Further experiments were performed using the catalyst
described in Example 6, following the procedure set out
in Example 3. Three experiments were carried out in an
equilibrium solvent mixture of methanol, water, acetic
acid and methyl acetate and two experiments, under
closely similar reaction conditions, were carried out
with acetic acid/water solvent mixtures. All experiments
were carried out using process conditions directed to
preparing a polymer with a target Mn of 3500 and ethylene
content of 50o mol, based on the total of olefin
incorporated into the polymer product. The experiments
are summarized, and results are shown in Table 4 below.
CA 02372519 2001-11-07
WO 00/68296 PCT/EP00/04216
-32-
O -v-~~ U is
+ ~ 4-a.~ FC-r1 t3~
b ~ is
(la S-I O ~ 01 u7 O W M
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CA 02372519 2001-11-07
WO 00/68296 PCT/EP00/04216
-33-
~ v s~
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+ ~ 4--I.~~C w-i
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a~ a5, r-I-~.~~ .-i
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U ?1 t0v E ~ ~ U p.,
CA 02372519 2001-11-07
WO 00/68296 - 3 4 - PCT/EP00/04216
r~vTnrtnT r. O
Synthesis of BDOMPP-S[Na]4Pd(OAc)2 catalyst
5.20 g of BDOMPP (9.8 mmol) was added to 21 ml of
sulphuric acid and stirred for 22 hours at room
temperature under a nitrogen atmosphere. The reaction
mixture was poured in 100 ml of water and after storage
at -20 °C, a white precipitate was formed. After
filtration, the resulting solid was washed with
2 portions of acetone (10 ml). After drying, 8.85 g of
BDOMPP-S, 3.4 H20, 0.7 H2S04 was obtained.
The portion was mixed with another portion of
BDOMPP-S (0.9o H2S04) and after washing with 2 portions
of methyl ethyl ketone a white solid was obtained with
the composition, BDOMPP-S, 4.1 H20, 0.25 H2S04.
A portion of the thus-obtained BDOMPP-S (1.01 g,
1.01 mmol) was dissolved in water (30 ml). Sodium
hydroxide (1.62 g, 4.05 mmol) was added. The mixture was
stirred for 15 minutes and then added to Pd(OAc)2
(216 mg, 0.96 mmol) dissolved in acetone (30 ml). The
solution, which turned yellow, was stirred at ambient
temperature for 2 hours. The solvents were removed under
vacuum and the residue was washed with diethyl ether
(40 ml) and then acetone (10 ml) to obtain the title
compound (860 mg).
EXAMPLE 9
Copolymerization of carbon monoxide and ethene using the
BDOMPP-S [Na]4Pd(OAc)2/trifluoroacetic acid catalyst
A suspension of methanol: water (1:1, by volume,
1 litre in total) and a polymer seed powder, which was an
alternating carbon monoxide/ethene/propene copolymer
(60 g), was placed in an autoclave. The autoclave was
heated to 90 °C and pressurized with 25 bar (2.5 MPa) of
ethene following by an additional 25 bar (2.5 MPa) of
carbon monoxide. The pressure was maintained constant at
CA 02372519 2001-11-07
WO 00/68296 _ 3 5 - PCT/EP00/04216
50 bar (5.0 MPa) using a 1:l mixture of carbon
monoxide/ethene.
A mixture of BDOMPP-S[Na]4Pd(OAc)2, as prepared in
accordance with Example 8 above, (16.5 mg, 14.2 ~mol,
1.5 mg Pd) and trifluoroacetic acid (6.7 ~1, 86 ~.mol) in
water (10 ml) was injected into the autoclave. The
copolymerization reaction was conducted for 1 hour at
90 °C at a constant pressure of 50 bar (5.0 MPa) carbon
monoxide/ethene. The reaction mixture was removed from
the autoclave, filtered and the polymer was dried at
100 mbar (10.0 kPa) pressure and 80 °C. 47.0 g of
copolymer was obtained and the average copolymerization
rate was 31.3 kg.gPd-l.h-1.
This copolymerization was repeated varying the
composition of the solvent. The further results are set
out in Table 6 below. Recycling mentioned in Table 5
involved removal of the polymer product by filtration and
repeating the copolymerization process using the same
catalyst/solvent, without recharge of the catalyst.
CA 02372519 2001-11-07
WO 00/68296 PCT/EP00/04216
36
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