Note: Descriptions are shown in the official language in which they were submitted.
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T 115
CATALYST CoMPOSITIONS
The invention relates to novel compositions which are suitable
for use as catalysts in the preparation of polymers of c~rhon
monoxide with one or more olefinically unsaturated organic compounds.
High moleculc~r weight linear polymers of carbon monoxide with
one or more olefinically unsaturated organic ccmpounds (for the
sake of brevity~referred to as A) in which the monc~,er units occur
in an alternating order and which therefore consist of units of th~
general formula -(CO)-A'- wherein A' represents a monomer unit from
a monomer A used, can be prepared by using catalyst compositions
l ~ased on:
a~ a palladium compound,
b) an acid with a pKa of less than 2, provided that the acid is
not a hydrohalogenic acid, and
c) a bidentate ligarld of the general formlla R1R -M-R-M-R3R ,
wherein ~M represents phosphorus, arsenic or antimony, R1, R ,
R and R represent hydrocarbyl groups which may or may not be
substituted with polar groups and R represents a bivalent
organic bridging group which contains at least two carbon
atoms in the bridge.
An investigation carried out by the Applicant into these
catalyst compositions has shown that their activity for the polymer-
ization of carbon monoxide with one or more olefinically unsaturated
organic ccmpounds can ke considerably enhanced by incorporating a
quinone into the composition~. Catalyst campositions based on
~; ~ 25 compon nts a~-c) and in addition a quinone, are novel.
The present patent application therefore relates to novel
catalyst compositions based on
a) a palladium ccmpound,~
b) an acid with a pKa of less than 2, provided that the acid is
;~ ~ 30~ not a hydrohalogenic acid,
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c) a bidentate ligand of the general formula RlR2-M-R-M-R3R4,
wherein M represents phosphorus, arsenic or antimony, Rl, R2,
R3 and R represent hydrocarbyl groups which may or may not be
substituted with polar groups and R represents a bivalent
organic bridging group containing at least two carbon ato~s in
the bridge, and
d) a quinone.
The patent application further relates to the u æ of these
catalyst co~positions in the preparation of polymers of carbon
monoxide with one or ~re olefinically unsaturated organic co~pounds
as well as to the polymers thus prepared and to shaped objects
which consist at least partly of these polymers.
Preferably the palladium compound used as component a) is a
palladium salt of a carboxylic acid and in particular palladium
acetate. Examples of suitable acids with a pKa of less than 2
~determlned in aqueous solution at 18 C~ are sulphuric acid,
perchloric acid, sulphonic acids, such as methanesulphonic acid,
trifluoromethanesulphonic acid and para-toluenesulphonic acid and
carboxylic acids, such as trichloroacetic acid, difluoroacetic acid
and txifluoroacetic acid. Preference is given to para-toluenesulphonic
acid and trifluoroacetic acid. Component b) is preferably applied
in a quantity of from 0.5 to 200 and in particular l.0 to lO0,
equivalents per gram atom of palladium.
In the bidentate ligand, M is preferably phosphorus. The
; 25 groups Rl, R2, R3 and R4 present in ~le bidentate ligand preferably
contain 6 to l4 carbon atoms. Special preference is given to
bidentate ligands in which the groups Rl, R2, R3 and R4 are phenyl
groups or aLkyl-substituted phenyl groups. The bivalent organic
bridging group R prefer~bly contains three carbon atoms in the
bridge. Examples of suitable bidentate ligands are: 1,3-bis(di-p-
tolylphosphino~propane, 1,3-bis(di-p-methoxyphenylphosphino)propane,
l,3-bis(diphenylphosphino)propane, and~2-methyl-2-(diphenylphos-
phinome-thyl)-l,3-bis(diphcnylphosphino)propane. Preferably either
one of the latter two bidentate ligands is used. ~he bidentate
~ ?3;~
ligand is preferably applied in a quantity of 0.1-5 and in particular
of 0.5-1.5 mol per mol of palladium compound.
As the component d) either 1,2- or 1,4-quinones may be used.
Preference is given to 1,4-quinones. Besides substituted or unsub-
stituted benzoquinones, other quinones, such as substituted orunsubstituted naphthaquinones and anthraquinones, are also eligible.
Preference is given to benzoquinones and to 1,4-benzoquinones in
particular. Examples of suitable ccmpounds of this type are:
2,6-dichloro-1,4-benzoquinone,
tetrachloro-1,4-benzoquinone,
2,3-dimethyl-1,4-benzoquinone,
2,6-dimethyl-1,4-benzoqu1none,
mono-~ethyl-1,4-benzo~uinone,
trichloro-1,4-benzoquinone,
2,5-dihydroxy-1,4-benzoquinone,
2,5-dihydroxy-3,6-dinitro-1,4-benzoquinone, and
mono-nitro-1,4-benzoquinone.
The preferred component d) is 1,4-benzoquinone. The preferred
quantity used is 1-10000 and in particular 10-5000 mol per gram
atom of palladium.
The polymerization using the catalyst compositions according
to the invention is preferably carried out in a liquid diluent.
Very suitable liquid diluents are lower alcohols such as methanol
and ethanol.
Eligible olefinically unsaturated organic cc~pounds that can
be polymerized with carbon monoxide with the aid of the catalyst
compositions according to the invention are both co~pounds which
sonsist exclusively of carbon and hydrogen and ccmpounds which, in
addition to carbon and hydrogen, contain one or more hetero-atoms.
By preference the catalyst compositions according to the invention
are used to prepare polymers of car~on monoxide with one or more
olefinically unsaturated hydrocarbons. Examples of suitable hydro-
carbon monomers are ethene and other ~-olefins, such as propene,
butene-l, hexene-1 and octene-l as well as styrene and aIkyl-
substituted styrenes, such as p-methyl styrene and p-ethyl styrene.
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The catalyst compositions according to the invention are especially
suitable for use in the preparation of copolymers of carbon monoxide
with ethene and in the preparation of terpolymers of carbon monoxide
with ethene and with an other olefinically unsaturated hydrocarbon,
in particular propene.
m e quantity of catalyst composition applied in the preparation
of the polymers may vary within wide ranges. Per mol of olefinically
unsaturated compound to be polymerized, a quantity of catalyst is
used which preferably contains 10 7-10 3 and in particular 10 6-10 4
gram atom of palladium.
Preferably, the preparation of the polymers is carried out at
a temperature of 20-200 C ana a pressure of 1-200 bar and in
particular at a temperature of 30-150 C and a pressure of 20-100
bar. In the mixture to be polymerized the molar ratio of the
olefinically unsaturated organic co~pounds relative to carbon
monoxide preferably is 10:1-1:5 and in particular 5:1-1:2. m e
carbon monoxide used in the preparation of the polymers according
; to the in~Jention need not be pure. It may contain contamunations,
such as hydrogen, carbon dioxide and nitrogen.
The invention will now be illustrated with the aid of the
following examples.
Example 1
A carbon monoxide/ethene copolymer was prepared as follows. A
magnetically stirred autoclave of 300 ml capacity was charged with
200 ml of methanol. After the contents of the autoclave were
brought to 65 C, A 1:1 carbon monoxide/ethene mixture was introduced
until a pressure of 55 bar was reached. Then the autoclave was
charged with a catalyst solution consisting of:
; 18 ml methanol,
0Oo3 D 1 of palladium acetate,
0.036 mmol of 1,3 bis(diphenylphosphino)propane, and
0.06 mmDl of p-toluenesulphonic a~id.
The pressure was maintained at 55 bar by introducing under pressure
: a 1:1 carbon ~onoxide/ethene mixture. After 1.5 hour the polymer-
ization was terminated by releasing the pressure. The polymer was
filtered off, washed with nethanol and dried at 70 C. The yield
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was 15 g of copolymer, so the polymerization rate was 3100 g of
copolymer/g of palladium/hour.
A carbon monoxide/ethene copolymer was prepared in substantially
the same manner as the copolymer in Example 1, except that now the
catalyst solution also contained 0.3 mm~l 1,4-benzoquinone. The
yield was 22 g of copolymert so the polymerization rate was 4600 g
of copolymer/g of palladiumlhour.
Example 3
.
A carbon monoxide/ethene copolymer was prepared in substantially
the same manner as the copolymer in Example 1, the differen oe s
being that
a) a catalyst solution was used comprising.
6 ml of methanol,
0.01 mmol of palladium acetate,
0.012 mm~1 of 1,3-bis(dlphenylphosphino)propane and
0.2 mmol of trifluoroacetic acid, and
b) the polymerization was terminated after 2 hours.
The yield was 6 g of copolymer, so the polymerization rate was
2800 g of copolymer/g of palladium~hour.
Example 4
A carbon monc~ide/ethene copolymer was prepared in substantially
the same m~nner as the copolymer in Example 3, the difference being
that now the catalyst solution also contained 1 mmol of 1,4-benzo-
2S quinone~
The yield was 12 g of copolymer, so the polymerization ratewas 5600 g of copolymer/g of palladium~hour.
A carbon monoxide/ethene/propene terpolymer was prepared as
follows. A mechanically stirred autoclave of 300 ml capacity was
charged with 140 ml of methanol and 86 ml of liquid propene. After
the contents of the autoclave had been brought to a temperature of
65 C, a 1:1 carbon m~nc~ide/ethene muxture was introduced until a
pressure of 55 bar was reached. Then the autoclave was charged with
a catalyst solution consisting of:
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6 ml of methanol,
0.01 mmol of palladium acetate,
0.012 mmol of 1,3-bis(diphenylphosphino)propane,
0.2 mmol of trifluoroacetic acid.
Introduction of a 1:1 carbon monoxide/ethene mixture kept the
pressure at 55 bar. After 4 hours the polymerization was terminated
by releasing the pressure. ~he polymer was filtered off, washed
with methanol and dried at 70 C.
The yield was 8 g of terpolym~r, so the polymerization rate
was l900 g of terpolymer/g of palladiumlhour.
Example 6
A carbon monoxide/ethenelpropene terpolymer was prepared in
substantially the same manner as the terpolymer in Example 5,
except that now the catalyst solution also contained 1 mmol of
1,4-benzoquinone.
The yield was 13 g of ter~olymer, so the polymerization rate
was 3100 ~ of terpolymer/g of palladi-~hour.
Of the polymers prepared according to Examples 1-6, only the
copolymers prepared according to Examples 2 and 4 and the terpolymer
prepared according to Example 6 are polymers according to ~he
invention. In thc preparation of these polymers use was made of
catalyst compositions according to the invention contai m ng a
quinone as the Eourth aomponent. The copolymers prepared according
to Examples 1 and 3 and the terpolymer prepared according to
Example 5 fall outside the scope of the invention and have been
included in the patent application for co~parison.
m e favourable effect which the incorporation into the catalyst
compositions according to the invention of a quinone as the fourth
oomponent has on the polymerization rate becomes evident upon
comparison of the results of Examples 2, 4 and 6 with those of the
Exa~ples 1, 3 and 5, resp~ctively.
All of the copolymers prepared according to Examples 1-4 had
melting points of 257 C. The terpolymer prepared according to
Example S had a melting point of 170 C, and the terpolymer prepared
according to Example 6 hac~ a melting point of 182 C.
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With the aid of C -NMR analysis it was established that the
carbon monoxide/ethene copolymers prepared according to Exa~ples
1-4 had a linear alternating structure and therefore consisted of
units of the formula -CO-~C2H4)-.
It was also established by C13-NMR analysis that the carbon
monoxide/ethene/propene terpolymers had a linear structure and
consisted of units of the formula -aO-(C2H4)- and units of the
formula -CC-(C3H6)-, which units occurred randomly distributed
within the terpolymers. The data produced by C13-NMR analysis
showed that in the terpolymer prepared according to Example 5 there
were 26 units based on propene to 74 units based on~e~hene, which
am~unts to a propene content in the terpolymer of 18.3 %w. Further-
more it was seen that in the terpolymer prepared according to
Example 6 there were 215 units based on prcp~ne to 785 units based
on ethene, which amounts to a propene content in the terpolymer of
15.3 ~w.
Ex_~ple 7 (for co~parison)
A CO/ethene copolymer was prepared in the way described in
Example l, except the following differences
20 a) catalyst solution of O.Ol9 ~mol Pd-acetate, 0.02 mmol l,3-
bis~di(p-methoxyphenyl)phosphino]`propane, 0.38 l trifluoro-
acetic acid in 18 ml ethanol;
b) polymerization t~p~rature lO0 C;
c) polymerization period 6.7 hours.
51.3 g of copolymer were produced, thus, the polymerization rate
was 3800 g.g Pd l.hr l.
Example 8
A CO/ethene copolymer was produced in the manner indicated in
Example l except the following differences
a) cat~lyst solution of O.Ol mmol Pd-acetate, 0.012 mmol 1.3-
bls[di(p-methoxyphenyl)phosphino]propane, 0.2 mmol trifluoro-
acetic acid, and 2 mm~l 1,4-benzoquinone in 18 ml ethanol;
b) poly~erization period 3 hours;
c) polymerization temperature 96 C.
29.6 g copolymer were cbtained, thus, the polymerization rate was
9300 g.g pd-l hr-l
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6 ml of methanol,
0.01 mmol of palladium acetate,
0.012 mmol of 1,3-bis(diphenylphosphino)pxopane,
0.2 mmol of trifluoroacetic acid.
Introduction of a 1:1 carbo~ monoxide/ethene mixture kept the
pres Æ e at 55 bar. After 4 hours the polymerization was terminated
by releasing the pressure. The polymer was filtered off, washed
with methanol and dried at 70 C.
The yield was 8 g of terpolymer, so the poly~erization rate
was l900 g of terpolymer/g of palladiun~hour.
Example 6
A carbon monoxide/ethene/propene terpolymer was prepaxed in
substantially the same manner as the terpolymer in Exa~ple 5,
except that now the catalyst solution also contained 1 mmol of
1,4-benzoquinone.
The yield was 13 g of terpolymer, so the polymerization rate
was 3100 g of terpolymer/g of palladiumlhour.
Of ~he polymers prepared according to Examples 1-6, only the
copolymers prepared according to Examples 2 and 4 and the terpolymer
prepared according to Example 6 are polymers according to the
mvention. In the preparation of these polymers use was made of
catalyst ccmpositions according to the invention containing a
quinone as the fourth component. The copolymexs prepared accordin~
to Examples 1 and 3 and the terpolymer prepared according to
Example S fall outside the scope of the invention and have been
included in the patent application for ccmparison.
m e favourable effect which the incorporation into the catalyst
compositions according to the invention of a quinone as the fourth
oomponent has on the polymerization rate becomes evident upon
comparison of the results of Examples 2, 4 and 6 with those of the
Examples l, 3 and 5, res~ectively.
All of the copolymers preFal^ed according to Examples 1-4 had
melting points of 257 C. The terpolymer prepared according to
EXample 5 had a melting point o~ 170 C, and the terpolymer prepared
according to Example 6 had a melting point of 182 C.
