CA1293241C - Catalyst compositions - Google Patents
Catalyst compositionsInfo
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- CA1293241C CA1293241C CA000529756A CA529756A CA1293241C CA 1293241 C CA1293241 C CA 1293241C CA 000529756 A CA000529756 A CA 000529756A CA 529756 A CA529756 A CA 529756A CA 1293241 C CA1293241 C CA 1293241C
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Abstract
A B S T R A C T
CATALYST COMPOSITIONS
Novel catalyst compositions, characterized in that they are based upon a) a palladium compound, b) an acid with a pKa of less than 2, provided that the acid is not a hydrohalogenic acid, c) a bidentate ligand of the general formula R1R2-M-R-M-R3R4, wherein M represents phosphorus, arsenic or antimony, R1, R2, R3 and R4 represent hydrocarbyl groups which may or may not be substituted with polar groups and R represents a bivalent organic bridging group having at least two carbon atoms in the bridge, and d) a quinone.
CATALYST COMPOSITIONS
Novel catalyst compositions, characterized in that they are based upon a) a palladium compound, b) an acid with a pKa of less than 2, provided that the acid is not a hydrohalogenic acid, c) a bidentate ligand of the general formula R1R2-M-R-M-R3R4, wherein M represents phosphorus, arsenic or antimony, R1, R2, R3 and R4 represent hydrocarbyl groups which may or may not be substituted with polar groups and R represents a bivalent organic bridging group having at least two carbon atoms in the bridge, and d) a quinone.
Description
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, :: : :
:: : :
., , .
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, :: : :
:: : :
., , .
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.
,, . ..~ .
32~1 _ 4 _ 63293-2759 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 'dA ' ' 32'~ -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:
-_ ~ ~3293-2759 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.
~ .
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.
,, . ..~ .
32~1 _ 4 _ 63293-2759 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 'dA ' ' 32'~ -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:
-_ ~ ~3293-2759 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.
~ .
3 2 L~
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 ~ .
~, 32~
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.
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 ~ .
~, 32~
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.
Claims (9)
1. Novel catalyst compositions, characterized in that they are based upon a) a palladium compound, b) an acid with pKa of less than 2, provided that the acid is not a hydrohalogenic acid, c) a bidentate ligand of the general formula R1R2-M-R-M-R3R4, wherein M represents phosphorus, arsenic or antimony, R1, R2, R3 and R4 represent hydrocarbyl groups which may or may not be substituted with polar groups and R
represents a bivalent organic bridging group having at least two carbon atoms in the bridge, and d) a quinone.
represents a bivalent organic bridging group having at least two carbon atoms in the bridge, and d) a quinone.
2. Catalyst compositions as claimed in claim 1, characterized in that they are based upon a palladium salt of a carboxylic acid as component a).
3. Catalyst compositions as claimed in claim 1, characterized in that they are based upon sulphonic acid or a carboxylic acid as component b).
4. Catalyst compositions as claimed in claim 1, characterized in that a component c) is used wherein M is phosphorus.
5. Catalyst compositions as claimed in claim 1, 2, 3 or 4, characterized in that a component c) is used wherein the groups are phenyl groups or alkyl-substituted phenyl groups, and wherein the bivalent organic bridging group R has three carbon atoms in the bridge.
6. Catalyst compositions as claimed in claim 1, 2, 3 or 4, characterized in that the component d) used is a 1,4-quinone.
7. Catalyst compositions as claimed in claim 6, characterized in that the component d) used is a substituted or unsubstituted benzoquinone.
8. Process for the preparation of copolymers, characterized in that a mixture of carbon monoxide and one or more olefinically unsaturated organic compounds is copolymerized by using a catalyst composition as claimed in claim 1, 2, 3 or 4.
9. Process as claimed in claim 7, characterized in that it is applied for the preparation of copolymers of carbon monoxide with ethene or terpolymers of carbon monoxide with ethene and an other olefinically unsaturated hydrocarbon such as propene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000529756A CA1293241C (en) | 1986-03-05 | 1987-02-16 | Catalyst compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8600563 | 1986-03-05 | ||
| CA000529756A CA1293241C (en) | 1986-03-05 | 1987-02-16 | Catalyst compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1293241C true CA1293241C (en) | 1991-12-17 |
Family
ID=4134976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000529756A Expired - Fee Related CA1293241C (en) | 1986-03-05 | 1987-02-16 | Catalyst compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1293241C (en) |
-
1987
- 1987-02-16 CA CA000529756A patent/CA1293241C/en not_active Expired - Fee Related
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