CATALYST COMPOSITIONS

Abstract: Novel catalyst compositions, characterized in that they are based upon a) a palladium compound, b) a non-noble transition metal salt of an acid with a pKa of less than 2, provided that the acid is not a hydrohalogenic acid, or a mixture of such a salt and such an 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, if desired.

Description: The invention relates to novel compositions which are suitable for use as catalysts in the preparation of polymers of carbon monoxide with one or more olefinically unsaturated organic compounds. High molecular weight linear polymers of carbon monoxide with one or more olefinically unsaturated organic compounds (for the sake of brevity referred to as A) in which the monomer units occur in an alternating order and which therefore consist of units of the general formula -(CO)-A'- wherein A′ represents a monomer unit from a monomer A used, can be prepared by using catalyst compositions based 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 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 which contains at least two carbon atoms in the bridge. An investigation carried out by the Applicant into these catalyst compositions has shown that when the acid mentioned as component b) is replaced by a non-noble transition metal or copper salt of the relevant acid, catalyst compositions are obtained which possess an attractive activity for the polymerization of carbon monoxide with one or more olefinically unsaturated organic compounds, which activity is in some cases even considerably better than that of the corresponding catalyst compositions based on the acid. Even partial replacement of the acid by the salt will in these cases result in a gain in activity. The investigation has further revealed that the activity of the catalyst compositions based on a salt or a mixture of a salt and an acid as component b) can in some cases be much improved by incorporating a quinone into these compositions. Catalyst compositions based on the components a) and c) and one of the salts mentioned hereinbefore as component b) are novel. Catalyst compositions based on the components a) and c) and a mixture of a salt and an acid as component b) are also novel as well as catalyst compositions based on the components a) and c), a salt or a mixture of a salt and an acid as component b) and in addition a quinone as component d). The novel catalyst compositions were used to prepare, inter alia: 1) copolymers of carbon monoxide with octene-1, and 2) terpolymers of carbon monoxide with ethene and with dodecene-1. The present patent application therefore relates to novel catalyst compositions based on a) a palladium compound, b) a non-noble transition metal or copper salt of an acid with a pKa of less than 2, provided that the acid is not a hydrohalogenic acid, or a mixture of such a salt and 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 containing at least two carbon atoms in the bridge, and d) optionally a quinone. The patent application further relates to the application of these catalyst compositions in the preparation of polymers of carbon monoxide with one or more olefinically unsaturated organic compounds 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 (determined 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 trifluoroacetic acid. Preference is given to para-toluene-sulphonic acid and trifluoroacetic acid. The salt of the non-noble transition metal is preferably applied in a quantity of from 0.5 to 200 and in particular 1.0 to 100, equivalents per gram atom of palladium. If an acid is used in addition to a salt, preference is given to compositions in which the ratio between the number of equivalents of salt and the number of equivalents of acid is higher than 1. In the present patent application non-noble transition metals should be taken to be all the transition metals including the actinides and lanthanides, but with the exclusion of the noble metals ruthenium, osmium, rhodium, iridium, palladium, platinum, silver and gold. Examples of transition metals whose salts are very suitable for use as component b) in the catalyst compositions according to the invention are the Group 4B metals titanium, zirconium and hafnium, the Group 5B metals vanadium, niobium and tantalum, the Group 6B metals chromium, molybdenum and tungsten, the Group 7B metal manganese, the Group 8 metals iron, cobalt and nickel, the Group 1B metal copper,the Group 2B metal zinc, the lanthanides cerium, lanthanum, praseodymium samarium, dysprosium, erbium and lutecium and the actinides actinium, thorium and uranium. Special preference is given to the use of salts of the following transition metals: the Group 4B metal zirconium, the Group 5B metal vanadium, the Group 6B metal chromium, the Group 8 metals iron and nickel, the Group 1B metal copper, the lanthanide cerium and the actinides thorium and uranium. In the bidentate ligand, M is preferably phosphorus. The groups R¹, R², R³ and R⁴ present in the bidentate ligand preferably contain 6 to 14 carbon atoms. Special preference is given to bidentate ligands in which the groups R¹, R², R³ and R⁴ are phenyl groups or alkyl-substituted phenyl groups. The bivalent organic bridging group R preferably 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, and 1,3-bis(diphenylphosphino)propane. Preferably the latter bidentate ligand is used. The bidentate ligand is preferably applied in a quantity of 0.5-5 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 unsubstituted benzoquinones, other quinones, such as substituted or unsubstituted naphthaquinones and anthraquinones, are also eligible. Preference is given to benzoquinones and to 1,4-benzoquinones in particular. Examples of suitable compounds 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-benzoquinone, mono-methyl-1,4-benzoquinone, 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 compounds that can be polymerized with carbon monoxide with the aid of the catalyst compositions according to the invention are both compounds which consist exclusively of carbon and hydrogen and compounds 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 carbon monoxide with one or more olefinically unsaturated hydrocarbons. Examples of suitable hydrocarbon monomers are ethene and other α-olefins, such as propene, butene-1, hexene-1 and octene-1 as well as styrene and alkyl-substituted styrenes, such as p-methyl styrene and p-ethyl styrene. 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. The 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 and 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 compounds relative to carbon monoxide preferably is 10:1-1:5 and in particular 5:1-1:2. The carbon monoxide used in the preparation of the polymers according to the invention need not be pure. It may contain contaminations, such as hydrogen, carbon dioxide and nitrogen. The invention will now be illustrated with the aid of the following examples. EXAMPLE 1 ["This experiment is beyond the scope of claim 1"] A carbon monoxide/ethene copolymer was prepared as follows. A magnetically stirred autoclave of 250 ml capacity was charged with a catalyst solution consisting of: 50 ml of methanol, 0.1 mmol of palladium acetate, 0.15 mmol 1,3-bis(diphenylphosphino)propane, and 2 mmol p-toluenesulphonic acid. Carbon monoxide was introduced into the autoclave until a pressure of 30 bar was reached and then ethene until a pressure of 60 bar was reached. Finally, the autoclave was heated to 50 °C. After two hours the polymerization was terminated by cooling down to room temperature and then releasing the pressure. The polymer was filtered off, washed with methanol and dried in vacuo at room temperature. The yield was 10 g of copolymer, so the polymerization rate was 500 g of copolymer/g of palladium/hour. EXAMPLE 2 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that: a) the catalyst solution contained 2 mmol of copper para-tosylate instead of 2 mmol of para-toluenesulphonic acid and b) the reaction time was 1.5 hour. The yield was 15 g of copolymer, so the polymerization rate was 1000 g of copolymer/g of palladium/hour. EXAMPLE 3 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 2, the differences being that a) the catalyst solution in addition contained 10 mmol of 1,4-benzoquinone and b) the reaction time was ¾ hour. The yield was 15 g of copolymer, so the polymerization rate was 2000 g of copolymer/g of palladium/hour. EXAMPLE 4 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 3, the differences being that a) the reaction temperature was 20 °C and b) the reaction time was 1 hour. The yield was 5 g of copolymer, so the polymerization rate was 500 g of copolymer/g of palladium/hour. EXAMPLE 5 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 2 mmol of copper perchlorate instead of 2 mmol of p-toluenesulphonic acid and b) the reaction time 1.5 hour. The yield was 12 g of copolymer, so the polymerization rate was 800 g of copolymer/g of palladium/hour. EXAMPLE 6 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 2 mmol of nickel perchlorate instead of 2 mmol p-toluenesulphonic acid, b) the reaction temperature was 55 °C and c) the reaction time was 1 hour. The yield was 13 g of copolymer, so the polymerization rate was 1300 g of copolymer/g of palladium/hour. EXAMPLE 7 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 0.5 mmol of chromium sulphate instead of 2 mmol of p-toluenesulphonic acid, b) the reaction temperature was 55 °C and c) the reaction time was 1 hour. The yield was 10.5 g of copolymer, so the polymerization rate was 1050 g of copolymer/g of palladium/hour. EXAMPLE 8 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 0.5 mmol of iron perchlorate instead of 2 mmol of p-toluenesulphonic acid, b) the reaction temperature was 55 °C and c) the reaction time was 1.5 hour. The yield was 13.5 g of copolymer, so the polymerization rate was 900 g of copolymer/g of palladium/hour. EXAMPLE 9 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 0.5 mmol of vanadyl sulphate instead of 2 mmol of p-toluenesulphonic acid, and b) the reaction temperature was 70 °C. The yield was 14 g of copolymer, so the polymerization rate was 700 g of copolymer/g of palladium/hour. EXAMPLE 10 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 9, except that now the catalyst solution in addition contained 2 mmol of tetramethyl-1,4-benzoquinone. The yield was 17 g of copolymer, so the polymerization rate was 850 g of copolymer/g of palladium/hour. EXAMPLE 11 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 0.5 mmol of zirconium sulphate instead of 2 mmol of p-toluenesulphonic acid and b) the reaction time was 2.5 hours. The yield was 20 g of copolymer, so the polymerization rate was 800 g of copolymer/g of palladium/hour. EXAMPLE 12 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 0.5 mmol of uranyl sulphate instead of 2 mmol of p-toluenesulphonic acid, b) the reaction temperature was 80 °C and c) the reaction time was 2.5 hours. The yield was 20 g of copolymer, so the polymerization rate was 800 g of copolymer/g of palladium/hour. EXAMPLE 13 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 12, the differences being that a) the catalyst solution in addition contained 2 mmol of 1,4-benzoquinone, b) the reaction temperature was 70 °C and c) the reaction time was 2 hours. The yield was 20 g of copolymer, so the polymerization rate was 1000 g of copolymer/g of palladium/hour. EXAMPLE 14 A carbon monoxide/ethene copolymer was prepared in substantially the same manner as the copolymer in Example 1, the differences being that a) the catalyst solution contained 0.5 mmol of cerium sulphate instead of 2 mmol of p-toluenesulphonic acid and b) the reaction time was 2.5 hours. The yield was 20 g of copolymer, so the polymerization rate was 800 g of copolymer/g of palladium/hour. EXAMPLE 15 A carbon monoxide/propene copolymer was prepared as follows. A magnetically stirred autoclave of 250 ml capacity was charged with a catalyst solution consisting of: 50 ml of methanol, 0.1 mmol of palladium acetate, 0.15 mmol of 1,3-bis(diphenylphosphino)propane and 2 mmol of copper para-tosylate. 30 ml of liquid propene was introduced into the autoclave, followed by carbon monoxide until a pressure of 40 bar was reached. Finally, the contents of the autoclave were brought to 85 °C. After 5 hours the polymerization was terminated and the polymer isolated as indicated in Example 1, except that now the contents of the reactor were cooled down to -20 °C before being filtered off. The yield was 15 g of copolymer, so the polymerization rate was 300 g of copolymer/g of palladium/hour. EXAMPLE 16 A carbon monoxide/octene-1 copolymer was prepared in substantially the same manner as the copolymer in Example 15, the differences being that a) 20 ml of octene-1 was introduced into the autoclave instead of 30 ml of propene, and b) the reaction temperature was 90 °C. The yield was 6 g of copolymer, so the polymerization rate was 120 g of copolymer/g of palladium/hour. EXAMPLE 17 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 monoxide/ethene mixture was introduced until a pressure of 55 bar was reached. Then the autoclave was charged with a catalyst solution consisting of: 6 ml of methanol, 0.01 mmol of palladium acetate, 0.012 mmol of 1,3-bis(diphenylphosphino)propane, 0.02 mmol of copper para-tosylate and 0.1 mmol of 1,4-benzoquinone. Introduction of a 1:1 carbon monoxide/ethene mixture kept the pressure at 55 bar. After 1 hour the polymerization was terminated by releasing the pressure. The polymer was filtered off, washed with methanol and dried at 70 °C. The yield was 5.7 g of terpolymer, so the polymerization rate was 5700 g of terpolymer/g of palladium/hour. EXAMPLE 18 A carbon monoxide/ethene/octene-1 terpolymer was prepared in substantially the same manner as the terpolymer in Example 17, the differences being that a) instead of 140 ml of methanol, 180 ml of the same compound was used, b) instead of 86 ml of propene, 78 ml of octene-1 was used, c) the quantity of catalyst solution was trebled, and d) the reaction time was 5 hours. The yield was 30 g of terpolymer, so the polymerization rate was 2000 g of terpolymer/g of palladium/hour. EXAMPLE 19 A carbon monoxide/ethene/dodecene-1 terpolymer was prepared in substantially the same manner as the terpolymer in Example 18, the differences being that a) instead of 78 ml of octene-1, 78 ml of dodecene-1 was used, and b) the reaction time was 3 hours. The yield was 20 g of terpolymer, so the polymerization rate was 2200 g of terpolymer/g of palladium/hour. EXAMPLE 20 A carbon monoxide/ethene/styrene terpolymer was prepared in substantially the same manner as the terpolymer in Example 18, the differences being that a) instead of 180 ml of methanol, 140 ml of the same compound was used, b) instead of 78 ml of octene-1, 63 ml of styrene was used, and c) the reaction time was 6 hours. The yield was 22 g of terpolymer, so the polymerization rate was 1200 g of terpolymer/g of palladium/hour. Of the polymers prepared according to Examples 1-20, the copolymers prepared according to Examples 2-16 and the terpolymers prepared according to Examples 17-20 are polymers according to the invention. In the preparation of these polymers use was made of catalyst compositions according to the invention containing a salt of a non-noble transition metal, or a copper salt. The catalyst compositions according to the invention used in the Examples 3, 4, 10, 13 and 17-20 in addition contained a quinone as the fourth component. The copolymer prepared according to Example 1 falls outside the scope of the invention and has been included in the patent application for comparison. The favourable effect which the replacement of an acid in the catalyst compositions by a non-noble transition metal or copper salt of the acid has on the polymerization rate becomes evident upon comparison of the results of Examples 1 and 2. The favourable effect which the incorporation into the catalyst compositions according to the invention of a quinone as the fourth component has on the polymerization rate becomes evident upon comparison of the results of Examples 2, 9 and 12 with those of the Examples 3, 10 and 13, respectively. All of the copolymers prepared according to Examples 1-14 had melting points of 257 °C. The terpolymers prepared according to Examples 17-20 had melting points of 183, 220, 235 and 225 °C, respectively. With the aid of ¹³C-NMR analysis it was established that the carbon monoxide/ethene copolymers prepared according to Examples 1-14, the carbon monoxide/propene copolymer prepared according to Example 15 and the carbon monoxide/octene-1 copolymer prepared according to Example 16 had a linear alternating structure and therefore consisted of units of the formulae -CO-(C₂H₄)-, -CO-(C₃H₆)- and -CO-(C₈H₁₆)-, respectively. It was also established by ¹³C-NMR analysis that the carbon monoxide/ethene/propene terpolymer, the carbon monoxide/ethene/octene-1 terpolymer, the carbon monoxide/ethene/dodecene-1 terpolymer and the carbon monoxide/ethene/styrene terpolymer prepared according to the Examples 17, 18, 19 and 20, respectively, had a linear structure and consisted of units of the formula -CO-(C₂H₄)- with in addition units of the formulae -CO-(C₃H₆)-, -CO-(C₈H₁₆)-, -CO-(C₁₂H₂₄)- and -CO-(C₈H₉)-, respectively, which units occurred randomly distributed within the terpolymers. The data produced by ¹³C-NMR analysis showed that the terpolymers were composed as follows. In the terpolymer prepared according to Example 17 there were 21 units based on propene to 79 units based on ethene, which amounts to a propene content in the terpolymer of 12.4 %w. In the terpolymer prepared according to Example 18 there were 75 units based on octene-1 to 925 units based on ethene, which amounts to an octene-1 content in the terpolymer of 12.6 %w. In the terpolymer prepared according to Example 19 there were 42 units based on dodecene-1 to 958 units based on ethene, which amounts to a dodecene-1 content in the terpolymer of 11 %w. In the terpolymer prepared according to Example 20 there were 33 units based on styrene to 967 units based on ethene, which amounts to a styrene content in the terpolymer of 5.7 %w.

Claims: Novel catalyst compositions, characterized in that they are based upon a) a palladium compound, b) a non-noble transition metal or copper salt of an acid with a pKa of less than 2, provided that the acid is not a hydrohalogenic acid, or a mixture of such a salt and such an 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, if desired. Catalyst compositions as claimed in claim 1, characterized in that they are based upon a palladium salt of a carboxylic acid, such as palladium acetate, as the component a). Catalyst compositions as claimed in claim 1 or 2, characterized in that they are based upon a salt of a sulphonic acid, such as a p-toluenesulphonic acid, or a salt of a carboxylic acid, such as trifluoroacetic acid, or a mixture of such a salt and such an acid as the component b). Catalyst compositions as claimed in one or more of claims 1-3, characterized in that the non-noble transition metal is chosen from the group formed by zirconium, vanadium, chromium, iron, nickel, cerium, thorium and uranium. Catalyst compositions as claimed in one or more of claims 1-4, characterized in that a component c) is used wherein M is phosphorus and wherein the groups R¹, R², R³ and R⁴ contain 6 to 14 carbon atoms, and wherein the bivalent organic bridging group R has three carbon atoms in the bridge. Catalyst compositions as claimed in one or more of claims 1-5, characterized in that the component d) used is a 1,4-quinone, preferably 1,4-benzoquinone. 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 any one of claims 1 to 6.

Inventors: DRENT, EIT, VAN BROEKHOVEN, JOHANNES ADRIANUS MARIA
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1987
Main classification: C08G67
IPC codes: C08G67, B01J31