Polyketone polymers

Abstract: Polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons bearing an alkylketo group at one end and a vinylketo group at the other end of their molecules, are prepared by carrying out the polymerization in the presence of a palladium based catalyst composition, dissolved in a diluent comprising one or more polar aprotic compounds.

Description: The invention relates to novel polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons, often referred to as polyketones. Linear polymers of carbon monoxide with one or more alpha-olefins (for the sake of brevity referred to as A) in which the monomer units occur alternately and which therefore consist of units of the general formula -(CO)-A'- in which A' represents a monomer unit derived from a monomer A used, can be prepared by using catalyst compositions on the basis of a) a palladium compound, b) an anion of an acid with a pKa of less than 4, and c) a phosphorus bidentate ligand of the general formula R₁R₂P-R-PR₃R₄, wherein R₁, R₂, R₃ and R₄ represent the same or different hydrocarbyl groups and R represents a bivalent organic bridging group containing at least two carbon atoms in the bridge. According to EP-A-222454, the preparation of the polymers by using the above-described catalyst compositions may be carried out by contacting the monomers at an elevated temperature and presure with a solution of the catalyst composition in a protic polar diluent in which the polymers are insoluble or virtually insoluble. The use of ketone and ethylene glycol diacetate containing diluents in the preparation of the polymers is the subject matter of the earlier non-prepublished patent applications EP-A-253416 and EP-A-301664. During the polymerization, the polymers are obtained in the form of a suspension in the diluent. After the desired degree of polymerization is reached, the polymerization is generally terminated by cooling and releasing the pressure. The polymers can be isolated from the suspension for instance by means of filtration or centrifugation. Lower aliphatic alcohols, such as methanol, have been found to be very suitable protic polar diluents. The type of diluent used has an effect on the terminal groups occurring in the polymers. Thus, when carbon monoxide is polymerized with ethene in methanol as the diluent, using the above-mentioned catalyst compositions, the resulting polymers are substantially of formula CH₃-CH₂-CO-(CH₂CH₂-CO-) n -CH₂-CH₂-CO-OCH₃, i.e. they are mainly polymers whose molecules bear an alkyl keto group at one end and an alkyl ester group at the other end. With a view to the possible uses of the polymers, it is desirable that either one of the terminal groups in at least part of the polymer molecules should contain an olefinically unsaturated double bond, so that the polymers can be suitably used as a component in radical polymerization processes with olefinically unsaturated monomers or with olefinically unsaturated polymers. The Applicant has carried out an investigation into the preparation of such polymers. Conversion of the alkyl ester groups which occur in the polymers as terminal groups into hydroxyl groups by means of catalytic hydrogenation followed by catalytic dehydration is not a suitable route to the introduction of an olefinically unsaturated double bond into either one of the terminal groups of the polymer molecules. Owing to various side reactions - for instance with the carbonyl groups present in the polymer chain - a polymer mixture will be formed in which much of the linearity of the polymers is lost, while the introduction of an olefinically unsaturated double bond into either of the two terminal groups of the polymer molecules remains minimal. Surprisingly, it has now been found that the above-mentioned palladium/phosphorus bidentate ligand catalyst compositions can be used to prepare polymers which are closely related to the carbon monoxide/alpha-olefin polymers mentioned hereinbefore but in which at least part of the polymer molecules contain an olefinically unsaturated double bond in either one of the terminal groups, namely when the polymerization is carried out in a diluent consisting for more than 50 %v of one or more aprotic polar compounds which are neither ketones nor ethylene glycol diacetate. Thus, the polymerization of carbon monoxide with ethene in dimethyl sulphoxide as the diluent and using catalyst compositions as mentioned hereinbefore will lead mainly to polymers which can be represented by the formula CH₃-CH₂-CO-(CH₂CH₂-CO-) n -CH₂-CH₂-CO-CH=CH₂, i.e. mainly polymers whose molecules bear an alkyl keto group at one end and a vinyl keto group at the other end. Recapitulating, the polymers to which the present invention relates may be defined as follows a) they have been prepared by polymerization of carbon monoxide with one or more alpha-olefins (A), b) they have a linear structure, c) they are made up of units of the formula -(C)-A'- wherein A' represents a monomer unit derived from a monomer A used, and d) more than 25% of the polymer molecules contain an olefinically unsaturated double bond in either of the two terminal groups. Polymers that satisfy the criteria a)-d) are novel polymers. The present patent application therefore relates to novel polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons, which polymers satisfy the criteria a)-d) mentioned hereinbefore. The patent application further relates to the preparation of these polymers. Preferably, more than 40% of the polymer molecules, of the polymers of the invention contain an olefinically unsaturated double bond in either of the two terminal groups. The alpha-olefins used in the preparation of the polymers of the invention preferably contain at most 10 carbon atoms in the molecule. Exemplary alpha-olefins which can be suitably used in the preparation of the polymers of the invention are ethene, propene and butene-1. Preferably, the polymers are prepared from a monomer mixture which, in addition of carbon monoxide, includes only one alpha-olefin, ethene in particular. For the preparation of the polymers of the invention it is preferred to use the palladium/phosphorus bidentate catalyst compositions mentioned hereinbefore. The palladium compound used in these catalyst compostions as component a) is preferably a palladium salt of a carboxylic acid and in particular palladium acetate. As examples of acids with a pKa of less than 4 (determined in aqueous solution at 18°C) whose anions should be present in the catalyst compositions as components b) may be mentioned, for instance, mineral acids such as perchloric acid, sulphuric acid, phosphoric acid and nitrous acid, sulphonic acids such as 2-hydroxypropane-2-sulphonic acid, para-toluenesulphonic acid, methanesulphonic acid and trifluoromethanesulphonic acid, and carboxylic acids such as trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, difluoroacetic acid, tartaric acid and 2,5-dihydroxybenzoic acid. As component b), the catalyst composition preferably contains an anion of an acid with a pKa of less than 2 and in particular an anion of a sulphonic acid, such as para-toluenesulphonic acid, or an anion of a carboxylic acid such as trifluoro acetic acid. Preferably, component b) is present in the catalyst compositions in a ratio of from 0.5 to 200 and in particular of from 1.0 to 100 equivalents per gram atom of palladium. Component b) may be incorporated in the catalyst compositions both in the form of an acid and in the form of a salt. Eligible salts include non-noble transition metal salts. When a salt of a non-noble transition metal is used as component b), preference is given to a copper salt, especially a cupric salt. Optionally, components a) and b) may be combined in a single compound. An example of such a compound is palladium para-tosylate. In the phosphorus bidentate ligands of the general formula R₁R₂P-R-PR₃R₄ which can be used in the catalyst compositions as components c), the hydrocarbon groups R₁, R₂, R₃ and R₄ preferably represent aryl groups. Further preference is given to phosphorus bidentate ligands in which the groups R₁, R₂, R₃ and R₄ are the same. Preferably the bridging groups R contains 3 atoms in the bridge, at least two of which are carbon atoms. Examples of suitable bridging groups R are the -CH₂-CH₂-CH₂- group, the -CH₂-C(CH₃)₂-CH₂- group, the -CH₂-Si(CH₃)₂-CH₂- group and the -CH₂-C(R₅)(R₆)-CH₂- group in which R₅ represents a methyl group and R₆ a diphenyl-phosphino-methyl group. A very suitable phosphorus bidentate ligand is 1,3-bis(diphenyl-phosphino) propane. The phosphorus bidentate ligands are preferably used in the catalyst compositions in a ratio of 0.1-3 and in particular of 0.75-2 mol per mol of palladium compound. The preparation of the polymers of the invention by using the palladium/phosphorus bidentate ligand catalyst compositions described hereinbefore should be carried out in a diluent which consists for more than 50 %v of one or more aprotic polar compounds which are neither ketones nor ethylene glycol diacetate. Preferably, the diluent used consists for more than 75 %v of one or more aprotic polar compounds. Examples of suitable aprotic polar diluents are dimethylsulphoxide, N-methylpyrrolidone, N,N-dimethylacetamide and acetonitriles. Preferred aprotic polar diluents are dimethylsulphoxide and N-methylpyrrolidone. In addition to one or more aprotic polar compounds, the diluent used may also contain one or more other compounds. Examples of such compounds are alcohols, such as isopropanol, and ketones, such as acetone. The amounts of palladium/phosphorus bidentate ligand catalyst composition used in the preparation of the polymers of the invention may vary within wide ranges. Per mol of olefinically unsaturated compound to be polymerized, such a quantity of catalyst is preferably used as to contain from 10⁻⁷ to 10⁻³ and in particular from 10⁻⁶ to 10⁻⁴ gram atom of palladium. The molar ratio of the olefinically unsaturated compounds relative to carbon monoxide is preferably 10:1-1:5 and in particular 5:1-1:2. The preparation of the polymers of the invention by using a palladium/phosphorus bidentate ligand catalyst is preferably 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. The carbon monoxide used in the polymer preparation of the invention need not be pure. It may contain such contaminants as hydrogen, carbon dioxide and nitrogen. The polymerization may be carried out either batch wise or continuously. The invention is now illustrated with the aid of the following examples. Example 1 A carbon monoxide/ethene copolymer was prepared as follows. A stirred autoclave of 250 ml content was charged with a catalyst solution comprising 50 ml of dimethyl sulphoxide, 0.1 mmol of palladium acetate, 2 mmol trifluoroacetic acid, and 0.15 mmol of 1,3-bis(diphenyl-phosphino) propane. After air present in the autoclave was removed by evacuation, compressed ethene was let in until a pressure of 20 bar was reached, followed by carbon monoxide until a pressure of 50 bar was reached. Next, the contents of the autoclave were brought to 80°C. After 5 hours the polymerization was terminated by cooling to room temperature and releasing the pressure. The copolymer formed was filtered off, washed with methanol and dried in vacuo at room temperature. The polymerization rate was 160 g copolymer/g Pd.hour. Example 2 A carbon monoxide/ethene copolymer was prepared substantially in the same way as the copolymer of Example 1, except for the following differences a) the catalyst solution comprised a mixture of 50 ml of N-methyl-pyrrolidone and 5 ml of isopropyl alcohol instead of 50 ml of dimethyl sulphoxide, and b) the reaction time was 3 hours instead of 5 hours. The polymerization rate was 460 g copolymer/g Pd.hour. Example 3 A carbon monoxide/ethene copolymer was prepared substantially in the same way as the copolymer of Example 1, except that the catalyst solution used included 50 ml of N-methyl-pyrrolidone instead of 50 ml of dimethylsulphoxide. The polymerization rate was 360 g copolymer/g Pd.hour. Example 4 A carbon monoxide/ethene copolymer was prepared substantially in the same way as the copolymer of Example 1, except for the following differences a) the catalyst solution comprised a mixture of 50 ml of N-methyl-pyrrolidone and 10 ml of acetone instead of 50 ml of dimethyl-sulphoxide, and b) the reaction time was 1 hour instead of 5 hours. The polymerization rate was 740 g copolymer/g Pd.hour. Example 5 A carbon monoxide/ethene copolymer was prepared substantially in the same way as the copolymer of Example 1, except for the following differences a) the catalyst solution comprised a mixture of 50 ml of N-methyl-pyrrolidone and 5 ml of isopropanol instead of 50 ml of dimethyl-sulphoxide, and 0.5 mmol of para-toluenesulphonic acid instead of 2 mmol of trifluoroacetic acid, and b) the reaction time was 2 1/2 hours instead of 5 hours. The polymerization rate was 300 g copolymer/g Pd.hour. With the aid of ¹³C-NMR analysis it was established that the carbon monoxide/ethene copolymers prepared in Examples 1-5 had a linear structure and were made up of units of the formula -(CO)-(C₂H₄)-. With the aid of ¹³C-NMR analysis it was further established that on average 70, 90, 100, 90, and 50%, respectively, of the polymer molecules of the polymers prepared according to Examples 1-5 contained an olefinically unsaturated double bond in either of the two terminal groups.

Claims: Novel polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons, that a) have been prepared by polymerization of carbon monoxide with one or more alpha-olefins (A), b) have a linear structure, and c) are made up of units of the formula -(CO)-A'- in which A' represents a monomer unit derived from a monomer A used, characterized in that d) more than 25% of the polymer molecules contain an olefinically unsaturated double bond in either of the two terminal groups. Polymers as claimed in claim 1, characterized in that more than 40% of the polymer molecules contain an olefinically unsaturated double bond in either of the two terminal groups. Process for the preparation of polymers as defined in claim 1, in which a mixture of carbon monoxide with one or more alpha-olefins is polymerized by contacting the mixture with a catalyst composition on the basis of a) a palladium compound, b) an anion of an acid with a pKa of less than 4, and c) a phosphorus bidentate ligand of the general formula R₁R₂P-R-PR₃R₄ wherein R₁, R₂, R₃ and R₄ represent the same or different hydrocarbyl groups and R represents a bivalent organic bridging group containing at least two carbon atoms in the bridge, characterized in that the catalyst composition is dissolved in a diluent which consists for more than 50 %v of one or more aprotic polar compounds which are neither ketones nor ethylene glycol diacetate. Process as claimed in claim 3, characterized in that a catalyst composition is applied which is based on a palladium salt of a carboxylic acid such as palladium acetate, as component a), and an anion of an acid with a pKa of less than 2 as component b). Process as claimed in claim 3 or 4, characterized in that a catalyst composition is applied which is based on an anion of a sulphonic acid, such as para-toluenesulphonic acid, or of a carboxylic acid, such as trifluoroacetic acid, as component b), and in that component b) is present in the catalyst composition in a ratio of from 1.0 to 100 equivalents per gram atom of palladium. Process as claimed in one or more of claims 3-5, characterized in that a catalyst composition is used in which the groups R₁, R₂, R₃ and R₄ present in component c) represent the same aryl group, and in that component c) is present in the catalyst composition in a ratio of 0.75-2 mol per mol of palladium compound. Process as claimed in one or more of claims 3-6, characterized in that a catalyst composition is used in which the bivalent bridging group R present in component c) contains three atoms in the bridge at least two of which are carbon atoms, such as the -CH₂-CH₂-CH₂- group in 1,3-bis(diphenyl-phosphino) propane. Process as claimed in one or more of claims 3-7, characterized in that the diluent used consists for more than 75 %v of one or more aprotic polar compounds, such as dimethyl-sulphoxide or N-methylpyrrolidone. Process as claimed in one or more of claims 3-8, characterized in that it is carried out at a temperature of 30-150°C, a pressure of 20-100 bar and a molar ratio of the olefinically unsaturated compounds relative to carbon monoxide in the mixture to be polymerized of 5:1-1:2, and in that per mol of olefinically unsaturated compound to be polymerized such a quantity of catalyst is used as to contain 10⁻⁶-10⁻⁴ gram atom of palladium.

Inventors: DRENT EIT, DRENT, EIT
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1988
Main classification: C08G67
IPC codes: C08G67, C08L73