Process for the preparation of copolymers of carbon monoxide with one or more olefinically unsaturated compounds

Abstract: Process for the preparation of copolymers of carbon monoxide with one or more olefinically unsaturated compounds, by copolymerising the monomers in the presence of a catalyst composition containing a Group-VIII metal and washing the formed copolymer by contacting the copolymer with a liquid which contains, dissolved in a solvent, a mono-, di- or tricarboxylic acid having up to 8 carbon atoms, or a zinc, aluminium or magnesium salt thereof.

Description: This invention relates to a process for the preparation of copolymers of carbon monoxide with one or more olefinically unsaturated compounds, by copolymerising the monomers in the presence of a catalyst composition containing a Group-VIII metal. The relevant copolymers are linear polymers and they are characterised by having a repeating structure [A-CO] which implies that a unit A is positioned left and right in between carbonyl units. A is a unit derived from the olefinically unsaturated compound. The term "copolymer" includes terpolymers in which different units A are present. Examples of suitable olefinically unsaturated compounds yielding a unit A are ethene, propene, butene, octene, styrene and acrylate esters. The copolymers mentioned above are known per se, cf. US-A-3,694,412, EP-A-121965, EP-A-181014, EP-A-229408 and EP-A-251373. Whilst these copolymers have attractive physical and mechanical properties such as yield stress, tensile strength, impact strength and flexural modulus, in some instances their processing properties may leave room for improvement. Copolymers with a high intrinsic viscosity, or limiting viscosity number (LVN), have better physical properties as engineering thermoplastic than copolymers with a lower intrinsic viscosity. Melt processing, e.g. extrusion, of copolymers, especially when they have an LVN of above 2.0 dl/g (measured at 60 °C in m-cresol), is adversely affected by a poor melt stability which is apparent from a notable increase of the viscosity of the melt during processing. In particular in fibre and sheet applications, melt-extrusion is a critical step, even for copolymers with a low LVN. It is evident that this problem of the instability of the copolymer melt needs to be solved. It is pointed out in the applicant's EP-A-228733, that the processability of the copolymers is unfavourably influenced by the presence of impurities in the copolymers as obtained from the copolymerisation reactor. Examples of such impurities are catalyst residues, copolymers with a relatively low molecular weight, i.e. oligomers, and trace impurities originating from the monomer feedstock and/or from the solvents used. Therefore, there is a need for a suitable work-up procedure by which said impurities may be removed from the polymer. EP-A-203092 disclosed a process for the removal of palladium catalyst remnants from the copolymers which comprises contacting the copolymers with a complexing agent for palladium, for example sodium acetate. A process for the preparation of copolymers of carbon monoxide with one or more olefinically unsaturated compounds, by copolymerising the monomers in the presence of a catalyst composition containing a Group VIII metal and washing the formed copolymer by contacting the copolymer with a liquid, wherein the washing is carried out in the absence of oxygen, is known from EP-A-228733. It has been shown that this procedure brings about a reduction in the content of impurities in the copolymer. It now appears desirable, however, that the melt stability of the polymer obtained by this work-up procedure is improved even further, especially for melt processing operations in commercial production of moulded parts and extrusion at commercial scale of fibres and sheets. It has now surprisingly been found that, by washing the copolymers with a liquid which contains a dissolved carboxylate, e.g., a carboxylic acid, a copolymer is obtained which possesses a better stability at the melt processing temperature, than a reference copolymer. This reference copolymer is treated in the same way, with the exception that the addition of the carboxylate to the washing liquid is omitted. This difference in stability is judged from the rate of weight loss of the copolymers upon heating in nitrogen and from colour development upon melt processing by compression moulding. Washing the copolymerisation product with a liquid which contains a dissolved carboxylate is relatively simply implemented in a manufacturing process for the production of the copolymers. It may be advantageous to carry out said washing in the absence of oxygen. The present invention therefore relates to a process for the preparation of copolymers of carbon monoxide with one or more olefinically unsaturated compounds, by copolymerising the monomers in the presence of a catalyst composition containing a Group VIII metal and washing the formed copolymer by contacting the copolymer with a liquid which contains, dissolved in a solvent, a mono-, di- or tricarboxylic acid having up to 8 carbon atoms, or a zinc or magnesium salt thereof. Mono-, di- or tricarboxylic acids consisting of carbon, hydrogen and oxygen and having up to 8 carbon atoms, as well as their zinc or magnesium salts may be used in the process of the invention. Examples of such compounds are formic acid, acetic acid, citric acid, magnesium acetate and zinc citrate. Although the use of these salts may assist in avoiding a high acidity in the polymer, it may be more difficult to remove them completely from the polymer by additional washings. Therefore, it is preferred to apply a liquid which contains a mono-, di- or tricarboxylic acid. More preferably, the liquid contains a dicarboxylic acid, for example malonic acid, barbituric acid or phthalic acid. It is advantageous to choose an acid which decomposes into volatile products when heated at a temperature in the range of from 100 to 300 °C. Washing with a liquid which contains oxalic acid gives a very good result. The skilled reader will understand that the liquid applied in the process of the invention contains a minor amount, i.e. less than 50%, of the carboxylic acid or the corresponding zinc or magnesium salt and a major amount, i.e. more than 50%, of a solvent. Suitably, the concentration of the mono-, di- or tricarboxylic acid or the zinc or magnesium salt thereof in the liquid amounts to 0.1 to 200 g/l, more suitably, the concentration amounts to 1 to 50 g/l, and most suitably 5 to 20 g/l. An excellent result has been obtained with a concentration of 10 g/l. The skilled reader will appreciate that the washing procedure of the invention involves more steps than contacting the copolymer with the liquid of the invention. Suitably, the slurry, obtained by contacting the copolymer with the liquid, is agitated and thereafter subjected to a suitable solid/liquid separation technique, such as filtration or centrifugation, in order to recover the copolymer. A substantial amount of the carboxylic acid or the salt will be removed from the copolymer upon applying said separation technique. It may be advantageous to reduce the amount of the remnants further, for example, by repeating the washing step using a liquid which does not contain the carboxylic acid or the salt. It may, therefore, be preferred to apply a procedure in which the washing which comprises contacting the copolymer with the liquid is followed by at least one washing which comprises contacting the copolymer with the solvent. The solvent to be applied in the liquid of the invention conveniently fulfils certain conditions. For example, it may be essentially a non-solvent for the copolymer while being a solvent for the carboxylic acid or the corresponding zinc or magnesium salt, to the extent that a sufficient amount of the acid or the salt can be dissolved. Since there is a preference for applying carboxylic acids in the liquid, the solvent is preferably essentially organic, i.e., containing carbon and hydrogen and, optionally, nitrogen and/or oxygen. Liquid alcohols are excellent solvents for carboxylic acids and when they possess 5 carbon atoms or less they are easily removable from the copolymer by evaporation, thus facilitating the final drying of the copolymer. Thus, more preferably, the solvent comprises a liquid alcohol having up to 5 carbon atoms, and, particularly, 3 carbon atoms. Very good results have been achieved with methanol. The copolymerisation step in the process of the invention is effected by catalyst compositions comprising a Group VIII metal, i.e. a metal selected from Group VIII of the Periodic Table, from which group, typically, palladium or nickel are chosen. Suitably, the catalyst composition contains a palladium compound, a dentate ligand and an anion of an acid with a pKa of less than 6. Suitable dentate ligands are those containing at least two phosphorus, nitrogen or sulphur dentate groups by which the dentate ligand can form a complex with the Group-VIII metal. Although the dentate ligands may have more than two ligand groups, such as 1,8-bis[bis(2-methoxyphenyl)phosphino]-2,7-bis[bis(2-methoxyphenyl)phosphinomethyl]octane, it is preferred to apply a bidentate ligand, in particular a phosphorus bidentate ligand, e.g., 1,3-bis(diphenylphosphino)propane and 1,3-bis[bis(2-methoxyphenyl)phosphino]propane. Anions of acids with pKa lower than 6 provide active catalyst compositions, however, there is preference for applying the anion of an acid which has a pKa of less than 2. Suitably the anion of the acid is present in a quantity of 1-100 mol per gram atom of palladium and in particular 2-50 mol per gram atom of palladium. The phosphorus bidentate ligand is preferably used in a quantity of 0.5-2 mol per gram atom of palladium, and in particular in a quantity of 0.75-1.5 mol per gram atom of palladium. The quantity of catalyst composition employed in the copolymerisation step may vary within wide limits. The quantity of catalyst composition comprising a palladium compound, a phosphorus bidentate ligand and an anion of an acid with a pKa of less than 6, which is used per mol of olefinically unsaturated compound to be polymerised preferably contains 10⁻⁷-10⁻³ and in particular 10⁻⁶-10⁻⁴ gram atom of palladium. The copolymerisation step is preferably carried out at a temperature of 40-120 °C and a pressure of 20-150 bar and in particular at a temperature of 50-100 °C and a pressure of 30-100 bar. The molar ratio of the olefinically unsaturated compounds relative to carbon monoxide in the mixture to be polymerised preferably is in the range of from 10:1 to 1:5 and in particular of from 5:1 to 1:2. The copolymer prepared by the process of the invention is a linear alternating copolymer of carbon monoxide with one or more olefinically unsaturated compounds. Typically, it is a copolymer of carbon monoxide with ethylene or it is a copolymer of carbon monoxide with ethylene and another olefinically unsaturated compound, the latter copolymer having a melting point in the range of from 150 to 245 °C. The olefinically unsaturated compound may contain functional groups like carboxylic ester and carboxylic amide groups, but preferably the olefinically unsaturated compound is a hydrocarbon having less than 10 carbon atoms, for example, an α-olefin, like octene-1 or decene-1, an aromatic olefin, like styrene, or an internal olefin, like norbornadiene. Most preferably, the olefinically unsaturated hydrocarbon is propylene. Obviously, the melting point of the copolymer is dependent of the olefinically unsaturated compound which has been incorporated. If there are more olefinically unsaturated compounds, the melting point also depends of the ratio at which they have been incorporated. Although the copolymers of carbon monoxide with ethylene and another olefinically unsaturated compound suitably have a melting point in the range of from 150 to 245 °C, there is a preference for preparing copolymers which have a melting point in the range of from 210 to 240 °C. As stated herein before, the limiting viscosity number of the copolymer is important with respect to a number of physical properties. Preferably, copolymers are prepared having a limiting viscosity number in the range of from 0.5 to 4.0 dl/g, or, more preferably, in the range of from 1.0 to 2.5 dl/g. The copolymers of this invention are very suitable ingredients in copolymer compositions because, in comparison with other copolymers, they improve the stability of the compositions at the temperatures applied in melt processing the compositions into shaped articles. One or more of the other components of the compositions may, for example, be chosen from polymers, mineral fillers, reinforcing fibres, and flame retardants. The polymers may be, for example, polyolefin, polyacetal or thermoplastic polyester. The compositions may also contain one or more additives which improve, e.g., oxidative stability or UV stability. Such additional additives may, for example, be selected from the group formed by sterically hindered phenolic compounds, aromatic amines, hydroxybenzophenones, hydroxyphenylbenzotriazoles, aluminium hydroxide, acid amides of carboxylic acids, and copolymers of ethylene and acrylic acid or methacrylic acid. Some of these may be well-known, commercially available additives for polymers. Suitably the hindered phenolic compounds are selected from 2,5-dialkylphenols, from esters of a straight chain alcohol and a hydroxy,dialkylphenyl-substituted carboxylic acid, from 1,2-bis(acetyl)hydrazines in which the acetyl group carries a hydroxy,dialkylphenyl substituent, from N,N'-bis-(acetoxyalkyl)oxalamides in which the acetyl group carries a hydroxy,dialkylphenyl substituent, and from alpha-N,omega-N-bis-(acetyl)diamines in which the acetyl group carries a hydroxy,-dialkylphenyl substituent. Suitable aromatic amines are selected from the group formed by the diphenylamines, such as 4,4'-bisbenzyldiphenylamines or anilino-diphenylamines, and diaminonaphthalenes, such as N,N,N',N'-tetraalkylaminonaphthalenes. The copolymers and compositions made thereof have been processed into shaped articles such as fibres, films, laminates, tubes, piping and articles having an intricate shape by conventional processing techniques, such as melt spinning, extrusion, and co-extrusion, injection moulding and compression moulding. It appeared that the copolymers of the invention perform better than copolymers which have been prepared by a different process, and that the process of the invention renders certain types of copolymers processable which were otherwise not processable due to insufficient stability under the conditions of the particular processing method. The invention is now illustrated by the following example. EXAMPLE A powder sample (30 g) of a terpolymer comprising ethylene, propylene and carbon monoxide, having an LVN of 1.5 dl/g (measured in m-cresol at 60 °C) and a crystalline melting point of 220 °C, was suspended in 100 ml methanol in which oxalic acid was dissolved at a concentration of 10 g/l. After agitating the suspension for 10 minutes, the polymer was recovered by filtration. The procedure was subsequently repeated three times using the same methanol but without dissolved oxalic acid. The polymer was dried at reduced pressure (less than 20 kPa) using a nitrogen purge. A sample of the dried material was analysed by thermal gravimetric analysis which involves monitoring of the weight of the sample under carefully controlled conditions. Over a 30 minutes period, the average weight loss at 260 °C in nitrogen amounted to 1.3%/hour. Another sample of the dried polymer was compression moulded in a press between glass-reinforced poly-perfuoroethylene sheets, using a 1-mm spacer between the sheets, by pressing at 250 °C for 10 minutes. A colourless moulding was obtained. COMPARATIVE EXAMPLE Another sample of the same polymer as used in the Example was treated in exactly the same way as described above, except that the solution of oxalic acid in methanol was replaced by pure methanol. The average weight loss amounted to 2.1 %/hour. A yellowish moulding was obtained. From the Example and the Comparative Experiment it is apparent that the washing step which comprises contacting the polymer with methanol containing oxalic acid has had a beneficial influence on the polymer's stability as judged from the rate of weight loss at high temperature and development of colour upon compression moulding.

Claims: Process for the preparation of copolymers of carbon monoxide with one or more olefinically unsaturated compounds, characterised by copolymerising the monomers in the presence of a catalyst composition containing a Group-VIII metal and washing the formed copolymer by contacting the copolymer with a liquid, which contains, dissolved in a solvent, a mono-, di- or tricarboxylic acid having up to 8 carbon atoms, or a zinc or magnesium salt thereof. Process according to claim 1, characterised in that the liquid contains a mono-, di- or tricarboxylic acid. Process according to claim 2, characterised in that the liquid contains a dicarboxylic acid, such as oxalic acid. Process according to claim 2 or 3, characterised in that the carboxylic acid is an acid which decomposes into volatile products when heated at a temperature in the range of from 100 to 300 °C. Process according to claim 1, characterised in that the concentration of the mono-, di- or tricarboxylic acid or the zinc, aluminium or magnesium salt in the liquid amounts to 1 to 50 g/l. Process according to claim 5, characterised in that the concentration amounts to 5 to 20 g/l. Process according to any of claims 1-6, characterised in that the washing which comprises contacting the copolymer with the liquid is followed by at least one washing which comprises contacting the copolymer with the solvent. Process according to any of claims 1-7, characterised in that the solvent comprises an alcohol having up to 3 carbon atoms, such as methanol. Process according to any of claims 1-8, characterised in that the catalyst composition contains a palladium compound, a phosphorus bidentate ligand and an anion of an acid with a pKa of less than 6. Process as claimed in claim 9, characterised in that the dentate ligand is used in a quantity of 0.75-1.5 mol per gram atom of palladium, the anion of the acid is used in a quantity of 2-50 mol per gram atom of palladium, in that the quantity of catalyst composition used per mol of olefinically unsaturated compound to be polymerised contains 10⁻⁶-10⁻⁴ gram atom of palladium and in that the polymerisation is carried out at a temperature of 50-100 °C, at a pressure of 30-100 bar and at a molar ratio of the olefinically unsaturated compounds relative to carbon monoxide in the mixture to be polymerised in the range of from 5:1 to 1:2. Process according to any of claims 1-10, characterised in that a copolymer is prepared having a limiting viscosity number in the range of from 1.0 to 2.5 dl/g which copolymer is a copolymer of carbon monoxide with ethylene or a copolymer of carbon monoxide with ethylene and another olefinically unsaturated hydrocarbon having less than 10 carbon atoms, the latter copolymer having a melting point in the range of from 210 to 240 °C.

Inventors: RICHTERS PETER, ROSENBRAND GERRIT GERARDUS, SYRIER JOHANNES LEOPOLD MARIE, RICHTERS, PETER, ROSENBRAND, GERRIT GERARDUS, SYRIER, JOHANNES LEOPOLD MARIE
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1991
Main classification: C08G67
IPC codes: C08G67