The present invention is concerned with the removal of palladium from polyketones.

It is known from EP 121864 and many subsequent patent applications that polyketones, which are linear polymers comprised of alternating units of (1) -CO- and (2) one or more divalent units derived from one or more corresponding olefins, can be prepared by polymerising carbon monoxide with one or more olefins in an appropriate solvent in the presence of a catalyst prepared from a source of palladium, a diphosphine and a source of the conjugate base (anion) of certain acids having a pKa of less than 2. The process, which can be carried out either batchwise or continuously is typically effected at elevated temperature and pressure. A preferred solvent is a lower aliphatic alcohol such as methanol in which the polyketone is insoluble. The synthesis of polyketones using the above-mentioned or similar palladium catalysts suffers from the disadvantage that significant levels of palladium are incorporated into the polymer mass during its preparation. This is a two-fold problem because firstly palladium is an expensive metal and secondly the incorporated palladium tends to adversely affect the subsequent processability of the polyketone. It would be desirable therefore to identify a method of recovering the palladium from the polyketone particularly if it can be.recovered in a form in which it can be re-used without further treatment. Ideally such a method should also be easy to operate on a large scale and not add undue

complexity to the polymerisation process.

A number of ways of solving this problem have been published in the art. For example, EP 224304 shows that under conditions where

95% of the palladium used was retained in the polymer, treatment with carbon monoxide followed by a washing step reduced the residual level of palladium to 29%. Similarily in EE 227135, treatment with a phosphine reduced the residual level to 37%.

In EP 283092, treatment of an ethylene/carbon monoxide copolymer with triethylamine reduced catalyst levels from 81 to 42% whilst treatment of an ethylene/propylene/carbon monoxide with triphenylphosphine reduced levels from 67 to 20%. For the same polymer, sodium acetate reduced catalyst levels from 67 to 27%. Finally, EP 285218 teaches phosphine and amine terminating agents with the additional point that the temperature must be raised after the additional reagent is introduced, giving improvements in catalyst losses of eg- 67 to 5% and 86 to 6%.

All these approaches to solving the problem have disadvantages. Phosphines, amines and acetates are reagents which cannot be directly recycled to the polymerisation reactor because under certain circumstances they adversely affect the catalyst.

Carbon monoxide, on the other hand, is more easily vented from an olefin/CO mixture; consequently the complexity of the polymerisation process can be reduced if the carbon monoxide is removed in preference to the olefin or olefins. A method of treatment has now been found which gives good catalyst recovery.

According to the present invention there is provided a process for removing palladium from a contaminated polyketone containing palladium which comprises contacting the contaminated polyketone with an olefin in the substantial absence of carbon monoxide at a temperature above the temperature at which the polyketone was formed and in a solvent in which the contaminated polyketone is insoluble. The present invention solves the problem defined above by contacting the contaminated polyketone with an olefin e.g. ethylene in the substantial absence of carbon monoxide in a solvent, e.g.

methanol, in which it is insoluble at a temperature above the temperature at which the polyketone was prepared. This causes the palladium to be extracted out of the polyketone into the solvent. Thereafter the polyketone and the solvent containing the palladium can be separated by filtration or other techniques which will be readily apparent to one of ordinary skill.

It is preferred that the υ-- "-cess of the present invention is carried out in the presence of . ^~ . acid.

By the term polyketone is n-sant a linear polymer comprised of alternating units of (1) -CO- and (2) one or more divalent units derived from one or more corresponding olefins. Specifically, it is a linear polymer comprised of alternating -CO- and -X- units where X is for example -CH2CH2-, in the case where carbon monoxide and ethylene are copolymerised or a random arrangement of -CH2CH2- and -CH2CH(R)- (R = C _j to C _β alkyl, phenyl or methyl or ethyl substituted phenyl) in the case where a mixture of carbon monoxide, ethylene and an olefin of formula RCH = CH2 are terpolymerised. In the case of the latter class of material it is preferred that R is Ci to C alkyl especially methyl or ethyl. For the terpolymer polyketones it is preferred that at least 70 mole%, most preferably at least 80 mole %, of the X units are -CH ₂ CH ₂ -.

The olefin used to effect the extraction is suitably a C2 to C5 aliphatic olefin preferably ethylene, propylene or mixtures thereof. Especially preferred is the use of the olefin or olefins used in the synthesis of the polyketone.

Whilst it is desirable that the olefin used to effect extraction is as pure as possible, the presence of minor amounts (preferably less than 1 bar e.g. 0.1 bar) of other gases such as hydrogen and carbon monoxide can be tolerated.

The process of the present invention is preferably carried out in the presence of an acid.

Any acid can in principle be used in the process, where the polyketone has been prepared using a catalyst comprising palladium, a phosphine and an acid of the type described above or its conjugate

base (anion), it is preferable that the corresponding acid of those anions forming part of the catalyst composition (vide infra) is used. The acid should be present in amounts such that the molar ratio of acid to palladium in the contaminated polyketone is in the range 0.5:1 to 5000:1 preferably 1:1 to 1000:1.

The process of the present invention is suitably carried out by suspending the contaminated polyketone in a solvent in which it is insoluble preferably in the presence of the acid. Since the polyketone tends to be insoluble in most solvents a wide choice of materials is available. Particular preference however is given to the solvent in which the polyketone was prepared since on a commercial scale this greatly simplifies the manufacturing process. Typical examples of preferred solvents therefore are lower aliphatic alcohols and glycols and mixtures of alcohols eg tertiary alcohols with ketones. Most preferred examples of these solvents are C _j to Cg aliphatic primary alcohols eg methanol, ethanol and n-propanol and mixtures of G to Cg aliphatic tertiary alcohols, preferably t-butanol, with ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. When the solvent in which the polyketone is prepared is used for the process of the present invention, either fresh solvent preferably with added acid can be employed once the original batch of reaction medium has been removed or alternatively the original reaction medium, which may be acidic, can be used. This latter embodiment has the advantage of further simplicity and avoids having to recover palladium from a separate batch of solvent. To operate such an embodiment, the polyketone-containing reaction medium is merely contacted with the olefin after the original gaseous reactants have been removed by depressurisation and flushing. Alternatively, near the end of the polymerisation the carbon monoxide but not the olefin supply can be limited. By doing this, the continuing polymerisation of the reactants progressively reduces the amount of residual carbon monoxide present.

The process of the present invention is easily effected by contacting the polyketone-containing solvent with the olefin at a

superatmospheric pressure of up to 50 bars and a temperature in the range 10 to lδCC preferably 80 to 150 ^β C,more preferably 90-110 ^β C e.g. 100 ^β C. In particular the temperature at which the process of the invention is carried out should be higher (e.g. at least 20 ^β C higher) than the temperature at which the polyketone was formed. The extraction can be monitored by periodic withdrawal of a sample of the polyketone for analysis but typically an extraction time in the range 0.1 to 20 hours e.g. 0.1 to 4 hours is adequate. After the extraction is complete, excess olefin is removed. The purified polyketone and solvent can then be separated by filtration or other standard methods. It is usually advantageous to wash or extract the purified polyketone to remove traces of the original solvent and soluble palladium. Again it is usually simplest to use a fresh batch of the original solvent. The polyketones employed in the process of the present invention are typically prepared by polymerising one or more olefins of the type defined earlier- with carbon monoxide in the presence of a solvent of the type described above and a palladium catalyst.

The purity of the carbon monoxide used in this process is not especially critical although it is preferred that it contains less than 20% by volume of other gases such as hydrogen.

Turning to the catalyst the process of the present invention is suitable for use with polyketones that have been prepared using a catalyst prepared from a source of palladium, preferably from a source of palladium, a diphosphine and a non-coordinating or weakly coordinating anion (vide infra). Whilst it is believed that the source of palladium is not critical it is preferred to use a palladium carboxylate salt e.g. palladium acetate, palladium propionate or palladium acetoacetonate. Sources of palladium containing strongly coordinating anions or ligands, e.g. palladium halides, can be used as precursors provided that the anions or ligands are removed from the catalyst composition before use.

A further component of the above preferred catalyst composition is an anion which is either non-coordinating or only weakly coordinating to palladium. Typical although not exhaustive examples

of such anions are (1) the conjugate bases of acids having a pKa of less than 2 as measured at 25 ^C C in water with the exception of hydrogen halides (EP 121965) or (2) the borate anions disclosed in EP 314309. Examples of suitable anions include para-toluenesulphonate, trifluoracetate, difluoroacetate, tetafluoroborate and borate anions of the type described in EP 314309.

As regards the phosphine of the above preferred catalyst composition, whilst this can include simple phosphines such as C _j to CJQ trialkylphosphines, Cg to C^Q triarylphosphines and the like it is preferred that the phosphine is a diphosphine thereby allowing it to adopt a bidentate coordination to palladium. Preferred examples are those having the formula (R^-^P-R -P(R )2 wherein the R groups are independently Cg to C^Q aromatic groups and R^ is a divalent bridging group of formula -(CH2) _n - where n -------- 2 to 8. The aromatic groups may optionally be substituted with polar groups such as -OR ³ , -SR ³ and the like where R ³ is C^ to C alkyl. Preferred diphosphines are those of formula (Ph)2P- CH2 _m -P h 2 where Ph - phenyl and m = 2 to 6 or corresponding compounds where one or more of the phenyl groups are Cj to C4 alkoxy substituted. Especially preferred diphosphines are those wherein m = 2 to 4.

The catalyst as described above can be generated in situ under the reaction conditions by charging sources of the three components to the polymerisation reactor. Alternatively it is possible to add a precursor palladium complex of formula ZPd(0Ac)2 or Z d Q)2^ ⁺ 2X~ which has been prepared beforehand. In these formulae Z is either two monophosphines or the diphosphine referred to above, X is the non- or weakly coordinating anion above and Q is a weakly coordinating ligand such as a nitrile. If the above catalyst is to be prepared in situ in the polymerisation reactor then in the case of the diphosphine it is preferred that the molar ratio of diphosphine to palladium charged is in the range 0.8:1 to 3.0:1 whilst the ratio of anion to palladium is in the range 2:1 to 500:1. Irrespective of how the catalyst is prepared it is preferred that the molar ratio of

palladium to total olefin(s) to be polymerised is in the range 10 ^" ^ to 1 to 10~ ³ to 1.

The polymerisation process is suitably carried out by feeding one or more liquid streams, which in total comprise (1) the components for generating the catalyst or an independently prepared precursor palladium complex, (2) the solvent and (3) any liquid olefin(s) employed, to a polymerisation reactor together with gaseous streams in total comprising carbon monoxide and any gaseous olefins used. The polymerisation reactor is suitably maintained at a temperataure in the range 40 to 150 ^β C preferably 50 to 110°C most preferably 65 to 85°C and at a pressure in the range 10 to 250 bars, preferably 20 to 150 bars, more preferably 20 to 80 bars. It is preferred that the molar ratio of ethylene to carbon monoxide in the polymerisation reactor is in the range 2:1 to 1:2. The polymerisation reactc can be operated either batchwise or continuously. Example 1 (according to the Invention)

A carbon monoxide/ethylene/propene terpolymer as prepared as follows. A mechanically stirred autoclave of 300ml capacity was charged with 27.6 mg of [Pd(l,3-bis(diphenylphosphino)propane)

( hCN)2] [BF4J2, 1.22g of hydrogen bis(salicylato)borate, 0.96g of benzoquinone and 80cm ³ of methanol. The autoclave was sealed and 21.97g propene condensed in at -78°C. The autoclave was warmed to ambient temperature and stirring commenced. A 1:1 mixture of CO and ethylene was admitted (8 bar gauge) before heating to 50 ^C C. The pressure was adjusted to 56 bar gauge and these conditions maintained for one hour. The vessel was then cooled to 34 ^β C and vented to 15 bar. The vessel was then charged to 35 bar with ethylene for one minute and vented to 5 bar, and this procedure repeated three more times. The vessel was then charged with ethylene to 35 bar, sealed and heated to 100 ^β C for one hour before cooling to 20"C and venting completely. The polymer product was collected on a Buchner filter and rinsed with methanol. After drying under vacuum the polymer mass of 6.87 g was analysed for palladium content. A Pd content of 50 microgrammes/g polymer was

found, corresponding to 11% of the original palladium charged to the reactor. The untreated polyketone prepared in a similar experiment was found to contain 53% of the palladium. Example 2 (according to the Invention) • A carbon monoxide/ethylene/propene terpolymer was prepared as follows:

A mechanically stirred autoclave of 300ml capacity was charged with 48.3mg of [Pd(l,3-bis(diphenylphosphino)propane) (PhCN)2][BF4]2, 3.0011g of hydrogen bis(salicylato)borate and 100cm ³ of 2:lv/v mixture of t-butanol/acetone. The autoclave was sealed and 22.03g propene condensed in at -78"C. Stirring was commenced. A 1:1 mixture of CO and ethylene was admitted (8 bar gauge) before heating to 70 ^β C. The pressure was adjusted to 53 bar gauge and these conditions maintained for two hours. The vessel was cooled to below 25 ^β C and vented to 2 bar. The vessel was then charged to 10 bar with ethylene for one minute and vented to 2 bar, and this procedure repeated twice more. The vessel was then vented to atmospheric pressure and charged with 1.5 bar ethylene, sealed and heated to 100*C for 17 hours. lO.Olg of polymer was isolated by filtration. This was soxhlet extracted with fresh t-butanol/acetone solvent, then dried in vacuo. A Pd content of 20ppm was found, corresponding to 3% of the original palladium charged to the reactor. Comparative Example 3 12.11g terpolymer was prepared according to the method in example 2 using 48.9mg of Pd catalyst. The polymer was isolated untreated and washed. A Pd content of 57ppm was found, corresponding to 57% of the original palladium charged to the reactor. Example 4 (according to the Invention)

11.14g terpolymer was prepared according to the method in example 2, except 34.9mg of Ed (1,3-bis(diphenylphosphino)proρane) acetate was used. The terpolymer was treated in a similar manner to that set out in Example 2 except that it was treated at 70 ^β C for 17 hours instead of 100 ^β C for 17 hours. • A Pd content of 184ppm was

found, corresponding to 36% of the original palladium charged to the reactor.