NL8800349A - New aromatic phosphide and aromatic phosphine cpds. - and use of new di:phosphine cpds. in catalyst for copolymerisation of carbon mon:oxide and unsatd. cpd. - Google Patents

Abstract

(i) New phosphides of formula R7R8PM (I) are claimed, and are prepd. by reacting an alkali metal (M) with a phosphine of formula R6R7R8P in liq. NH3. (ii) New phosphines of formula (R6)2R8P and new diphosphines of reacting (I) with a cpd. of formula X-R-X or X-R-PR9R10. M = alkali metal; R6 = aromatic hydrocarbon gp. with 1 or more polar substits. only in the o- and m-positions w.r.t. P, and with at least 1 substit. in the o-position w.r.t. P; R7 = aromatic hydrocarbon gp., opt. polar-substd.; R8 = aliphatic hydrocarbon gp., opt. polar-substd., with no =C=C= gp. linked to P through only 1 C; X = Cl or Br; R = at least 2C divalent bridging gp.; R9,R10 = hydrocarbon gps., opt. polar-substd. at least 1 of which is not =R7 and R8. (iii) New catalyst compsns. contain (a) a Pd cpd. (pref. a carboxylate, e.g. Pd acetate), (b) an anion of an acid with pKa less than 6 (pref. of a sulphonic acid, e.g. p-toluene sulphonic acid, or a carboxylic acid, e.g. trifluoroacetic acid), and (c) a diphosphine of formula R7R8P-R-PR7R8 or R7R8P-R-PR9R10, and opt. (d) a promoter, e.g. a 1,4-quinone, and (iv) prepn. of polymers by polymerising a mixt. of CO and an olefinically unsatd. cpd. (pref. ethylene or a mixt. of ethylene and another olefinically unsatd. hydrocarbon, e.g. propylene) are claimed, as are the polymers, and shaped articles (partly) prepd. from them.

Description

*

T 363 NET

PREPARATION OF PHOSPHIDS

The invention relates to a process for the preparation of phosphides which are suitable for use in the preparation of diphosphines. The latter compounds find use as a component in catalyst compositions intended for the preparation of polymers of carbon monoxide with one or more olefinically unsaturated compounds.

High molecular weight linear polymers of carbon monoxide with one or more olefinically unsaturated compounds (for the sake of brevity referred to as A) in which the monomer units exist alternately and which therefore consist of units of the general formula - (CO) —A'— wherein A 'represents a monomer unit derived from a monomer A used, can be prepared using catalyst compositions based on a) a palladium compound, b) an anion of an acid with a pKa less than 6, and c) a diphosphine of the general formula R 1, PR-PR 3 R 4 wherein R 1 through R 4 represent equal or different aromatic hydrocarbyl groups and R is a divalent bridge group containing at least two carbon atoms in the bridge.

20

Very suitable diphosphines for use as component c) in the catalyst compositions are those of the general formula R-1-P-R-PR] wherein R 1 and R 2 represent identical or different aromatic hydrocarbyl groups. Insofar as the groups R 1 and R 2 are equal and the diphosphines can therefore be represented by the general formula (R 2> 2P-RP (R 1) 2, their preparation can take place either by reaction of an alkali metal di (hydrocarbyl) phosphide ( RPM with a dihalogen compound XRX, or by reaction of a hydroearbylalkall metal compound RjM with a tetrahalodiphosine fine X2P-R-PX2 For example, 1,3-bis (diphenylphosphino) propane can be prepared or by reaction of (Cg ^ ^ PNa with 01- (012) 3-01, or by reaction of CgHjLi with C ^ P-iCI ^) 3PCI2.

Considering the simple one-step synthesis of the phosphorus-containing starting material for the first preparation method, namely by reaction in liquid ammonia of an alkali metal M with a .8800349 - - 2 - ί * tri (hydrocarbyl) phosphine (R ^ ^ P) and the very laborious multi-step synthesis of the phosphorus-containing starting material for the second preparation method, the first preparation method is by far preferred.

5 The Applicant has conducted an investigation in the past regarding the above catalyst compositions. In addition, it has been found that their behavior can be improved in a number of cases by including a diphosphine with the general formula R ^ R ^ PR-PR ^ R ^ as component c), wherein R] is an aromatic hydrocarbyl group and R5 is a aliphatic hydrocarbyl group. When comparing the behavior of catalyst compositions which contain as component c) a diphosphine of the general formula (R-PR-PCRi ^ such as 1,3-bis (diphenylphosphino) propane with corresponding catalyst compositions which, however, as component c ) containing a diphosphine of the general formula R1R5P-R-PR1R5 such as 1,3-bis (phenyl, n-butylphosphino) propane, it appears that at a reaction temperature equal for both compositions with higher molecular weight polymers are obtained.

The applicant has conducted an investigation into the preparation of diphosphines of the general formula RjR ^ P-R-PR ^ R ^. Since for these diphosphines as well as for the diphosphines of the general formula (Rl ^ PR-PCRi ^ it holds that the preparation method by reaction of hydrocarbylalkali metal compounds with tetrahalo diphosphines is not very attractive in view of the very difficult multi-step synthesis of the required phosphorus-containing starting material, also goes for the preparation of the diphosphines of the general formula Rj ^ PR-PR ^ Rj, preference is given to the aforementioned method in which an alkali metal di (hydrocarbyl) -30 phosphide is reacted with a dihalogen compound.

As mentioned above in the discussion of the preparation of diphosphines of the general formula (R ^ ^ PR-PiRi ^), the phosphorus-containing starting material necessary for its synthesis can be obtained in a simple manner by reacting in liquid ammonia an alkali metal M with a Tri (hydrocarbyl) phosphine .8800349-3 - (R1> 3P. In this way, for example, triphenylphosphine can be converted in quantitative yield into an alkali metal diphenylphosphide. The investigation has shown that application of this method starts from a tri (hydrocarbyl) phosphide of the general formula for the preparation of an alkali metal di (hydrocarbyl) phosphide of the general formula R-R-R PM is not very attractive in view of the low yield of phosphide For example, starting with diphenyl, iso-propylphosphine was reacted in liquid ammonia with sodium, the desired sodium phenyl, iso-10-propylphosphine in a yield of less than 15%.

In further research on this subject, it has now been found that alkali metal di (hydrocarbyl) phosphides of the general formula RjRgM can be prepared in very high yield by applying the cleavage reaction with an alkali metal in liquid ammonia to a tri (hydrocarbyl) phosphine with the general formula R-jRjRgP in which Rg represents an aromatic hydrocarbyl group containing one or more polar substituents which can only occupy the ortho and meta positions with respect to the phosphorus atom and at least one of which is ortho-standing with respect to

20 phosphorus. In the investigation it was further found that for the successful progress of this preparation method it is necessary that the aliphatic hydrocarbyl group does not contain a> C = C <group which is bound to the phosphorus atom via only one carbon atom.

Finally, in the investigation it has been found that the above described preparation method is also very suitable for the preparation of alkali metal di (hydrocarbyl) phosphides in which the aliphatic hydrocarbyl group is polar substituted and for example a 3-ethoxypropyl group and / or in which the aromatic hydrocarbyl group is polar substituted and for example a 2,6-dimethoxy-30-phenyl group. In the further argument, the optionally polar substituted aromatic hydrocarbyl groups which occur in the phosphides to be prepared will be referred to as Ry and the optionally polar substituted aliphatic hydrocarbyl groups which will exist in the phosphides to be prepared as Rg.

. 880 034 9 # - 4 -

The present patent application therefore relates to a process for the preparation of phosphides in which phosphides of the general formula RyRgPM are prepared by reacting in liquid ammonia an alkali metal M with a phosphine of the general formula RgR.7R.gP, in which general formulas Rg represents an aromatic hydrocarbyl group containing one or more polar substituents which can occupy only the ortho and meta positions with respect to the phosphorus atom and at least one of which is ortho-position with respect to phosphorus, R7 is an optionally polar substituted aromatic hydrocarbyl group and Rg is an optionally polar substituted aliphatic hydrocarbyl group in which there is no> C «C <group attached to the phosphorus atom via only one carbon atom. To the extent that in the phosphides of the general formula RyRgPM, the group Ry and / or the group Rg contains one or more polar substituents, these phosphides are new compounds. The present patent application also relates to these new compounds. Examples of these new phosphides are sodium (2-methoxyphenyl), n-butyl phosphide, sodium (2-methoxyphenyl), 3-ethoxypropyl phosphide, and sodium (2,6-dimethoxyphenyl), n-butyl phosphide.

The phosphides of the general formula (RyRgPM prepared according to the invention are primarily intended to be used as starting material for the preparation of diphosphines of the general formula RyRgP-R-PRyRg, ie diphosphines in which the two groups which are one phosphorus atom are the same as the two groups which are on the other phosphorus atom For this purpose, the phosphides may be reacted with a dihalogen of the general formula XRX wherein X represents chlorine or bromine, provided that in the diphosphines of the general formula RyRgP- R-PRyRg the group R7 and / or the group Rg contains one or more polar substituents, these diphosphines are new compounds The present patent application also relates to these diphosphines as new compounds.

Examples of these new diphosphines are .8800349 * - 5 - 1,3-bis [(2-methoxyphenyl), n-butylphosphino] propane, and 1,3-bis [(2-methoxyphenyl), 3-ethoxypropylphosphino] propane.

The phosphides of the general formula RyRgPM prepared according to the invention are furthermore suitable for use as starting material for the preparation of diphosphines of the general formula RyRgP-R-PRgR ^ g in which Rg and R ^ q have the same or different optionally polar substituted hydrocarbyl groups. proposals of which at least one is not equal to Ry and Rg.

For this purpose, the phosphides can be reacted with a monohalogen compound of the general formula X-R-PRgRj ^ Q.

The present patent application further relates to new catalyst compositions based on a) a palladium compound, b) an anion of an acid with a pKa less than 6, and c) a diphosphine of the general formula RyRgP-R-PRyRg or R7RgP- R-PR9R10.

The present patent application finally relates to the use of these new catalyst compositions in the preparation of polymers of carbon monoxide with one or more olefinically unsaturated compounds, as well as to the polymers and shaped articles thus prepared which at least partly consist of these polymers.

In the process of the invention, compounds of the general formula RyRgPM are prepared from compounds of the general formula RgRyRgP. In the general formula RgRyRgP, Rg is preferably a phenyl group containing one or two polar substituents ortho to the phosphorus atom. Suitable polar substituents include dialkylamino groups such as dimethylamino groups and alkoxy groups such as methoxy groups. As the polar substituents, one or two alkoxy groups and more particularly one or two methoxy groups are preferably present in the aromatic hydrocarbyl group Rg. Examples of suitable groups Rg are the 2-methoxyphenyl group and the 2,6-dimethoxyphenyl group. In the general formula RgRyRgP, Ry is preferably equal to Rg, ie the process according to the invention preferably starts from a phosphine of the general formula (Rg ^ RgP. Phosphines of the general formula (.8800349-6). Rg ^ RgP are new compounds Examples of these new phosphines are di (2-methoxyphenyl), n-butylphosphine, 5 di (2-methoxyphenyl), 3-ethoxypropylphosphine, and di (2,6-dimethoxyphenyl), n-butylphosphine. In the general formula RgRyRgP, Rg is an optionally polar substituted aliphatic hydrocarbyl group in which there is no> CC <group attached to the phosphorus via only one carbon atom.

Therefore, in the process according to the invention, phosphines which contain an allyl group as group Rg are not suitable as starting material. Examples of suitable groups Rg are alkyl groups such as the n-butyl group and polar substituted alkyl groups such as the 3-ethoxypropyl group.

The phosphides according to the invention are prepared by reaction in liquid ammonia of an alkali metal M with a phosphine. Lithium, potassium and sodium can be used as alkali metals. Preference is given to the use of sodium as the alkali metal. Preferably at least 2 moles of alkali metal are used per mole of phosphine to be converted. The amount of liquid ammonia can vary within wide limits. Preferably 1 to 125 ml and in particular 10 to 40 ml of liquid ammonia are used per mmole of alkali metal. In view of the fact that liquid ammonia boils at atmospheric pressure at about -33 eC, the process, if conducted at atmospheric pressure, should be below -33 eC. Preferably, the process is carried out at a temperature from -100 to -35 eC and in particular from -80 to -35 C.C. If the process is carried out under pressure, it is possible to work at temperatures above -33 ° C if desired. In some cases, the yield of phosphide can be increased by adding an ether to the liquid ammonia in which the reaction is carried out. As ethers, especially cyclic ethers and in particular tetrahydrofuran are very suitable. Preferably 2.5 to 75 and in particular 5 to 50 ml of ether are used per 8800349 * - 7 - 100 ml of liquid ammonia.

As stated above, the present patent application also relates to new catalyst compositions for the preparation of polymers of carbon monoxide with one or more olefinically unsaturated compounds, which catalyst compositions are based on a) a palladium compound, b) an anion of an acid with a pKa of less than 6, and 10 c) a diphosphine of the general formula RyRgP-R-PRyRg or

RyRgP-R — PRgR ^ Q.

The palladium compound used as component a) in the catalyst compositions is preferably a palladium salt of a carboxylic acid and in particular palladium acetate. As component b) 15, an anion of an acid with a pKa of less than 4 (measured in aqueous solution at 18 ° C) is preferably used in the catalyst compositions and in particular an anion of an acid with a pKa of less than 2 More particularly preferred is an anion of a sulfonic acid such as para-toluenesulfonic acid or an anion of a carboxylic acid such as trifluoroacetic acid. Component b) can be included in the catalyst compositions in the form of an acid and / or in the form of a salt. Non-precious transition metal salts such as copper salts are suitable as salts. As the component c), a diphosphine is preferably used in the catalyst compositions, in which the divalent bridge group R is a - (0 ^) 3 group. In addition to components a), b) and c), the catalyst compositions may also contain promoters. A 1,4-quinone and in particular a 1,4-naphtho-30 quinone are preferably used for this purpose.

Suitable olefinically unsaturated compounds which can be polymerized with carbon monoxide using the catalyst compositions described above include compounds consisting exclusively of carbon and hydrogen and compounds containing one or more heteroatoms in addition to carbon and .8800349 hydrogen. . Preference is given to the preparation of polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons. Examples of suitable hydrocarbon monomers are ethylene and other α-olefins such as propylene, butene-1, hexene-1 and octene-1. The catalyst compositions of the invention are especially suitable for use in the preparation of copolymers of carbon monoxide with ethylene and for the preparation of terpolymers of carbon monoxide with ethylene and with another olefinically unsaturated hydrocarbon such as propylene. The polymerization 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 polymerization is generally carried out by contacting the monomers with a solution of the catalyst composition in an organic liquid in which the polymers are not or practically insoluble. If desired, the polymerization can also be carried out in the gas phase.

The invention is now illustrated by the following examples.

Example 1

Sodium phenyl, isopropyl phosphide was prepared as follows. To 100 ml of liquid ammonia present in a mechanically stirred reaction vessel, which was kept at -78 ° C by cooling, 8 mmoles of sodium and 4 mmoles of diphenyl, isopropylphosphine were successively added. After 4 hours, 4 mmol of ammonium chloride was added to the reaction mixture. After 15 minutes, ammonia was removed by evaporation. Analysis of the residue showed that the diphenyl, iso-30-propyl phosphine was 12% converted to sodium phenyl, iso-propyl phosphide.

Example 2

Sodium (2-methoxyphenyl), n-butyl phosphide was prepared essentially in the same manner as the sodium phenyl, isopropyl phosphide in Example 1, but with the following differences. 8800349-9 - *

V

a> di (2-methoxyphenyl), η-butylphosphine was used in place of diphenyl, isopropylphosphine, and b) the addition of ammonium chloride took place after 1 hour instead of after 4 hours.

The di (2-methoxyphenyl), n-butylphosphine was found to be 67% converted to sodium (2-methoxyphenyl), n-butylphosphide.

Example 3

Sodium (2-methoxyphenyl), n-butyl phosphide was prepared essentially in the same manner as the sodium phenyl, iso -propyl phosphide in Example 1, but with the following differences a) di (2-methoxyphenyl), η-butyl phosphine was substituted of diphenyl, iso-propylphosphine, and b) 12 mmol sodium instead of 8 mmol were used, c) 8 mmol ammonium chloride instead of 4 mmol 15 were used, and d) the addition of ammonium chloride took place after 2 hours instead of after 4 hours.

The di (2-methoxyphenyl), η-butylphosphine was found to be quantitatively converted to sodium (2-methoxyphenyl), n-butylphosphide.

20 Example 4

Sodium (2-methoxyphenyl), 3-ethoxypropylphosphide was prepared essentially in the same manner as the sodium phenyl, isopropylphosphide in Example 1, but with the following differences a) di (2-methoxyphenyl), 3-ethoxypropylphosphine was substituted for 25 of diphenyl, isopropylphosphine, b) 40 ml of tetrahydrofuran were added together with the phosphine, and c) the addition of ammonium chloride took place after 30 minutes instead of after 4 hours.

The di (2-methoxyphenyl), 3-ethoxypropylphosphine was found to be quantitatively converted to sodium (2-methoxyphenyl), 3-ethoxypropylphosphide.

.8800349 ψ - 10 -

Example 5

Sodium (2,6-dimethoxyphenyl), n-butyl phosphide was prepared essentially in the same manner as the sodium phenyl, isopropyl phosphide in Example 1, but with the following differences 5 a) di (2,6-dimethoxyphenyl), n -butylphosphine instead of diphenyl, isopropylphosphine used, and b) the addition of ammonium chloride took place after 3 hours instead of after 4 hours.

The di (2,6-dimethoxyphenyl), n-butylphosphine was quantitatively converted to sodium (2,6-dimethoxyphenyl), n-butylphosphide. Example 6 1.3-bis [(2-methoxyphenyl), n, butylphosphino] propane was prepared as follows. Sodium (2-methoxyphenyl), n-butyl phosphide prepared according to example 2 was converted by hydrolysis to 2-methoxyphenyl, n-butyl phosphine. 3.9 g of this phosphine was dissolved in 100 ml of tetrahydrofuran and 12.5 ml of a 1.6 molar solution of n-butyl lithium in n-hexane were added dropwise to this solution at room temperature with stirring. After stirring at room temperature for 30 minutes, the reaction mixture was cooled to -78 ° C and 2.02 g of 1,3-dibromopropane was added. Tetrahydrofuran was distilled off and 100 ml of water and 100 ml of diethyl ether were added to the residue. The organic layer was separated and washed twice with water. Diethyl ether was distilled off and dichloromethane was added to the residue. Filtration and removal of the solvent gave 1.6 g of 1,3-bis [(2-methoxyphenyl), n-butylphosphinoipropane.

Example 7 1.3-bis [(2-methoxyphenyl), 3-ethoxypropylphosphino] propane was prepared essentially in the same manner as the 1,3-bis [(2-methoxyphenyl), n-butylphosphino] propane in Example 6, however with the following differences a) Sodium (2-methoxyphenyl), 3-ethoxypropylphosphide prepared according to example 4 was converted by hydrolysis into (2-methoxyphenyl), 3-35-ethoxypropylphosphine, and .8800349 ντ - 11 -: b) at 4 3 g of this phosphine, 11.9 ml of the n-butyl lithium solution was added and 1.82 g of 1,3-dibromopropane was added to the reaction product.

1.2 g of 1,3-bis [(2-methoxyphenyl), n-butylphos-5 fino] propane were obtained.

Example 8

A carbon monoxide / ethylene copolymer was prepared as follows. 230 ml of methanol were placed in a mechanically stirred autoclave with a capacity of 300 ml. After the content of the autoclave was brought to 90 ° C, a 1: 1 carbon monoxide / ethylene mixture was pressed in until a pressure of 55 bar was reached. A catalyst solution was then introduced into the autoclave consisting of: 4.5 ml of methanol, 1.5 ml of toluene, 0.02 mmol of palladium acetate, 0.400 mmol of trifluoroacetic acid, and 0.024 mmol of 1,3-bis [(2-methoxyphenyl), n-butylphosphino] propane .

During the polymerization, the pressure was maintained at 55 bar by pressing a 1: 1 carbon monoxide / ethylene mixture. After 17.7 hours, the polymerization was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The copolymer was filtered off, washed with methanol and dried at 50 ° C. 10.03 g of copolymer was obtained. The polymerization rate was 270 g copolymer / g palladium. hour.

25 Example 9

A carbon monoxide / ethylene copolymer was prepared essentially in the same manner as the copolymer in Example 8, but with the following differences a) the catalyst solution contained 0.405 mmol para-toluenesulfonic acid instead of 0.400 mmol trifluoroacetic acid and 0.024 mmol 1,3 bis [(2-methoxyphenyl), 3-ethoxypropylphosphino] propane instead of 1,3-bis [(2-methoxyphenyl), n-butylphosphino] propane, and b) the reaction time was 17.17 hours instead of 17, 7 hours.

.8800344

F

- 12 -

8.60 g copolymer was obtained. The polymerization rate was 230 g copolymer / g palladium. hour.

Of Examples 1-9, Examples 2-9 are according to the invention. Example 1 is outside the scope of the invention and is included in the patent application for comparison. This example shows the low yield of sodium phenyl, isopropyl phosphide when diphenyl, isopropyl phosphine is used in its preparation. Examples 2-5 concern the preparation according to the invention of new phosphides starting from new phosphines. Examples 6-9 concern the preparation of two new diphosphines as well as their use in catalyst compositions for the preparation of carbon monoxide / ethylene copolymers. Using 1 C-NMR analysis, it was determined that the carbon monoxide / ethylene copolymers prepared according to Examples 8 and 9 had a linear alternating structure and therefore consisted of units of the formula - (00) - (02 ^) -.

8800349

Claims (31)

1. Process for the preparation of phosphides, characterized in that phosphides of the general formula R ^ RgPM are prepared by reaction in liquid ammonia of an alkali metal M with a phosphine of the general formula RgR ^ RgP, in which general formulas Rg represents an aromatic hydrocarbyl group containing one or more polar substituents which can occupy only the ortho and meta positions with respect to the phosphorus atom and of which at least one occurs ortho-position with respect to phosphorus, Rj is an optionally polar substituted aromatic hydrocarbyl group and Rg is a optionally polar substituted aliphatic hydrocarbyl group in which there is no> C = C <group attached to the phosphorus atom via only one carbon atom. A method according to claim 1, characterized in that Rg is a phenyl group containing one or two polar substituents ortho to the phosphorus atom. Process according to claim 1 or 2, characterized in that the polar substituents in Rg are alkoxy groups. Process according to claim 3, characterized in that Rg is a 2-methoxyphenyl group or a 2,6-dimethoxyphenyl group. Process according to one or more of Claims 1 to 4, characterized in that a phosphine of the general formula (Rg, RgP. Process according to one or more of claims 1-6, characterized in that Rg is an alkyl group such as the n-butyl group or an alkoxyalkyl group such as the 3-ethoxypropyl group. Process according to one or more of claims 1 to 6, characterized in that the alkali metal H is sodium. Process according to one or more of claims 1 to 7, characterized in that at least 2 moles of alkali metal are used per mole of phosphine to be converted. 9. Process according to one or more of claims 1-8, characterized in that 1-125 ml of liquid ammonia are used per mole of alkali metal. .8800349 9 - 14 - ί 10. Process according to claim 9, characterized in that 10-40 ml of liquid ammonia is used per mmol of alkali metal. 11. Process according to one or more of claims 1-10, characterized in that the reaction is carried out at a temperature of -100 to -35 ° C. Process according to claim 11, characterized in that the reaction is carried out at a temperature of -80 to -35 ° C. 13. Process according to one or more of claims 1-12, characterized in that an ether is added to the liquid ammonia in an amount of 2.5 to 75 ml per 100 ml of liquid ammonia. 13. V Method according to claim 13, characterized in that per 100 ml of liquid ammonia, 5 to 50 ml of ether are used. 15. A process according to claim 13 or 14, characterized in that a cyclic ether is used as ether. Process according to claim 15, characterized in that tetrahydrofuran is used as cyclic ether. 17. A process for the preparation of phosphides according to claim 1, essentially as described above and in particular with reference to examples 2-5. Phosphides prepared according to claim 17. 19. New phosphides of the general formula RyRgM, in which M represents an alkali metal, Ry is an aromatic hydrocarbyl group and Rg is an aliphatic hydrocarbyl group in which no> C = C <group 25 occurs which is bound to the phosphorus atom via only one carbon atom and in which Ry and / or Rg contains one or more polar substituents. 20. As the new phosphides of claim 19, sodium (2-methoxyphenyl), n-butyl phosphide, sodium (2-methoxyphenyl), 3-ethoxypropyl phosphide, and sodium (2,6-dimethoxyphenyl), n-butyl phosphide. 21. New phosphines of the general formula (Rg ^ RgP, wherein Rg represents an aromatic hydrocarbyl group containing one or more polar substituents which can occupy only the ortho and 35 meta sites relative to phosphorus and Rg an optionally .8800349 - 15 - * polar substituted aliphatic hydrocarbyl group in which there is no> CC <group attached to the phosphorus atom via only one carbon atom. 22. As new phosphines according to claim 21, 5 di (2-methoxyphenyl), 2-butylphosphine, di (2-methoxyphenyl), 3-ethoxypropylphosphine, and di (2,6-dimethoxyphenyl), n-butylphosphine, 23. Process for the preparation of diphosphines, characterized in that a phosphide according to claim 18 is reacted either with a compound of the general formula XRX or with a compound of the general formula XR-PRgR ^ g, in which general formulas X represents chlorine or bromine, R is a divalent bridging group containing at least two carbon atoms in the bridge and Rg and Rg represent equal or different optionally polar substituted hydrocarbyl groups of which at least one is unequal to Ry and Rg. 24. New diphosphines of the general formula RyRgP-R-PRyRg in which Ry is an aromatic hydrocarbyl group, Rg is an aliphatic hydrocarbyl group in which no> C = C <group occurs which is bound to the phosphorus atom via only one carbon atom, R a divalent bridge group is containing at least two carbon atoms in the bridge and wherein Ry and / or Rg contains one or more polar substituents. The novel diphosphines of claim 24, 25, 1,3-bis [(2-methoxyphenyl), n-butylphosphino] propane, and 1,3-bis [(2-methoxyphenyl), 3-ethoxypropylphosphino] propane. 26. New catalyst compositions, characterized in that they are based on a) a palladium compound, b) an anion of an acid with a pKa less than 6, and c) a diphosphine of the general formula RyRgP-R-PRyRg or RyRgP-R-PRgR ^ O where Ry is an optionally polar substituted aromatic hydrocarbyl group, Rg is an optionally polar substituted aliphatic hydrocarbyl group which does not contain a 35 C 1 C group passing through only one carbon atom. 880 0349 * - 16 - the phosphorus atom is bonded, Rg and R ^ q are the same or different optionally polar substituted hydrocarbyl groups at least one of which is unequal to Ry and Rg, and R is a divalent bridging group containing at least two carbon atoms in the bridge. Catalyst compositions according to claim 26, characterized in that they are based on a) a palladium salt of a carboxylic acid such as palladium acetate, b) an anion of a sulfonic acid such as para-toluenesulfonic acid or of a carboxylic acid such as trifluoroacetic acid, c) a diphosphine in which the divalent bridge group R is a - ((^ 2) 3 group), and d) optionally a promoter such as a 1.4 quinone. 28. Process for the preparation of polymers, characterized in that a mixture of carbon monoxide with one or more olefinically unsaturated compounds is polymerized using a catalyst composition according to claim 26 or 27. 29. Process according to claim 28, characterized in that the olefinically unsaturated compounds used are hydrocarbons such as ethylene or a mixture of ethylene with another olefinically unsaturated hydrocarbon such as propylene. Polymers prepared according to a method as described in claim 28 or 29. 31. Molded articles which at least partly consist of the polymers according to claim 30, 8800349