WO2000009521A1

WO2000009521A1 - Catalyst compositions and process for the preparation of polyketones

Info

Publication number: WO2000009521A1
Application number: PCT/EP1999/005986
Authority: WO
Inventors: Eit Drent; Alexander Willem Van Der Made
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 1998-08-13
Filing date: 1999-08-11
Publication date: 2000-02-24
Anticipated expiration: 2001-02-13
Also published as: AU5852299A

Abstract

Catalyst compositions based on a source of a Group VIII metal and a ligand, together capable of forming a complex of formula (I) wherein Z represents a Group VIII metal selected from palladium, cobalt and nickel and (R?1R2)M1-R-M2(R3R4¿) represents the ligand, in which M?1 and M2¿, independently, represent a phosphorus, nitrogen, arsenic or antimony atom; R?1, R2, R3 and R4¿, independently, represent either identical or different, optionally polar substituted hydrocarbyl groups; and R represents a divalent organic bridging group in which the bridge connecting M?1 and M2¿ consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge. A process for preparing polymers of CO and one or more olefinically unsaturated compounds by contacting the monomers with said catalyst composition.

Description

CATALYST COMPOSITIONS AND PROCESS FOR THE PREPARATION OF POLYKETONES

The present invention relates to catalyst compositions suitable for use in the preparation of polymers of carbon monoxide with one or more olefinically unsaturated compounds. Polymers of carbon monoxide and one or more olefinically unsaturated compounds, generally referred to as poly etones or polyketone polymers, are well known in the art. The class of linear alternating polymers of- carbon monoxide and at least one olefinically unsaturated compound are of particular interest among polyketone polymers. This class of polymers is disclosed in numerous patent documents, exemplified by US-A-4880865 and US-A-4818811.

It is known that polymers of carbon monoxide (hereafter referred to as "CO") and one or more olefinically unsaturated compounds can be prepared by contacting the monomers at elevated temperature and pressure with a catalyst composition comprising a Group VIII metal and a ligand with the general formula (R¹R²) ¹-R-M² (R³R⁴) , wherein M¹ and M², independently, represent phosphorus, nitrogen, arsenic or antimony, R represents a divalent organic bridging group and R^-, R²,

R³ and R⁴ are identical or different hydrocarbyl groups.

The polymerisation rates obtained with this kind of catalyst compositions are good, but leave room for further improvement.

EP-A-489 473 describes the use of specific catalyst compositions as defined above for the preparation of linear alternating polymers of CO and one or more olefinically unsaturated compounds. In EP-A-489 473 it is shown that the polymerisation rate decreases significantly when in the catalyst composition a bisphosphine ligand containing three atoms in the bridge connecting the phosphorus atoms is replaced by a bisphosphine ligand containing four atoms in said bridge. However,

EP-A-489 473 also teaches that there is an exception. When CO is polymerised with an α-olefin containing at least three carbon atoms, optionally in combination with ethene, good polymerisation rates can be obtained with a catalyst composition of which the ligand has four atoms in the bridge, provided that this ligand obeys two specific criteria. Firstly, the substituents on the phosphorus atoms must be alkyl groups and secondly, in the bridge connecting the two phosphorus atoms no two atoms may be present which together form part of a single cyclic structure within the bridging group.

The teaching of EP-A-489 473 is in agreement with EP-A-384 517, which discloses the preparation of linear alternating copolymers of CO and -olefins having at least three carbon atoms. The examples of EP-A- 384 517 unequivocally show that the use of catalyst compositions comprising a ligand having four atoms in the bridge of which two atoms form part of a single cyclic structure within the bridging group, results in decreased polymerisation rates compared to catalyst compositions of which the ligand has three atoms in the bridge.

Notwithstanding the teachings of both EP-A-489 473 and EP-A-384 517 it has now surprisingly been found that a high polymerisation rate of CO with an olefinically unsaturated compound can be accomplished when a catalyst composition is used, of which the ligand has four atoms in the bridge, which bridge forms part of a single, specific cyclic structure within the bridging group. This high polymerisation rate is independent of whether the substituents on the atoms M^ and ² are alkyl or aryl groups. This finding is the more surprising in view of EP-A-489 473. Namely, the catalyst compositions according to the present invention do not only give a better polymerisation rate compared to catalyst compositions of which the ligand has three atoms in the bridge, they also outperform the specific catalyst compositions disclosed in EP-A-489 473 comprising a ligand having four atoms in the bridge which do not form part of a single, cyclic structure within the bridging group.

Accordingly, the present invention relates to catalyst compositions based on a source of a Group VIII metal and a ligand, together capable of forming a complex of the following formula I

2+ (I)

R R wherein Z represents a Group VIII metal selected from palladium, cobalt and nickel and (R-R² ) Mi-R-M² (R³R⁴ ) represents the ligand, in which

M- and M , independently, represent a phosphorus, nitrogen, arsenic or antimony atom;

R , R², R³ and R⁴ , independently, represent either identical or different, optionally polar substituted hydrocarbyl groups; and

R represents a divalent organic bridging group in which the bridge connecting M^ and M² consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge .

The present invention also relates to a process for the preparation of polymers of CO and one or more olefinically saturated compounds by using a catalyst composition as defined in the previous paragraph.

The skilled person will appreciate that the complex of the formula I may be a cationic complex, a neutral complex or an anionic complex, dependent on any net charge present on the ligand. Typically the ligand is not charged, in which case the complex is a bivalent cationic complex .

The Group VIII metal is selected from palladium, cobalt, and nickel. Preferably, the group VIII metal is selected from palladium and nickel. Most preferably, the Group VIII metal is palladium. The Group VIII metal is typically employed as a cationic species. As the source of Group VIII metal cations conveniently a Group VIII metal salt is used. Suitable salts include salts of mineral acids such as hydrochloric acid, sulphuric acid, nitric acid and phosphoric acid, and organic salts, such as acetylacetonates and salts of sulphonic acids. Preferably, a salt of a carboxylic acid is used, for example a carboxylic acid with up to 8 carbon atoms, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid and citric acid. Palladium (II) acetate and palladium (II) trifluoro-acetate represent particularly preferred sources of palladium cations. Another suitable source of Group VIII metal cations is a compound of the Group VIII metal in its zero-valent state .

The ligand { R¹^ ) Mi-R-M (R³R⁴ ) represents a multidentate ligand, e.g. a bidentate, tridentate or tetradentate ligand. Preferably (R-R² ) M^R-M² (R³R⁴ ) is a bidentate ligand. M^ and M² , independently, represent a phosphorus, nitrogen, arsenic or antimony atom.

Preferably, one of M¹ or M² is a phosphorus atom, more preferably both M^ and M² represent a phosphorus atom.

Most preferably, the ligand (R!R² ) i-R-M² (R³R⁴ ) is a bisphosphine compound.

Ri, R², R³ and R , independently, represent either identical or different hydrocarbyl groups such as alkyl, aryl, aralkyl or cycloalkyl groups. Throughout this patent document, the term "aryl group" includes

(cyclo) alkylaryl groups. Typically, the groups R¹, R², R³ and R⁴ contain not more than 15 carbon atoms, more typically not more than 10 carbon atoms. In a first preferred embodiment of the present invention, at least one of R^-, R² , R³ and R⁴ represents an aryl group, preferably polar substituted. Suitable polar substituents are halogens and groups of the general formula R5-O-, R5-S-, R5-CO-, R5-CO-O-, RsRgN-, R₅RgN-CO-, R5-O-CO-NH- and R5-O-CO-NR5-, wherein R₅ and

Rg represent similar or dissimilar hydrocarbyl groups like methyl, ethyl, propyl, isopropyl. Preference is give to polar groups selected from R5-O-, R5-S-, R5-CO-,

R5-CO- 0-, R5R5N-, R5-O-CO-NH-, wherein R5 and Rg represent similar or dissimilar hydrocarbyl groups. It is more preferred that each of R^-, R² , R³ and R⁴ represent an aryl group, typically a phenyl group, substituted with a polar group in particular at an ortho position with respect to M¹ and M . Most preferred, Rl, R² , R³ and R⁴ are phenyl groups which contain an alkoxy group and more in particular a methoxy group as polar substituent ortho with respect to the M¹ and M² atoms. Moreover, catalyst compositions are preferred in which the groups R^-R⁴ are identical to one another.

The present invention also relates to ligands represented by the general formula (R^-R² ) M!-R-M² (R³R⁴ ) and which are capable of forming a complex of the formula I, wherein M¹ and M² , independently, represent a phosphorus, nitrogen, arsenic or antimony atom, R¹-, R²,

R³ and R⁴, independently, represent either identical or different aryl groups containing a polar substituent at an ortho position with respect to the M¹ and M² atom, and R represents a divalent organic bridging group in which the bridge connecting M^- and M² consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge.

The formation of a complex of the formula I can be determined by ^ C-NMR, as will be appreciated by the skilled person.

In a second preferred embodiment of the invention, the groups R^ and R² and/or the groups R³ and R⁴ are alkyl groups which are interconnected by a chemical bond, additional to the connection via atom M^ and/or the atom

M², respectively, such that (R¹R²)M¹ and/or (R³R⁴)M² represent a cyclic structure. This cyclic structure is in particular a bicyclononane group wherein one methylene group is replaced by an atom M^ or an atom M², respectively. This means that, when taking for M^ or M² phosphorus, which is preferred, the particular cyclic structure is a 9-phosphabicyclononyl group. Preferably both of (R¹R²)M¹ and (R³R⁴)M² represent a cyclic structure, in particular a 9-phosphabicyclononyl group. The 9-phosphabicyclononyl group may occur in various isomeric structure, in particular as 9-phosphabicyclo- [4, 2, 1] -nonyl and 9-phosphabicyclo- [3, 3, 1] -nonyl . Both isomeric structures may occur together in a single molecular of the ligand. The present invention also relates to ligands of the formula (R^-R² ) Mi-R-M (R³R⁴ ) which are capable of forming a complex of the formula I and wherein (R-*-R²)M1 and

(R³R )M² independently represent a bicyclononane group wherein one methylene group is replaced by an atom M^ or an atom M² respectively, M¹ and M² independently represent a phosphorus, nitrogen, arsenic or antimony atom, and R represents a divalent organic bridging group in which the bridge connecting M^ and M² consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge.

R represents a divalent organic bridging group in which the bridge connecting M^- and M² consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge. Throughout this patent document, a "single cyclic structure" is understood to be one structure which is monocyclic or polycyclic. Furthermore, "bridging group" is understood to be the complete moiety that connects the M¹ and M² atoms. "Bridge", being a part of the bridging group, is understood to consist of the shortest chain of atoms that connects M¹ and M². The bridging group R of the present invention is an organic group comprising 5-30 carbon atoms. The bridge of the present invention consists of four atoms, of which at least two are carbon atoms which together form an unsaturated carbon-carbon bond. The remaining atoms in the bridge may be carbon atoms or they may be heteroatoms such as oxygen, sulphur, silicon or nitrogen. Preferably, all four atoms of the bridge connecting M¹ and M² are carbon atoms .

The bridging group R may be represented by the general formula:

- R⁷ - Y - R⁸ - wherein Y represents a bivalent cyclic hydrocarbon group comprising an unsaturated carbon-carbon bond, which bond is part of the bridge connecting M^ and M². Preferably, Y is an aromatic structure, which may or may not be fused, such as phenylene, naphthylene, phenantrylene . Most preferably Y is a 1, 2-phenylene group. Typically, Y will contain from 4 to 20 carbon atoms, preferably from 6-20 carbon atoms, most preferably from 6-14 carbon atoms. Furthermore, Y may optionally be substituted with e.g. alkyl groups or polar groups and may contain heteroatoms such as oxygen, nitrogen, phosphorus and sulphur. R⁷ and R⁸, independently of one another, may be absent or may represent a methylene or 1,2-ethylene group, or a heteroatom such as oxygen, nitrogen, silicon or sulphur. Optionally, R⁷ and R⁸ may be substituted with substituents, such as alkyl substituents having up to 4 carbon atoms. Preferably, both R7 and Rg represent a methylene group. A most preferred bridging group according to the present invention is a 1, 2-methylenebenzene bridging group.

Examples of suitable ligands according to the invention, wherein M^ and M² are phosphorus, are

1, 2-bis { [bis (2-ethoxyphenyl) phosphino] methyl } cyclo- butene;

1, 2-bis [ (diphenylphosphino) methyl] cyclopentene;

2, 3-bis [ (9-phosphabicyclononyl) methyl] naphthalene;

1, 2-bis { [bis (2-methoxyphenyl) phosphino] methyl } - benzene; 1, 2-bis { [bis (2, 4-dimethoxyphenyl ) phosphino] methyl }- benzene;

1, 2-bis [ ( 9-phosphabicyclononyl ) methyl] benzene ;

1, 2-bis { [bis (2, 6-dimethoxyphenyl) phosphino] methyl } - 4,5-dimethyl benzene;

1, 2-bis [ (diphenylphosphino) oxy] maleic anhydride;

2, 3-bis { N [bis (2-methoxyphenyl) phosphino] amino}- norbornene;

2, 3-bis { [bis (3-butylphenyl) phosphino] methyl } -5, 6- dicarboxylic acid anhydride-norbornene;

2,3-bis{ [bis ( 4- tert-butylphenyl) phosphino] methyl } - 1, 4-endoxo-cyclohexene;

1 , 10-bis (di-n-butylphosphino) phenantrene;

1- ( 9-phosphabicyclononyl) -8- [ (diphenylphosphino) - methyl] naphthalene;

1- (diphenylphosphino) -2- [2- (diphenylphosphino) - ethyl] benzene .

Examples of ligands according to the invention with which very favourable results can be obtained are: l,2-bis{[bis (2-methoxyphenyl) phosphino] methyl } - benzene; and

1 , 2-bis [ ( 9-phosphabicyclononyl) methyl] enzene, which is understood to be a mixture of 1, 2-P, P ' -bis- [( 9-phosphabicyclo- [4 , 2 , 1] -nonyl) methyl] benzene with 1,2- P, P ' -bis [ ( 9-phosphabicyclo- [3,3,1] -nonyl) methyl] benzene and with 1-P- [( 9-phosphabicyclo- [4 , 2, 1] -nonyl) methyl] -2- P- [ ( 9-phosphabicyclo- [3,3,1] -nonyl) methyl] enzene .

These ligands can be prepared by using standard chemistry which is well known to the skilled person. In the catalyst composition according to the present invention the bidentate ligand is preferably present in a quantity of 0.5-2, preferably 0.75-1.5, and most preferably 1.0-1.5 mol per gram atom Group VIII metal.

The Group VIII metal catalyst composition of the present invention is typically based on a source of anions as a further catalyst component. The skilled person will appreciate that suitable anions are those which are non- or only weakly co-ordinating with the Group VIII metal under the conditions of the copoly- merization. Examples of suitable anions are anions of protic acids, which include acids which are obtainable by combining a Lewis acid and a protic acid, and acids which are adducts of boric acid and a 1,2-diol, a catechol or a salicylic acid. Preferred acids are strong acids, i.e. those which have a pKa of less than 6, in particular less than 4, more in particular less than 2, when measured in aqueous solution at 18 °C. Examples of suitable protic acids are the above mentioned acids which may also participate in the Group VIII salts, e.g. trifluoroacetic acid and maleic acid. Examples of Lewis acids, which can be combined with a protic acid, are as the Lewis acids defined and exemplified hereinafter, in particular boron trifluoride, antimony pentafluoride, phosphorus pentafluoride, tin dichloride, tin tetrachloride, tin difluoride, tin di (methylsulphonate) , aluminium trifluoride and arsenic pentafluoride, triphenylborane, tris (perfluorophenyl) borane and tris [3, 5-bis ( trifluoro- methyl) phenyl] borane . Examples of protic acids which may be combined with a Lewis acid are sulphonic acids and hydrohalogenic acids, in particular hydrogen fluoride.

Very suitable combinations of a Lewis acid with a protic acid are tetrafluoroboric acid and hexafluorophos- phosphorus acid (HBF4 and HPFg) . Other suitable anions are anions of which it appears that there are no stable conjugated acids, such as tetrahydrocarbylborate anions or carborate anions. Borate anions may comprise the same or different hydrocarbyl groups attached to boron, such as alkyl, aryl, aralkyl, and cycloalkyl groups. Preferred are tetraarylborates, such as tetraphenylborate, tetrakis [3, 5-bis ( trifluoromethyl) phenyl] borate and tetrakis (perfluorophenyl) borate, and carborate

⁽B11CH12-⁾ •

The source of anions may be an acid from which the anions are derivable, or their salts. Suitable salts are, for example, cobalt, nickel salts and silver salts. Other sources of anions are suitably Lewis acids, such as halides, in particular fluorides, of boron, tin, phosphorus, antimony, aluminium or arsenic. Boron trifluoride and phosphorus pentafluoride are very suitable. Other suitable Lewis acids are hydro- carbylboranes . The hydrocarbylboranes may comprise one hydrocarbyl group or two or three of the same or different hydrocarbyl groups attached to boron, such as alkyl, aryl, aralkyl, and cycloalkyl groups, preferably aryl groups . They may also comprise hydrocarbyloxy or hydroxy groups or halogen atoms attached to boron. Examples of very suitable hydrocarbylboranes are tri- phenylborane, tris (perfluorophenyl) borane and tris [3,5- bis (trifluoromethyl) phenyl] borane . Again other suitable compounds which may function as a source of anions are aluminoxanes, in particular methyl aluminoxanes and t- butyl aluminoxanes.

The quantity of the source of anions is preferably selected such that it provides in the range of from 0.1 to 50 equivalents of anions per gram atom of Group VIII metal, in particular in the range of from 0.5 to 25 equivalents of anions per gram atom of Group VIII metal. However, the aluminoxanes may be used in such a quantity that the molar ratio of aluminium to the Group VIII metal is in the range of from 4000:1 to 10:1, preferably from 2000:1 to 100:1 most preferably from 500:1 to 200:1.

The performance of the catalyst composition may be improved by incorporating therein an organic oxidant promoter, such as a quinone . Preferred promoters are selected from the group consisting of benzoquinone, naphthoquinone and anthraquinone . The amount of promoter is advantageously in the range of from 1 to 500, preferably in the range of from 1 to 100 mole per gram atom of metal of Group VIII.

The amount of catalyst used in the process of the invention is not critical and may vary between wide limits. It is advantageous to employ the least quantity of catalyst composition as possible in relation to the quantity of copolymer to be prepared. Recommended quantities of catalyst composition are in the range of

10^~8 to 10^-2, calculated as gram atoms of metal of Group VIII per mole of olefinically unsaturated compound to be copolymerized with CO. Preferred quantities are in the range of 10^-7 to 10^{"" 3} on the same basis.

Eligible olefinically unsaturated organic compounds that can be polymerised with CO with the aid of the catalyst composition of the present invention are both compounds consisting exclusively of carbon and hydrogen and compounds which in addition contain one or more hetero atoms such as oxygen, nitrogen, sulphur. The olefinically unsaturated compounds comprise typically up to 20 carbon atoms, more typically up to 12 carbon atoms, in particular up to 8 carbon atoms. The catalyst composition of the present invention is particularly useful for the preparation of linear alternating polymers of CO and one or more olefinically unsaturated compounds. Examples of the later are ethene and other α-olefins, such as propene, butene-1, hexene-1, octene-1 and decene-1, as well as styrene and alkyl-substituted styrenes, such as p-methylstyrene and p-ethyl styrene. The catalyst compositions according to the present invention are especially suitable for use in the preparation of polymers of CO and ethene and polymers of CO, ethene and an other α-olefin, preferably propene, butene-1 or octene-1.

The polymerisation according to the invention is preferably carried out at a temperature in the range of 20-200 °C, preferably at a temperature in the range of 30-150 °C . The reaction is conveniently performed at a pressure in the range of 2 to 200 bar, preferably at a pressure in the range of 5 to 100 bar. The process may be carried out as a batch process or as a continuous process. In the latter case it is advantageous to apply two or more reactors connected in series, because this increases the quantity of polymer which can be prepared within a given period of time using a certain reaction volume and a certain quantity of catalyst .

The monomers may be contacted with a solution of the catalyst composition in a liquid diluent, in which case the liquid phase is the continuous phase of the polymerization mixture. Preferably a diluent is used in which the admixed catalyst composition is soluble and in which the copolymer to be prepared forms a suspension. The latter implies that a diluent may be selected in which the copolymer is insoluble or virtually insoluble. Examples of liquid diluents are ketones (e.g. acetone), chlorinated hydrocarbons (e.g. chloroform or dichloromethane) , aromatics (e.g. toluene, benzene, chlorobenzene) and protic diluents, such as the lower alcohols. Lower alcohols are understood to be alcohols having 1 to 4 carbon atoms, e.g. methanol and ethanol. Mixtures of liquid diluents may be used as well, for example protic diluents may comprise aprotic compounds. In certain embodiments the process of this invention may also be carried out as a gas phase process, in which case the gas phase is the continuous phase of the polymerization mixture.

In the mixture to be polymerised, the molar ratio of the olefinically unsaturated compounds relative to CO is preferably 10:1-1:10, and in particular 5:1-1:5.

When the process of this invention is carried out such that the prepared copolymer is formed as a suspension in a liquid diluent it is advantageous to have a solid particulate material suspended in the diluent before the monomers are contacted with the catalyst composition. Typically a powder of copolymer of CO and an olefinically unsaturated compound is used as the solid particulate material, in particular a copolymer which is based on the same monomers as the copolymer to be prepared. The latter means that, for example, when a linear alternating copolymer of CO, ethene and propene will be prepared a linear alternating copolymer of CO, ethene and propene from an earlier polymer preparation will be suspended in the diluent. Other suitable solid particulate materials may be inorganic or organic materials, such as silica, alumina, talc, soot and polymers, for example polyethene, polypropene and polystyrene .

The polyketone polymers of number average molecular weight from 1,000 to 200,000, particularly those of number average molecular weight from 20,000 to 90,000 as determined by gel permeation chromatography are of particular interest. The physical properties of the polymer will depend in part upon the molecular weight, whether the polymer is based on a single or on a plurality of ethylenically unsaturated compounds and on the nature and the proportion of the ethylenically unsaturated compounds. Typical melting points for the polymers are from 175 °C to 300 °C, typically from 175 °C to 270 °C, more typically from 190 °C to 240 °C, as determined by differential scanning calorimetry.

Some of the performance properties of the polymers prepared according to the present invention depend on their molecular weight. In view hereof, it is important that the polymers have a molecular weight suitable for the application envisaged. Various methods have been proposed by which the molecular weight of the polymer can be influenced. One method involves the selection of the polymerisation temperature. If one would desire to decrease the molecular weight, this may be effected by increasing the temperature. However, a disadvantage of applying a higher temperature is that the stability of the catalyst composition may become a problem. As an additional advantage, the catalyst compositions according to the present invention have been found to yield polymers having a relatively low molecular weight compared to catalyst compositions which differ therefrom by having three carbon atoms in the bridge of the ligand, or four carbon atoms which do not form part of a single cyclic structure within the bridging group. This holds in particular for catalyst compositions according to the present invention in which R^-R⁴ represent aryl groups. The molecular weight of the polymers may be expressed by their Limiting Viscosity Number (LVN value) ; the lower the LVN value, the lower the molecular weight of the polymers .

As a second additional advantage, in case of the preparation a polymer of CO, ethene and an α-olefin having three or more carbon atoms, e.g. propene, octene-1 or decene-1, the catalyst compositions according to the present invention are more effective in incorporating this α-olefin compared with catalyst compositions having three carbon atoms in the bridge of the ligand, or four carbon atoms which do not form part of a single cyclic structure within the bridging group. This holds in particular for catalyst compositions according to the present invention in which RI-R⁴ represent alkyl groups, and more in particular for catalyst compositions in which the groups R! and R² and/or the groups R³ and R⁴ are alkyl groups which are interconnected by a chemical bond, such that (R¹R )M¹ and/or (R³R )M² represent a cyclic structure . The polymers may be recovered from the polymerisation mixture by any suitable conventional technique, e.g. washing with methanol and drying.

Additives which are well known in the art may be added to the polymers prepared according to the present invention. For instance, antioxidants, fillers, extenders, lubricants, pigments, plasticisers and other

(polymeric) materials can be added to linear alternating polyketones to improve or otherwise alter the properties of the polymer. The polymer prepared according to the present invention may further be processed according to known techniques, like extrusion, stretching (e.g. of sheet to form film), by thermofor ing, blow moulding, injection moulding . The present invention will now be demonstrated by the following examples .

Example 1 (for comparison)

A linear alternating polymer of CO with ethene was prepared as follows. An autoclave with a volume of 0.5 litre was charged with 330 ml methanol, and 5.4 gram of a powder of a linear alternating copolymer of CO, ethene and propene.

Subsequently, a catalyst solution was introduced which consisted of: 40 ml of a mixture of methanol/acetone, 0.1 mmol palladium acetate,

0.115 mmol 1, 3-bis [bis (2-methoxyphenyl) phosphino] propane, and 0.5 mmol trifluoroacetic acid.

The autoclave was closed, and stirring was started. The autoclave was purged with N₂ at 50 bar. At atmospheric pressure the autoclave was heated to 90 °C . When the temperature reached 88 °C, 24 bar CO and 24 bar ethene was forced in until a pressure of 50 bars was achieved. During the polymerisation, an 1/1 (mol/mol) CO/ethene mixture was supplied continuously to the autoclave to maintain a pressure of 50 bar. After 1 hour, the polymerisation was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The polymer was filtered off, washed with methanol and dried .

The polymerisation rate was 12.7 kilogram polymer/gram palladium. hour . The LVN (dL/g, measured at 60 °C in m-cresol was 1.6.

Example 2 (according to the invention)

Example 1 was repeated with the difference that instead of 1, 3-bis [bis (2-methoxyphenyl) phosphino] - propane, 1, 2-bis { [bis (2-methoxyphenyl) phosphino] - methyl (benzene was used.

The polymerisation rate was 22.0 kilogram polymer/gram palladium. hour .

The LVN (dL/g, measured at 60 °C in m-cresol) was 1.0. Example 3 (for comparison)

A linear alternating polymer of CO with ethene was prepared as follows. An autoclave with a volume of 250 litre was charged with 90 ml methanol. Subsequently, a catalyst solution was introduced which consisted of: 10 ml methanol, 0.01 mmol palladium acetate,

0.012 mmol 1, 3-bis ( 9-phosphabicyclononyl) propane, containing 80 % by weight of the isomer 1, 3-P, P' -bis [9- phosphabicyclo- [3,3,1] -nonyl] propane, and 0.2 mmol trifluoroacetic acid. The autoclave was closed and stirring was started.

The autoclave was evacuated, flushed three times with CO and heated to 70 °C . Subsequently, 20 bar of ethene and 30 bar CO were forced in until a pressure of 50 bar was reached. After 4 hours the polymerisation was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The polymer was filtered off, washed with methanol and dried.

The reaction rate was 0.7 kg polymer/gram palladium. our . Example 4 (according to the invention)

Example 3 was repeated with the difference that instead of 1, 3-bis ( 9-phosphabicyclononyl ) propane, 0.012 mmol 1, 2-bis [( 9-phosphabicyclononyl ) methyl] benzene containing 80% by weight of the isomer 1 , 2-P, P' -bis [ ( 9- phosphabicyclo- [3, 3, 1] -nonyl) methyl] benzene was used.

The polymerisation reaction was terminated after two hours .

The reaction rate was 8.5 kg polymer/gram palladium. hour . Example 5 (for comparison)

A linear alternating terpolymer of CO with ethene and propene was prepared as follows .

An autoclave with a volume of 1.25 litre was charged with 690 ml methanol, 11 grams of water and 33.6 gram of a linear alternating copolymer of CO, ethene and propene. Subsequently, a catalyst solution was introduced which consisted of:

40 ml of a mixture of methanol/acetone, 0.1 mmol palladium acetate,

0.115 mmol 1, 3-bis [bis (2-methoxyphenyl ) phosphino] propane, and

0.5 mmol trifluoroacetic acid.

The autoclave was closed, and stirring was started. The autoclave were purged with N2 at 50 bar. At atmospheric pressure, the autoclave is flushed three times with CO and 72 gram propene are added. Next, 10 bars of CO were introduced and the autoclave is heated to 76 °C . When the polymerisation temperature is reached the autoclave is pressurised with ethene to reach a final pressure of 46. After 6 hours, the polymerisation was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The polymer was filtered off, washed with methanol and dried. The polymerisation rate was 5.5 kilogram polymer/gram palladium. hour .

The LVN (dL/g, measured at 60 °C in o-cresol) was 1.6. Example 6 (according to the invention) Example 5 was repeated with the difference that instead of 1, 3-bis [bis (2-methoxyphenyl) phosphino] propane, 1, 2-bis { [bis (2-methoxyphenyl ) phosphino] methyl } benzene was used.

The polymerisation rate was 19.2 kilogram polymer/gram palladium. hour .

The LVN (dL/g, measured at 60 °C in o-cresol) was 0.86. Example 7 (for comparison)

A linear alternating terpolymer of CO with ethene and propene was prepared as follows.

An autoclave with a volume of 250 litre was charged with 90 ml methanol. Subsequently, a catalyst solution was introduced which consisted of: 90 ml methanol, 0.05 mmol palladium acetate,

0.06 mmol 1, 4-bis ( 9-phosphabicyclononyl) butane, containing 80% by weight of the isomer 1, 4-P, P' -bis (9- phosphabicyclo- [3,3,1] -nonyl) butane, and 0.5 mmol trifluoroacetic acid.

The autoclave was closed, and stirring was started. The autoclave was evacuated, flushed three times with CO and subsequently 30 ml propene was added. Next, 20 bars of CO and 20 bar of ethene were introduced until a pressure of 50 bar was reached and the autoclave was heated to 60 °C . After 2.5 hours, the polymerisation was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The polymer was filtered off, washed with methanol and dried.

The reaction rate was 1.5 kilogram polymer/gram palladium. hour .

The ratio C3/C2 in the final polymer (determined with ¹³C-NMR) was 0.06.

Example 8 (according to the invention)

Example 7 was repeated with the exception that instead of 1, 4-bis ( 9-phosphabicyclononyl) butane, 0.06 mmol 1, 2-bis [( 9-phosphabicyclononyl) methyl] benzene containing 80% by weight of the isomer 1, 2-P, P' -bis [ ( 9- phosphabicyclo- [3, 3, 1] -nonyl) methyl] benzene was used.

The polymerisation reaction was terminated after 0.5 h. The reaction rate was 7.5 kilogram polymer/gram palladium. hour .

The ratio C3/C2 in the final polymer was (determined with ¹³C-NMR) was 0.11.

In all cases, it was confirmed with ^³C NMR that the resulting polymers were linear alternating polymers of CO and the olefinically unsaturated compounds (ethene, propene) .

Claims

C L A I M S

1. Catalyst compositions based on a source of a Group VIII metal and a ligand, together capable of forming a complex of the following formula I

M

\

2+ (I)

wherein Z represents a Group VIII metal selected from palladium, cobalt and nickel and (R!R² ) M^R-M² (R³R⁴ ) represents the ligand, in which

Ml and M², independently, represent a phosphorus, nitrogen, arsenic or antimony atom;

R¹, R², R³ and R⁴, independently, represent either identical or different, optionally polar substituted hydrocarbyl groups; and

R represents a divalent organic bridging group in which the bridge connecting M^ and M² consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge.

2. Catalyst composition as claimed in claim 1, wherein both M^- and M² are a phosphorus atom.

3. Catalyst composition as claimed in claims 1 or 2 wherein R^, R², R³ and R⁴ are phenyl groups which contain an alkoxy group, in particular a methoxy group, as polar substituent ortho with respect to the M¹ and M² atom.

4. Catalyst composition as claimed in claim 1 or 2 , wherein the groups R! and R² and/or the groups R³ and R⁴ are alkyl groups which are interconnected by a chemical bond, such that (R¹R )M¹ and/or (R³R⁴)M² represent a cyclic structure.

5. Catalyst composition as claimed in claim 4, wherein

(R!R )M1 and (R³R )M² represent a 9-phosphabicyclononyl group.

6. Catalyst composition as claimed in any of claims 1-4, wherein the bridging group R may be represented by the general formula:

- R₇ - Y - R₈ - wherein Y represents a bivalent cyclic hydrocarbon group having 4 to 20 carbon atoms, comprising an unsaturated carbon-carbon bond, which bond is a part of the bridge connecting M^ and M² and R7 and Rg, independently of one another may be absent or may represent a methylene group or a 1,2-ethylene group.

7. Catalyst composition as claimed in claim 5, wherein Y represents an aromatic structure, which may or may not be fused, having 6-20 carbon atoms.

8. Catalyst composition as claimed in claim 6, wherein Y represents a 1, 2-phenylene group and both R7 and Rg represent a methylene group.

9. Catalyst composition as claimed in claim 3, wherein the ligand is 1, 2-bis { [bis (2-methoxy phenyl) phosphino] - methyl (benzene .

10. Catalyst composition as claimed in claim 4, wherein the ligand is 1, 2-bis [ (9-phosphabicyclononyl) methyl] - benzene .

11. Catalyst composition as claimed in any of claims 1-9, comprising in addition an anion of an acid with a pKa of less than 6, in a quantity of 0.1 to 50 equivalents of anions per gram atom of Group VIII metal.

12. Catalyst composition as claimed in any of claims 1-10, wherein the Group VIII metal is palladium.

13. Process for the preparation of polymers of CO and one or more olefinically saturated compounds by contacting the monomers with a catalyst composition as defined in any of claims 1-11.

14. Process according to claim 12, characterized in that it is carried out at a temperature in the range of 30-150 °C, at a pressure of in the range of 5 to 100 bar and that per mol of olefinically unsaturated compound to be polymerised a quantity of catalyst composition is used which contains 10^_7-10^-3 gram atom Group VIII metal.

15. Ligands represented by the general formula

(R¹R²)M¹-R-M (R³R⁴) which are capable of forming a complex of the formula I as defined in claim 1, and wherein

M-*- and M² , independently, represent a phosphorus, nitrogen, arsenic or antimony atom;

Ri, R , R³ and R , independently, represent either identical or different aryl groups containing a polar substituent at an ortho position with respect to the M^ and M² atom; and

R represents a divalent organic bridging group in which the bridge connecting M^ and M² consists of four atoms, and which bridging group contains a single cyclic structure that shares an unsaturated carbon-carbon bond with said bridge.

16. Ligands represented by the formula

(R!R²) M!-R-M² (R³R⁴) which are capable of forming a complex of the formula I as defined in claim 1 and wherein

(R¹R²)M¹ and (R³R⁴)M², independently, represent a bicyclononane group wherein one methylene group is replaced by an atom M^ or an atom M²;

Ml and M² , independently, represent a phosphorus, nitrogen, arsenic or antimony atom; and