JPH08302008A - Method of copolymerizing carbon monoxide and unsaturated olefin compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolymer useful for fibers, films, packaging materials, or the like, in a manner for reducing the introduction of terminal groups derived from a boron hydrocarbyl compound used as a catalyst by bringing carbon monoxide and an olefinically unsaturated compound into contact with a specified catalyst under a specified hydrogen partial pressure.

SOLUTION: Carbon monoxide (A) and an olefinically unsaturated compound (B) such as ethene or a mixture of ethene with an α-olefin (e.g. propene or butene-1) are brought into contact with a catalyst (D) based on a source of a group VII metal (e.g. palladium) and a boron hydrocarbyl compound {e.g. a compound of the formula: BXYZ [wherein X, Y, and Z are each a (substituted) hydrocarbyl such as an aryl]} in the presence of hydrogen (C) having a pressure of at least 0.01 MP to copolymerize component A with component B.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for copolymerizing carbon monoxide with an olefinically unsaturated compound.

[0002]

2. Description of the Related Art European Patent Publication No. 619335 discloses a method for copolymerizing carbon monoxide with an olefinically unsaturated compound, wherein the monomer is a catalyst based on a Group VIII metal source and a boron hydrocarbyl compound. Disclosed is a method comprising contacting with. This method is suitable for preparing a linear copolymer of carbon monoxide and an olefinically unsaturated compound. This copolymer is in particular an alternating copolymer, ie a copolymer in which the monomer units derived from carbon monoxide alternate with the monomer units derived from an olefinically unsaturated compound. This copolymerization method is typically carried out in the absence of hydrogen.

[0003]

The copolymers prepared by this method have hydrocarbyl end groups, which are derived at least in part from a boron hydrocarbyl compound which is one of the catalyst components. It is a thing. This is a disadvantage because at least a part of the boron hydrocarbyl compound is consumed in the copolymerization. The formation of such end groups is particularly disadvantageous when the hydrocarbyl group in question contains a heteroatom such as halogen or nitrogen. This drawback is also related to the environmental meaning of having a heteroatom in the copolymer, for example when the copolymer is incinerated.

[0004]

It has now been found that when the copolymerization method is carried out in the presence of hydrogen, the introduction of terminal groups derived from the boron hydrocarbyl compound is significantly reduced. That is, the present invention is a method for copolymerizing carbon monoxide and an olefinically unsaturated compound, which comprises at least 0.01
The process comprises contacting the monomer with a Group VIII metal source and a catalyst based on a boron hydrocarbyl compound in the presence of hydrogen having a pressure of MP (0.1 bar). European Patent Publication No. 619335 discloses an excess of a boron hydrocarbyl compound relative to a Group VIII metal, for example, a boron hydrocarbyl compound having a molar ratio of boron / Group VIII metal of about 50: 1. The use of compounds is recommended. In the process of the invention, the introduction of end groups derived from boron hydrocarbyl compounds is reduced, so that the boron / Group VIII metal molar ratio is lower than that described in EP 619335, for example , Less than 25: 1 can be advantageously implemented. In the present specification, “VIII
"Group metal" is intended to encompass the noble metals ruthenium, rhodium, palladium, osmium, iridium and platinum, as well as the iron group metals iron, cobalt and nickel. Suitable catalyst compositions for use in the method of the invention are based on the cation sources of the above metals. Suitable cation sources for Group VIII metals include salts of mineral acids such as sulfuric acid, nitric acid and phosphoric acid, and salts of sulfonic acids such as methanesulfonic acid and para-toluenesulfonic acid. Suitable sources are carboxylic acids, especially carboxylic acids having up to 6 carbon atoms such as acetic acid, propionic acid and trifluoroacetic acid. If desired, it is also possible to use the metal in the zero-valent state in atomic form or in complex form, such as a complex in which the Group VIII metal is covalently bonded to one or two hydrocarbyl groups, as the cation source. I can. Such covalently bonded hydrocarbyl groups can be aliphatic or aromatic and typically contain up to 12 carbon atoms. Suitable covalently bonded hydrocarbyl groups include aliphatic,
In particular, there are n-alkyl groups such as methyl and n-butyl groups.

Catalyst compositions based on the noble metal Group VIII metal are preferred, and those based on palladium are most preferred. A preferred source of palladium is palladium (II) acetate. In addition to the Group VIII metal, the catalyst composition contains a boron hydrocarbyl compound. The boron hydrocarbyl compound is typically represented by the general formula: BXYZ (wherein X, Y, and Z are each a substituted or unsubstituted hydrocarbyl group, a hydroxy group, a substituted or unsubstituted hydrocarbyloxy group). A group or a halogen atom,
At least one of X, Y, and Z is a substituted or unsubstituted hydrocarbyl group. The hydrocarbyl group or the hydrocarbyloxy hydrocarbyl group is an aliphatic or aromatic group and typically contains up to 12 carbon atoms. Suitable hydrocarbyl groups are
It is a substituted or unsubstituted aryl group. Suitable substituents for the hydrocarbyl group are electron withdrawing groups such as trihalomethyl groups, nitro groups and halogen atoms. Hydrocarbyl groups in which all hydrogen atoms are replaced are also included in the term "hydrocarbyl group". The hydrocarbyl group is in particular a phenyl group, in particular a perfluorophenyl or 3,5-bis (trifluoromethyl) phenyl group. Examples of suitable aliphatic groups include:
There are ethyl, n-butyl and n-hexyl groups. Halogen atoms X, Y, and Z are preferably fluorine. Examples of hydrocarbylboranes are phenyldifluoroborane, phenylboronic acid and hexylboronic acid. It is preferred that all three of X, Y and Z are hydrocarbyl groups. Suitable examples include triphenylborane, tris (perfluorophenyl) borane and tris [3,5-bis (trifluoromethyl) phenyl] borane. Other suitable boron hydrocarbyl compounds are salts containing one or more borate anions per molecule. For example, the general formula: MeBZ ¹ Z ² Z
³ Z ⁴ (in the formula, Me is an alkali metal such as lithium or sodium, and Z ¹ , Z ² , Z ³ and Z ⁴ are each a substituted or unsubstituted hydrocarbyl group). .
The hydrocarbyl groups Z ¹ , Z ² , Z ³ and Z ⁴ may be of the same type or may be the preferred examples as described above for the X, Y and Z groups. Examples are lithium tetraphenylborate and sodium tetrakis (perfluorophenyl).
There is a borate. The amount of boron hydrocarbyl compound used varies widely. However, as already mentioned, the boron / Group VIII metal molar ratio is less than 25: 1. In particular, this ratio is preferably 0.1-20, more preferably 0.5-
15, especially in the range of 1-10.

The present inventor has experienced that a polymerization reaction using a catalyst composition based on a Group VIII metal source and a boron hydrocarbyl compound borane causes a decrease in the polymerization rate. Thus, feeding a portion of the boron hydrocarbyl compound during the polymerization is beneficial because the polymerization rate is maintained at the initial level. For example, 40% or less, preferably 5-
30% of the boron hydrocarbyl compound is fed at the beginning of the polymerization reaction and the rest at a later time, continuously or stepwise.

The catalyst composition of the process of the invention is preferably
As an additional component, it is based on a ligand which forms a complex with a Group VIII metal. It appears that two complexing sites in one ligand molecule can contribute significantly to the activity of the catalyst. Therefore, it is preferable to use a ligand having at least two coordinations that form a complex with the Group VIII metal. Although less preferred, it is also possible to use monovalent ligands, which are compounds having a single coordination complex with the Group VIII metal. Divalent ligands containing two coordination groups containing phosphorus, nitrogen or sulfur are suitable. 1-
It is also possible to use divalent mixed ligands such as diphenylphosphino-3-ethylthiopropane.

Suitable divalent ligands have the general formula: R ¹ R ² M ¹ -RM
² R ³ R ⁴ (I) (wherein, M ¹ and M ² are each a phosphorus, arsenic or antimony atom, and R ¹ , R ² , R ³ and R ⁴ are each 1
It represents an unsubstituted or polar substituted hydrocarbyl group of up to 0 carbon atoms, and R represents a divalent organic bridging group containing at least 2 carbon atoms in the bridge. ).
In the ligand of general formula (I), M ¹ and M ² preferably represent phosphorus atoms. R ¹ , R ² , R ³ and R ⁴ are each,
It represents a polar-substituted alkyl, aryl, alkaryl, aralkyl or cycloalkyl group. Preferably,
One of R ¹ , R ² , R ³ and R ⁴ is aromatic, in particular aromatic substituted with a polar group.

Suitable polar groups include halogen atoms such as fluorine and chlorine, alkoxy groups such as methoxy and ethoxy, and alkylamino groups such as methylamino, dimethylamino and diethylamino. Alkoxy and alkylamino groups are especially those having up to 5 carbon atoms in their alkyl groups. R ¹ , R ² ,
One or more of R ³ and R ⁴ , in particular each of R ¹ , R ² , R ³ and R ⁴ is an aryl group, preferably a phenyl group, an alkoxy group in the ortho position with respect to M ¹ or M ² , especially methoxy. It is preferably substituted with a group. This results in an advantageous improvement in maintaining the polymerization rate at the initial level. In the ligands of general formula (I), R is preferably a divalent organic bridging group, containing 2 to 4 bridging atoms, at least 2 of which are carbon atoms. Examples of such R include -CH ₂ -CH _2- , -CH ₂ -C
_{H 2 -CH 2 -, - CH} 2 -CH 2 -CH 2 -CH 2 - it is. Preferably R is a trimethylene group. Suitable ligands are 1,3-bis [bis (2,4-dimethoxyphenyl) phosphino] propane and 1,3-bis [bis (2,4,6-trimethoxyphenyl) phosphino] propane, more preferably Is 1,3-bis [bis (2-methoxyphenyl) phosphino] propane. Other suitable divalent ligands have the general formula:

Embedded image Wherein X ¹ and X ² each is an organic bridging group containing 3 or 4 bridging atoms, at least 2 of which are carbon atoms. There may be additional bridging groups connecting the bridging groups X ¹ and X ² . Examples of such compounds include 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine,
4,4'-dimethoxy-2,2'-bipyridine, 1,1
0-phenanthroline, 4,7-diphenyl-1,10
-Phenanthroline and 4,7-dimethyl-1,10-
There is phenanthroline. The preferred compound is 2,2'-
Bipyridine and 1,10-phenanthroline.

Still other suitable divalent ligands are of the following general formula R ⁵ SQ-SR ⁶ (III) where R ⁵ and R ⁶ are each a substituted or polar substituted hydrocarbyl group. , Q is a divalent bridging group having 2 to 4 carbon atoms in the bridging group). R ⁵ and R ⁶ are preferably each an alkyl group, in particular having up to 10 carbon atoms. Particularly suitable bisthio compounds are 1,2-bis (ethylthio) ethane and 1,2-bis (propylthio) ethene. As a monovalent ligand, the following general formula R ⁷ R ⁸ R ⁹ M ³ (IV) (wherein M ³ represents a phosphorus, arsenic or antimony atom, R ⁷
And R ⁸ and R ⁹ each represent an n-alkyl group and an aryl group, in particular a substituted or polar substituted hydrocarbyl group, such as a phenyl group, in particular having up to 11 carbon atoms. It is preferred to use the compounds of). Possible substituents include alkoxy groups such as methoxy and ethoxy groups. Suitable monovalent ligands are tris (o-tolyl) phosphine, tris (2-methoxyphenyl) phosphine, trinaphthylphosphine and tris (n).
-Butyl) phosphine.

The amount of divalent ligand added will vary considerably, but will usually depend on the amount of Group VIII metal present in the catalyst composition. A suitable amount of divalent ligand, other than nitrogen divalent ligands, is 0.5-8, preferably 0.5-2 moles per gram atom of Group VIII metal. In the case of nitrogen divalent ligands, it is 0.5-200, preferably 1-50 mol per gram atom of Group VIII metal. The monovalent ligand is preferably 0.5-50, especially 1-25 mol per gram atom of Group VIII metal. The activity of the catalyst composition can be improved by including an organic oxidation promoter such as quinone. Suitable accelerators are selected from the group consisting of benzoquinone, naphthoquinone and anthraquinone. The promoter is advantageously used in the range of 1-50, preferably 1-10 mol per gram atom of Group VIII metal. The amount of catalyst composition used in the process of the invention can vary within wide limits. Recommended amounts of catalyst composition are in the range of 10 ^-8 -10 ^-2 , calculated as gram atoms of Group VIII metal per mole of olefinically unsaturated compound which copolymerizes with carbon monoxide. . Suitable amounts are in the range 10 ^-7 -10 ^-3 , based on the same criteria.
In the present invention, the copolymerization reaction is preferably carried out in the presence of a protic compound. The advantage of using protic compounds is that the rate of polymerization is better maintained at the initial level. Examples of protic compounds are acids (eg sulphonic acid, carboxylic acid, boric acid and glycol or salicylic acid adducts), alcohols and water. If they have carbon atoms, then they are 15 or less. The preferred acid is 1 in aqueous solution.
Those having a pKa, measured at 8 ° C., of less than 6, more preferably less than 4, especially less than 2. Suitable protic compounds are primary, secondary and tertiary fatty acid alcohols and alcohols such as phenols. They can be monohydric alcohols or polyhydric alcohols.

Suitable alcohols are the lower alcohols which are usually understood as monohydric alcohols which are completely miscible with water, in particular methanol and ethanol. The amount of protic compound used varies widely. A suitable amount of acid is
0.5-200 per gram atom of Group VIII metal, especially 1.0-5
0, more particularly 1.0-10 equivalents. When the protic compound is an alcohol, especially a lower alcohol, it functions as a liquid diluent in the copolymerization or is incorporated therein, for example, 50% by volume or less based on the total volume of the diluent. , Especially 5-30% by volume.

The olefinically unsaturated compounds used as monomers in the copolymerization process of the present invention include compounds consisting only of carbon and hydrogen, and also compounds such as esters containing heteroatoms. Unsaturated hydrocarbons are preferred. Examples of suitable monomers are olefins having 2 to 6 carbon atoms such as ethene, propene and butene-1, i.e. lower olefins, cyclic olefins such as cyclopentene, fragrances such as styrene and α-methylstyrene. There are group compounds and vinyl esters such as vinyl acetate and vinyl propionate. Ethene and ethene and other α-olefins such as propene or butene-1
A combination with is preferred.

In copolymerizing carbon monoxide with ethene and other olefinically unsaturated compounds, the addition of hydrogen to the copolymerization mixture has the further advantageous effect according to the invention. The effect is that the other olefinically unsaturated compound is more efficiently incorporated, and as a result, a copolymer having an increased molar ratio of the other olefinically unsaturated compound to ethene is obtained. Generally, the molar ratio of carbon monoxide to olefinically unsaturated compound ranges from 1: 5 to 5: 1. Preferably, the molar ratio is 1: 1.5
To 1.5: 1, with substantially equimolar ratios being most preferred. The copolymerization method of the present invention is typically preferably carried out in the presence of a liquid diluent. Preferably, a diluent is used in which the copolymer prepared will form a suspension therein. In such cases, a diluent can be chosen such that the copolymer is insoluble or substantially insoluble. Examples of said liquid diluents are ketones (eg acetone), chlorinated hydrocarbons (eg chloroform or dichloroform), aromatics (eg toluene, benzene, chlorobenzene) and lower alcohols (methanol and ethanol). There is a protic diluent. For example, a mixture of liquid diluents can be used as well. For example, the aprotic diluent can be mixed with an aprotic diluent. In particular, aromatic diluents and protic diluents are particularly preferable because they have an improving effect on maintaining the polymerization rate at the initial level. The method of the present invention can also be carried out by gas phase polymerization.

When the process of the present invention is practiced so that the copolymer prepared forms a suspension in a diluent, the solid particulate material is suspended in the diluent before the monomer is contacted with the catalyst composition. Turbidity is advantageous. This embodiment is advantageous because it provides an improved effect with respect to maintaining the polymerization rate at the initial level. In this embodiment, the catalyst composition is preferably used as a solution, preferably in a diluent. Alternatively, it is preferable to use a catalyst deposited on the solid particulate matter or a catalyst chemically bound to the solid particulate matter. This latter type of catalyst is known, for example, from EP 511713, 404228 and 619334. A catalyst deposited on such solid particulate material,
Alternatively, the catalyst chemically bound to the solid particulate material can also be used advantageously when the polymerization reaction is carried out by a gas phase process.

Copolymers of carbon monoxide and olefinically unsaturated compounds are typically used as the solid particulate material, especially those based on the same monomers as the copolymer prepared. That is, for example, when a linear alternating copolymer of carbon monoxide and ethene is prepared, the linear alternating copolymer of carbon monoxide and ethene obtained from the previous polymerization is suspended in a diluent. Let them do it. Other suitable solid particulate materials are inorganic or organic materials such as silica, alumina, talc, soot, and polymers such as polyethene, polypropene and polystyrene. The solid particulate material is
Suitably 0.1-20w%, more suitably 0.5-, relative to diluent
Used in an amount of 10w%. The bulk density of the solid particulate material is typically 50-1000 kg / m ³ , especially 100-500 kg / m ³ .
Its average particle size is 10 ^-6 -10 ^-3 m, preferably 10 ^-6 -5 x
It is 10 ^-4 m. The average particle size of the solid granular material is determined as follows. A commercial particle size analyzer is used to determine the cumulative weight distribution of a representative sample of the solid particulate material as a function of particle size. This cumulative weight distribution function is converted into a cumulative surface area distribution function (Terence Allen in Particle Size Measuremen
t, Chapman and Hall, London, 1981, p.122 ff). The average particle size is obtained as the median (median) of the cumulative surface area distribution function.

According to the invention, the copolymerization reaction is at least
It is carried out in the presence of hydrogen with a pressure of 0.01 MPa (0.1 bar). Suitably, the hydrogen pressure is 0.05-5.0 MPa (0.5-50
Bar), more suitably in the range 0.1-3.0 MPa (1-30 bar). A suitable hydrogen to carbon monoxide partial pressure ratio is 1: 10-
It is in the range of 2: 1 and especially 1: 5-1: 1. When the method of the present invention is carried out in the presence of a liquid diluent, typically the stirring power transferred to the polymerization mixture is at least 0.25 KW /
m ³ , especially at least 0.5 KW / m ³ . Stirring power is 0.25K
If it is less than W / m ³ , the monomer in the liquid phase, particularly carbon monoxide, is deficient, resulting in a decrease in the copolymerization reaction rate.
If the stirring power is at least 0.25 KW / m ³ , this situation will be improved. At least 0.5K if a diluent is used and the copolymer prepared in it is suspended.
It is recommended to apply a stirring power of W / m ³ , especially at least 1.0 KW / m ³ . The maximum practical power density is 20 W / m ³ . The preferred power density range is from 1.5 to 15 W / m ³ . Stirring power can be transmitted to the polymerization mixture by any means such as, for example, a stirrer, jet mixer or gas stream. The copolymerization method of the present invention is usually carried out in the range of 20 to 200 ° C, preferably 30 to 150 ° C. The reaction is conventionally carried out in the pressure range of 0.2-20.0 MPa (2-200 bar), preferably 2.0-10.0 MPa (20-100 bar). Typically, the method of the present invention will be carried out on a scale such that, if a liquid diluent is present, greater than 10 kg. In particular, when there is an improvement in the stability of the polymerization rate by using one or more means of the present invention, residence times of more than 1 hour, especially 1.5 hours and even 3.5 hours are achieved. It is advantageous to employ. The process of the invention can be carried out batchwise or in a continuous process. In the latter case, the use of two or more consecutively coupled reactors increases the amount of polymer prepared in a given amount of time using a given amount of catalyst and a given amount of reaction volume. Therefore, it is advantageous. The copolymers prepared by the method of the present invention are useful as fibers, films or sheets, or thermoplastics for injection molding, compression molding and blow molding. The thermoplastics are used in the automotive industry, packaging materials for food and beverages and in various domestic applications.

[0018]

The invention will be described in more detail with reference to the following examples. The diluent was of analytical quality and was purchased as received. Example 1 (Comparative Example) A copolymer of carbon monoxide, ethene and propene was prepared as follows. Tris (perfluorophenyl) borane
(0.247g, 0.48mmol) was weighed in air, placed in a dry Schlenk tube and dissolved in 100ml dichloromethane. This solution was charged with a baffle and a tilted blade stirrer.
Transferred to 0 ml autoclave. In this autoclave
25 g of propene were added and a pressure of 4.0 MPa (40 bar) was applied with premixed carbon monoxide and ethene (molar ratio 1: 1). The stirring power was about 3 W / m ³ . The autoclave was heated to 70 ° C. L ₂ Pd (C in 10 ml of dichloromethane
_{H 3 CO 2) 2 (0.0154g} , 0.025mmol) (L 2 is 1,3-bis (diphenylphosphino) shown propane) was injected into the autoclave. The pressure was maintained by adding a mixture of carbon monoxide and ethene. After 1 hour, the pressure was released and the autoclave was allowed to cool to room temperature. The polymer product was filtered, washed with dichloromethane and dried. ^{13 of a} copolymer using hexafluoroisopropanol as a solvent
According to C-NMR analysis, the amount of pentafluorophenyl end groups was 20 mol% based on all the end groups. The molar ratio of propene-derived monomer units to ethene-derived monomer units was 0.15: 1.

Example 2 (Example) A copolymer of carbon monoxide, ethene and propene was premixed with carbon monoxide and ethene (molar ratio 1: 1) at 4.0 MPa.
A pressure of (40 bar) is applied, followed by hydrogen at 5.0 MPa (50
Prepared as in Example 1, except that pressure was applied up to bar). The pressure was maintained by adding a mixture of carbon monoxide and ethene. The amount of pentafluorophenyl end groups based on all the end groups was 12.5 mol%. The molar ratio of propene-derived monomer units to ethene-derived monomer units is 0.2.
It was 0: 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) The inventor, Jane Jyutz, The Netherlands 1031 C.M.Amsterdam, Bathoeusuehi 3 (72) The inventor, Peter Schiermann, The Netherlands 1031 C.A.M.Amsterdam, Bathuisueh 3 (72) Invention Rudolf Jacobs Wierngaarden Netherlands 1031 Seem Am Sterdam, Bathoeusueich 3

Claims (10)

[Claims] 1. A method for copolymerizing carbon monoxide and an olefinically unsaturated compound, wherein the monomer is added to a group VIII metal source and a boron hydrocarbyl compound in the presence of hydrogen having a pressure of at least 0.01 MP. Said method comprising contacting with a catalyst based on. 2. The Group VIII metal is palladium, and the boron hydrocarbyl compound is represented by the general formula: BXYZ (wherein X, Y, and Z are each a substituted or unsubstituted hydrocarbyl group, preferably an aryl group. Is shown.)
2. The method according to claim 1, characterized in that it is hydrocarbylborane. 3. The molar ratio of boron to Group VIII metal is 2
In an amount less than 5, especially in the range 0.1-20,
Method according to claim 1 or 2, characterized in that a boron hydrocarbyl compound is used. 4. A general formula: R ¹ R ² M ¹ -RM ² R ³ R ⁴ (I) (wherein, M ¹ and M ² each represent a phosphorus, arsenic or antimony atom, and R ¹ , R ² ,, R ³ and R ⁴ are, in particular,
Shows unsubstituted or polar substituted hydrocarbyl groups of up to 10 carbon atoms, provided that one or more of R ¹ , R ² , R ³ and R ⁴ is an alkoxy group in the ortho position with respect to M ¹ or M ^2. In particular, it represents an aryl group substituted with a methoxy group, preferably a phenyl group, and R represents a divalent organic bridging group containing at least 2 carbon atoms in the bridge. 4. The method according to any one of claims 1 to 3, characterized in that the divalent ligand of)) is used as an additional catalyst component. 5. The method according to any one of claims 1 to 4, characterized in that the ligand diluent is an aromatic diluent or a protic diluent. 6. The olefinically unsaturated compound is ethene or, more preferably, a mixture of ethene and another olefinically unsaturated compound such as an α-olefin, for example propene or butene-1. The method according to any one of claims 1 to 5, characterized in that 7. The molar ratio of carbon monoxide to olefinically unsaturated compound is 1: 5 to 5: 1, preferably 1: 1.
The amount of catalyst composition ranges from 5 to 1.5: 1, calculated as gram atoms of Group VIII metal per mole of olefinically unsaturated compound to be copolymerized, from 10 ^-8 to 10
^-2 , preferably in the range of 10 ^-7 to 10 ^-3 , the temperature is selected from the range of 20 to 200 ° C, preferably 30 to 150 ° C, and the pressure is 0.2 to 20.0 MPa, preferably , 2.0 to 10.0 MPa, 7. The method according to claim 1, wherein the method is selected from the range of 2.0 to 10.0 MPa. 8. Process according to claim 1, characterized in that the hydrogen pressure is in the range of 0.05 to 5.0 MPa, preferably 0.1 to 3.0 MPa. 9. A diluent is present to form the suspension in which the copolymer is prepared, and the stirring power transmitted to the polymerization mixture is at least 0.5 KW / m ³ , in particular at least 1.0 KW / m.
Method according to any one of claims 1 to 8, characterized in that it is in the range of ³ , preferably 1.5 KW / m ³ to 15 KW / m ³ . 10. A solid particulate material is suspended in a liquid diluent prior to contacting the monomer with the catalyst composition, a suitable solid particulate material being a copolymer of carbon monoxide and an olefinically unsaturated compound. 10. The method according to claim 9, characterized in that it is, in particular, based on the same monomers as the copolymer prepared.