NL8901311A - New palladium catalyst contg. bidentate ligand and supported acid - prepd. by reacting carrier contg. hydroxy gps. with e.g. poly-basic acid, used in prepn. of copolymers from carbon mon:oxide and olefin! - Google Patents

Abstract

New catalyst compsns. are based on (a) a Pd component, (b) a bidentate ligand component which can form a complex with (a) through 2 dentate gps. contg. P, N or S, and (c) an acid on a carrier, obtd. by reaction of a solid carrier contg. OH gps. with a polybasic organic acid or anhydride with at least 1 COOH or carboxylic anhydride gp., when the gps. react together to form carboxylic ester gps. (a) is pref. a Pd salt of a carboxylic acid. e.g. Pd acetate, is pref. (b) (i) The component is 0.5-100 (1-50) mols, w.r.t 1 mol of Pd, of a cpd. of formula R1S-R-SR1 or a gp. of formula (P) or (ii) 0.5-2 (0.75-1.5) mols, w.r.t 1 mol of Pd, of R12P-R-PR12, e.g. 1,3-bis(bis(2-methoxyphenyl phosphino)propane (I). where R1 = hydrocarbon gp., opt. polar substd.; R = divalent bridging gp. contg. at least 2C; X = organic bridging gp. with 3-4 atoms including at least 2C; in (ii), esp. R1 = aryl gp., carrying an alkoxy gp. in the o-position to P; and R has 3 atoms in the bridge.

Description

CATALYST COMPOSITIONS

The invention relates to new catalyst compositions suitable for use in the preparation of polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons.

Linear polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons in which polymers, on the one hand, the units originating from carbon monoxide and, on the other hand, the units originating from the olefinically unsaturated hydrocarbons used, may alternately be prepared by the monomers in an reactor at elevated temperature and contact pressure with a catalyst solution in a diluent in which the polymers are insoluble or practically insoluble and which catalyst composition is based on a) a palladium-containing component, b) a bidentate ligand component which, via two phosphorus, nitrogen or sulfur-containing dentate groups, containing the palladium-containing dentate groups component can form a complex, and c) an acidic component.

During the polymerization, the polymers are obtained in the form of a suspension in the diluent. A problem with the above-described polymer preparation is the reactor fouling. During the polymerization, some of the polymers formed deposit on parts of the reactor that are below the liquid level, such as the reactor wall, the baffles, the agitator shaft, the agitator blades, the cooling and heating coils and the diving pipes. When the polymer slurry is removed from the reactor, these deposited polymers remain in the reactor and cannot be removed by rinsing the reactor with diluent. This reactor fouling can take very serious forms in some cases and, when the polymerization is carried out on a technical scale, can in extreme cases amount to about 40%, which means that of the polymer prepared only about 60% leaves the reactor in the form of a suspension, while about 40% remains deposited thereon on the reactor parts. This can seriously impede the application of polymerization on a technical scale.

The Applicant has conducted extensive research on this problem in the past. It has been found, among other things, that the reactor fouling can be combated somewhat by depositing, polishing or coating the surfaces on which the polymer tends to be coated with certain materials such as polypropylene, Teflon or nylon. Although these measures can reduce reactor fouling to a small extent, they are not suitable for combating the fouling problem effectively. The investigation further found that more effective control of reactor fouling can be achieved by suspending a solid in the diluent prior to contacting the monomers with the catalyst solution. As the solid used has a higher average particle size and a higher bulk density, a larger weight amount per liter of diluent should be suspended therefrom to effect a given reduction in reactor fouling. Finally, it has been found in the investigation that a very effective control of the reactor fouling can be achieved by replacing component c) in the catalyst composition with a polymer which does not or hardly dissolves in the diluent, and which contains sulfonic acid groups. Examples of such polymers are perfluorinated polymeric sulfonic acids of the Nafion type and sulfonated styrene / divinylbenzene copolymers of the Amberlite and Dowex type.

Further investigation has established that the use of the polymeric sulfonic acids used by the Applicant as component c) in the catalyst compositions poses a serious drawback, so that the application of this measure does not qualify on a technical scale. It has been found that the polymeric sulfonic acid used as a catalyst component has completely entered the polymer prepared after the polymerization has ended and cannot be easily removed therefrom. The presence of the acid in the polymer can have a very detrimental effect on the properties of the polymer in high-temperature processing and, for example, lead to discoloration and decomposition.

Upon further research by the Applicant on this subject, it has now been found that the aforementioned drawbacks associated with the use of an diluent-insoluble acid catalyst component c) which enters completely into the polymer prepared can be avoided by using component acid c) to use which is not or practically insoluble in the diluent and which can be obtained by reacting a solid support containing hydroxyl groups with a polybasic organic acid or anhydride containing at least one carboxyl or carboxylarhydride group, in which reaction said groups react with each other to form carboxyester groups. Using these solid acids as component c) containing free acid groups such as carboxylic or sulfonic acid groups, an equally effective control of the reactor fouling can be achieved as previously observed when using the polymeric sulfonic acids. Compared to the latter acids, however, they have the great advantage that during the polymerization, either by transesterification with a lower aliphatic alcohol present in the diluent or by hydrolysis with water present in the diluent, they are present at the carboxyester groups present in the compounds. are essentially cleaved, whereby the acid-reacting parts of the compound substantially dissolve and only a small amount of the hydroxyl group-containing support material remains in the polymer prepared. The presence of the latter material in the polymers does not adversely affect its properties in high temperature processing. The amount of solid which is introduced into the diluent according to the invention as a catalyst component is generally considerably less than the amount of any other solid which is to be suspended therein according to the reactor filling process previously found to provide a realize a corresponding reduction in reactor fouling.

Catalyst compositions based on the aforementioned components a) and b) and as component c) a supported acid as described above are new.

The present patent application therefore relates to new catalyst compositions which are based on a) a palladium-containing component, b) a bidentate ligand component which can form a complex with the palladium-containing component via two phosphorus, nitrogen or sulfur-containing dentate groups present therein, and c) a acid on support which can be obtained by reacting a support containing hydroxyl groups with a polybasic organic acid or anhydride containing at least one carboxyl or carboxyl anhydride group, in which reaction said groups react with each other to form carboxyester groups.

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

In the catalyst compositions according to the invention, component a) is preferably a palladium salt of a carboxylic acid and in particular palladium acetate.

If in the catalyst compositions according to the invention as component b) a bidentate ligand is used which can form a complex via two sulfur-containing dentate groups with component a) present therein, preference is given to a component b) of the general formula R ^ SR-SR ^ wherein R 1 represents an optionally polar substituted hydrocarbon group and R represents a divalent organic bridging group containing at least two carbon atoms in the bridge. Examples of such compounds are 1,2-bis (ethylthio) ethane, cis-1,2-bis (benzylthio) ethylene and 1,2-bis (phenylthio) propane.

If in the catalyst compositions according to the invention component b) is used, a bidentate ligand which can form a complex with component a) via two nitrogenous dentate groups present therein, is preferred a component

wherein X represents a nent b) of the general formula organic bridging group containing three or four atoms in the bridge of which at least two are carbon atoms. Examples of such compounds are 2,2'-bipyridine and 1,10-phenanthroline.

Preferably, in the catalyst compositions according to the invention, as component b), a bidentate ligand is used which can form a complex with component a) via two phosphorus-containing dentate groups present therein. When using such a bidentate ligand as component b), further preference is given to a compound of the general formula (R 1 ^ PR-PCR 1. Wherein R and R 1 have the previously indicated meaning. In this case, particular preference is given to a compound in which R 1 represents an aryl group ortho to the phosphorus atom to which it is bonded contains an alkoxy group as a substituent and in which R contains 3 atoms in the bridge An example of such a compound is 1,3-bis [bis (2-methoxyphenyl) phosphino] propane.

If in the catalyst compositions according to the invention component b) is used, a bidentate ligand which can form a complex with component a) via two sulfur or nitrogen-containing dentate groups contained therein, the amount used is preferably 0.5-100 and in particular 1 - 50 moles per mole of palladium. When using a bidentate ligand which can form a complex via two phosphorus-containing dentate groups with component a), the amount used is preferably 0.5-2 and in particular 0.75-1.5 mol per mol palladium.

The supported acid used as component c) in the catalyst compositions of the invention can be obtained by reacting a solid support containing hydroxyl groups with a polybasic organic acid containing at least one carboxyl or carboxyl anhydride group at which reaction said groups react with each other to form carboxyester groups. As examples of suitable carrier materials containing hydroxyl groups, polyvinyl alcohol and cellulose can be mentioned. Preferably, as the support material containing hydroxyl groups, a material is used that has similarities in structure with the polymer to be prepared. Preference is therefore given to carrier materials which can be prepared from linear polymers of carbon monoxide with one or more olefinically unsaturated hydrocarbons in which polymers, on the one hand, the units originating from carbon monoxide and, on the other hand, the units originating from the olefinically unsaturated hydrocarbons used, alternate in these polymers. convert at least a portion of the carbonyl groups to secondary alcohol groups. For example, one can prepare a suitable support material containing hydroxyl groups by contacting a linear alternating carbon monoxide / ethylene copolymer with sodium borohydride at room temperature.

As examples of suitable polybasic organic acids containing at least one carboxyl or carboxyl anhydride group, mention may be made of hexafluoroflutaric anhydride, hexafluoroflutaric acid, tetrafluorobamic acid and sulfoacetic acid. Preference is given to the use of a dicarboxylic acid anhydride, and in particular the use of hexafluoroblutaric anhydride. Preferably, the catalyst compositions according to the invention use such an amount of the acid on a support that the composition contains 1 to 50 and in particular 2 to 25 equivalents of acid per mole of palladium.

To increase the activity of the catalyst compositions according to the invention, a further 1,4-quinone can be incorporated therein as component d '). 1,4-benzoquinone and 1,4-naphthoquinone are very suitable for this purpose. The amount of 1,4-quinone used is preferably 5-5000 and in particular 10-1000 mol per mol palladium.

The polymer preparation using the catalyst compositions according to the invention is carried out by contacting the monomers at elevated temperature and pressure with a suspension of the catalyst composition in a diluent in which the polymers are not or practically insoluble and which diluent has a lower aliphatic contains alcohol and / or water. Very suitable diluents are lower aliphatic alcohols such as methanol and mixtures of water and an aprotic polar liquid such as acetone and tetrahydrofuran, which mixtures contain 5 to 15% by volume of water.

As examples of olefinically unsaturated hydrocarbons which can be polymerized with carbon monoxide using the catalyst compositions of the invention, mention may be made of ethylene, propylene, butene-1, hexene-1, octene-1, cyclopentene and styrene. The catalyst compositions are particularly well suited for use in the preparation of carbon monoxide copolymers with ethylene and in the preparation of carbon monoxide copolymers with ethylene and propylene.

The amount of catalyst composition used in the preparation of the polymers can vary within wide limits. Per mole of olefinically unsaturated hydrocarbon to be polymerized, an amount of catalyst composition is used which preferably contains 10 "- 10 - 10, and in particular 10 - 10 - 10, mole palladium.

The preparation of the polymers is preferably carried out at a temperature of 40-120 ° C and a pressure of 20-150 bar and in particular at a temperature of 50-100 ° C and a pressure of 30-100 bar. The molar ratio of the olefinically unsaturated hydrocarbons to carbon monoxide in the mixture to be polymerized is preferably 10: 1 to 1: 5 and especially 5: 1 to 1: 2.

The invention is now illustrated by the following examples.

Example 1

A carbon monoxide / ethylene copolymer was prepared as follows. 180 ml of methanol were placed in a 300 ml mechanically stirred autoclave. After the contents of the autoclave were brought to 90 ° C, a 1: 1 carbon monoxide / ethylene mixture was pressed in until a pressure of 55 bar was reached. Then a catalyst solution containing 24.5 ml of methanol, 1.5 ml of toluene, 0 was introduced into the autoclave. .01 mmol palladium acetate, 0.012 mmol 1,3-bis [bis (2-methoxyphenyl) phosphino] propane, and 0.20 mmol trifluoroacetic acid.

The autoclave pressure was maintained by pressing a 1: 1 carbon monoxide / ethylene mixture. After 2.58 hours, the polymerization was terminated by cooling to room temperature and releasing the pressure.

A polymer slurry containing 2.00 g copolymer was obtained. 4.22 g of copolymer remained in the autoclave. The reactor fouling in this experiment was therefore 2.00 + 4.22 x 100 ”68%

The polymerization rate was 2.3 kg copolymer / g palladium, hour.

Example 2

A catalyst composition containing as an acidic component a Nafion type perfluorinated polymer sulfonic acid having an acid strength of 0.8 meq / g was prepared as follows. 0.1 mmol of palladium acetate, 0.11 mmol of 1,3-bis [bis (2-methoxyphenyl) phosphino] propane and 4.1 g of the sulfonic acid were combined in 60 ml of methanol. After stirring at room temperature for 12 hours, the resulting catalyst composition was filtered off, washed with methanol and dried. The resulting catalyst composition contained 0.4 mg palladium / g.

Example 3

A carbon monoxide / ethylene copolymer was prepared as follows. 180 ml of methanol and 1.21 g of the catalyst composition prepared according to Example 2 were introduced into a mechanically stirred autoclave with a capacity of 300 ml. After the contents of the autoclave were brought to 90 ° C, a 1: 1 carbon monoxide / ethylene mixture was pressed in until a pressure of 55 bar was reached. The autoclave pressure was maintained by pressing a 1: 1 carbon monoxide / ethylene mixture. After 17.83 hours, the polymerization was terminated by cooling to room temperature and releasing the pressure. A polymer slurry containing 26.43 g copolymer was obtained. No reactor fouling had occurred in this case. The polymerization rate was 3.08 kg copolymer / g palladium hour. Example 4

A solid support containing hydroxyl groups was prepared as follows. 5 g of a linear alternating carbon monoxide / ethylene copolymer and 1 g of sodium borohydride were combined in 100 ml of methanol. After stirring at room temperature for 60 hours, the resulting partially hydrogenated copolymer was isolated by filtration, washed successively with methanol, dilute hydrochloric acid, water and methanol and dried.

Example 5

A supported acid was prepared as follows. In 100 ml of dry tetrahydrofuran, 2.4 g of hexafluoroblutaric anhydride and 4.6 g of the partially hydrogenated copolymer prepared according to Example 4 were combined. After stirring at room temperature for 3 hours, the resulting solid acid was isolated by filtration and five times to remove unreacted anhydride. washed with tetrahydrofuran. After drying, 5.6 g of the supported acid were obtained. The supported acid had an acid strength of 0.8 meq acid / g. Example 6

A catalyst composition containing as acidic component the acidic support obtained according to Example 5 was prepared as follows. 0.1 mmol of palladium acetate, 0.11 mmol of 1,3-bis [bis (2-methoxyphenyl) phosphinoipropane and 1 g of the supported acid were brought together in 60 ml of dry tetrahydrofuran. After stirring at room temperature for 2 hours, the resulting catalyst composition was isolated by filtration, washed with tetrahydrofuran and dried.

The resulting catalyst composition contained 8.7 mg palladium / g. Example 7

A carbon monoxide / ethylene copolymer was prepared essentially in the same manner as in Example 3, but with the following differences a) in the autoclave, 200 mg of the catalyst composition prepared according to Example 6 was substituted for the catalyst composition prepared according to Example 2, and b the reaction time was 5.03 hours instead of 17.83 hours.

A polymer slurry containing 17.80 g copolymer was obtained. 0.74 g of copolymer remained in the autoclave, so that the reactor fouling in this case was 4%. The polymerization rate was 2.1 kg copolymer / g palladium hour. Example 8

A catalyst composition containing the acidic support obtained according to Example 5 as an acidic component was prepared essentially in the same manner as in Example 6, but with the following differences a) in the 60 ml dry tetrahydrofuran were combined 0.183 mmol palladium acetate, 0.2 mmol 1,3-bis [bis (2-methoxyphenyl) phosphino] propane, and 1.8 gm of the supported acid.

b) Stirred for 70 hours instead of 2 hours.

The resulting catalyst composition contained 10 mg palla-diura / g.

Example 9

A carbon monoxide / ethylene copolymer was prepared essentially in the same manner as in Example 3, but with the following differences a) Into the autoclave, 100 mg of the catalyst composition prepared according to Example 8 was substituted for the catalyst composition prepared according to Example 2, and b the reaction time was 2.07 hours instead of 17.83 hours.

A polymer slurry containing 4.43 g copolymer was obtained. 0.41 g of copolymer had remained in the autoclave, so that the reactor fouling in this case was 8%. The polymerization rate was 2.3 kg copolymer / g palladium, hour.

Example 10

A carbon monoxide / ethylene copolymer was prepared essentially in the same manner as in Example 1, but with the following differences a) 200 ml of methanol was added to the autoclave instead of 180 ml and additionally 100 mg of the linear alternating carbon monoxide / ethylene copolymer which in Example 4 was used as starting material, and b) the reaction time was 2.68 hours instead of 2.58 hours.

A polymer slurry containing 2.91 g copolymer was obtained. 2.95 g of copolymer was left in the autoclave, so that the reactor fouling in this case was 51%. The polymerization rate was 2.0 kg copolymer / g palladium hour.

Of Examples 1-10, Examples 6-9 are according to the invention. Examples 6 and 8 concern the preparation of catalyst compositions according to the invention which contain, as component c), an acid on a support. In Examples 7 and 9, these catalyst compositions are used in the preparation of carbon monoxide / ethylene copolymers. Examples 1-5 and 10 are outside the scope of the invention. They are included in the patent application for comparison. Examples 1 and 10 concern the classic preparation of a carbon monoxide / ethylene copolymer by contacting the monomers with a solution of a catalyst composition. Examples 2 and 3 relate to the preparation and use of a catalyst composition containing as component c) a polymeric sulfonic acid of the Nafion type.

Examples 4 and 5 concern the preparation of a solid support containing hydroxyl groups as well as the preparation of a catalyst component c) according to the invention by reacting this solid support with hexafluoroblutaric anhydride.

It was determined by C-NMR analysis that the carbon monoxide / ethylene copolymers prepared according to Examples 1,3,7,9 and 10 consisted of linear chains in which units from carbon monoxide on the one hand and units from ethylene on the other hand alternated.

The effective control of the reactor fouling when using a catalyst composition according to the invention is evident when the results of Example 1 (68% reactor fouling) are compared with the results of Examples 7 and 9 according to the invention (4 and 8% reactor respectively). pollution). This comparison of the results of Examples 9 and 10 shows that this sharp decrease in reactor fouling is not caused by the presence of a solid in the reactor. Despite the presence of an amount of solid in the reactor, it is the same as that in Example. 9 when the solid catalyst composition used gave rise to a reactor fouling of only 8%, for example 10 a reactor fouling of 51% was observed.

Claims (26)

New catalyst compositions, characterized in that they are based on a) a palladium-containing component, b) a bidentate ligand component which can form a complex with the palladium-containing component via two phosphorus, nitrogen or sulfur-containing dentate groups contained therein, and c) a supported acid which can be obtained by reacting a solid support containing hydroxyl groups with a polybasic organic acid or anhydride containing at least one carboxyl or carboxyl anhydride group, in which reaction said groups react with each other to form carboxyester groups. Catalyst compositions according to claim 1, characterized in that they are based on a palladium salt of a carboxylic acid such as palladium acetate, as component a). Catalyst compositions according to claim 1 or 2, characterized in that they are based on a compound of the general formula R ^ SR-SR ^ as component b), in which general formula represents an optionally polar substituted hydrocarbon group and R represents a divalent organic represents a bridging group containing at least two carbon atoms in the bridge. Catalyst compositions according to claim 1 or 2, characterized in that they are based on a compound of the general formula

as component b), in Which general formula X represents an organic bridging group containing three or four atoms in the bridge of which at least two are carbon atoms. Catalyst compositions according to claim 3 or 4, characterized in that they contain 0.5-100 mol component b) per mole of palladium. Catalyst compositions according to claim 5, characterized in that they contain 1 to 50 moles of component b) per mole of palladium. Catalyst conpositions according to claim 1 or 2, characterized in that they are based on a compound of the general formula (¾) 2P-RP (¾) 2 a s component b), in which general formula R] is an optional polar substituted hydrocarbon group and R represents a divalent organic bridging group containing at least two carbon atoms in the bridge. Catalyst compositions according to claim 7, characterized in that they are based on a compound of the general formula (R1) 2P-R-P (Ri) 2 as component b), in which general formula represents an aryl group which is ortho-position relative to the phosphorus atom to which it is bonded, it contains an alkoxy group and R contains three atoms in the bridge, such as 1,3-bis [bis (2-methoxyphenyl) phospho] propane. Catalyst compositions according to claim 7 or 8, characterized in that they contain 0.5-2 mole component b) per mole palladium. Catalyst compositions according to claim 9, characterized in that they contain 0.75-1.5 mol component b) per mole of palladium. Catalyst compositions according to one or more of claims 1 to 10, characterized in that in the preparation of the acid on support, use is made of a solid support obtained in a linear polymer of carbon monoxide with one or more olefinically unsaturated hydrocarbons in which polymer, on the one hand, the units originating from carbon monoxide and, on the other hand, the units originating from the olefinically unsaturated hydrocarbons used, alternately convert at least part of the carbonyl groups into secondary alcohol groups. Catalyst compositions according to one or more of claims 1-11, characterized in that use is made of a dicarboxylic anhydride such as hexafluoroblutaric anhydride in the preparation of the acid on support. Catalyst compositions according to one or more of claims 1 to 12, characterized in that they contain an amount of component c) that contains 1 to 50 equivalents of acid per mole of palladium. Catalyst compositions according to claim 13, characterized in that they contain an amount of component c) that contains 2-25 equivalents of acid per mole of palladium. Catalyst compositions according to one or more of claims 1 to 14, characterized in that they additionally contain as component d) a 1,4-quinone, such as 1,4-benzoquinone or 1,4-naphthoquinone. Catalyst compositions according to claim 15, characterized in that they contain 5-5000 moles 1,4-quinone per mole palladium. Catalyst compositions according to claim 16, characterized in that they contain 10-1000 moles 1,4-quinone per mole palladium. Catalyst compositions according to claim 1, substantially as described above and in particular with reference to examples 6 and 8. Process for the preparation of polymers, characterized in that a mixture of carbon monoxide with one or more olefinically unsaturated hydrocarbons is contacted at elevated temperature and pressure with a suspension of a catalyst composition according to one or more of claims 1— 18 in a diluent in which the polymers are insoluble or practically insoluble and which diluent contains a lower aliphatic alcohol and / or water. Method according to claim 19, characterized in that the diluent used is a lower aliphatic alcohol such as methanol or a mixture of water with an aprotic polar liquid such as acetone or tetrahydrofuran, which mixture contains 5 to 15% by volume of water. Process according to claim 19 or 20, characterized in that it is used for preparing copolymers of carbon monoxide with ethylene or terpolymers of carbon monoxide with ethylene and with another olefinically unsaturated hydrocarbon such as propylene. Process according to one or more of claims 19 to 21, characterized in that it is carried out at a temperature of 40-120 ° C, a pressure of 20-150 bar and a molar ratio of the olefinically unsaturated hydrocarbons to carbon monoxide in the polymerizable mixture of 10: 1 to 1: 5 and using an amount of catalyst composition containing 10-7 to 10 moles of palladium per mole of olefinically unsaturated hydrocarbon to be polymerized. Process according to claim 22, characterized in that it is carried out at a temperature of 50-100®C, a pressure of 30-100 bar and a molar ratio of the olefinically unsaturated hydrocarbons to carbon monoxide in the mixture to be polymerized from 5: 1 to 1: 2 and using an amount of catalyst composition containing 10 "to 10" moles of palladium per mole of olefinically unsaturated hydrocarbon to be polymerized. A process for the preparation of polymers according to claim 19, essentially as described above and in particular with reference to Examples 7 and 9. Polymers prepared according to one or more of claims 19-24. Shaped articles which at least partly consist of polymers according to claim 25.