Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
  • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds

Definitions

• the invention relates to a process for the preparation of copolymers of carbon monoxide and one or more ethylenically unsaturated compounds.
• Linear copolymers of carbon monoxide with one or more ethylenically unsaturated compounds in which copolymers the units originating from carbon monoxide on the one hand and the units originating from the ethylenically unsaturated compound(s) on the other hand occur in a substantially alternating arrangement, can be prepared by reacting the monomers under polymerization conditions in the presence of a suitable palladium comprising catalyst system.
• the linear copolymers, thus prepared are eminently suitable for use in various outlets for thermoplastics. They may be further processed by means of conventional techniques into films, sheets, plates, fibres and shaped articles for domestic use and for parts in the car industry.
• a suitable method for the preparation of the said copolymer which is usually performed in batch operation, is described in EP-A-181014 and EP-A-121965.
• a catalyst obtained by reaction of, in particular, a palladium compound, an anion of a carboxylic acid with a pKa lower than 2 and a bidentate ligand of the general formula Q-*-Q ⁇ M-X-MQ 3 Q ⁇ , wherein M represents phosphorus, arsenic or antimony, X represents a divalent organic bridging group having at least two carbon atoms in the bridge, none of which carries steric hindrance causing substituents, and Q ⁇ -, Q ⁇ , Q 3 and Q ⁇ are similar or dissimilar hydrocarbon groups.
• the catalyst and the polymerization conditions had to be selected such that copolymers with high molecular weights are formed, since in general products with higher molecular weights are more suitable for the above-mentioned uses.
• the formation of high molecular weight copolymers is enhanced by performing the reaction at a low reaction temperature.
• the activity of the initially used catalysts often proved to be inadequate for achieving a viable production rate.
• the rate of copolymer formation could be improved, but the molecular weight of the copolymers will then drop.
• reaction rate is significantly increased by using a bisphosphine ligand of the formula Q 5 Q 6 P-X-PQ 7 Q 8 , wherein at least one of the groups Q ⁇ .. Q° represents an aryl group containing at least one polar substituent in an ortho-position with respect to phosphorus.
• a process of this type is disclosed in EP-A-319083 and in EP-A-257663. It would further appear that the activity of catalysts comprising a bidentate ligand of the general formula Q 1 Q 2 M-X 1 -MQ 3 Q 4 wherein X 1 represents a bivalent bridging group containing three atoms in the bridge, viz.
• the bulk density expressed in kg copolymers per m 3 reaction medium, represents an important property of the copolymers at issue.
• the bulk density plays an important role both in the preparation of the copolymers and in the treatment, storage, transport and processing thereof.
• US-A-5010170 disclosed that in the palladium/bidentate ligand catalyzed copolymerization of carbon monoxide with olefins the use of a mixture of phosphorus bidentate ligands leads to a decrease of reactor fouling.
• the ligand mixture comprises a bidentate ligand carrying at the phosphorus atoms four ortho-alkoxy substituted aryl groups and a bidentate ligand carrying at the phosphorus atoms four aryl groups which are free of alkoxy substitution.
• An example of a ligand with ortho-alkoxy substitution is 1,2-bis [bis (2,4-diethoxy- phenyDphosphino]ethane. This document does not provide any teaching which could bring the skilled person to the present invention.
• the present invention relates to a catalyst system suitable for the copolymerization of carbon monoxide with an ethylenically unsaturated compound which catalyst system is based on
• the quantity of bidentate ligands of the general formula (I) in the ligand mixture is preferably at least 95 %-mole, in particular more than 98 %-mole, relative to the total quantity of the bidentate ligands.
• Such a ligand mixture may comprise a bidentate ligand of the general formula (I) wherein each of R 1 , R 2 , R 3 and R 4 carries an alkoxy group at an ortho-position with respect to the phosphorus atom and a bidentate ligand of the general formula R 5 R 6p_ ⁇ 2_ PR 7 R 8 W erein R 5 , R 6 , R 7 and R 8 independently represent aryl groups, typically of up to 10 carbon atoms, which are free of alkoxy substituents and X 2 represents a divalent hydrocarbyl group typically having 2-4 carbon atoms in the bridge.
• R 5 , R 6 , R 7 and R 8 independently represent aryl groups, typically of up to 10 carbon atoms, which are free of alkoxy substituents and X 2 represents a divalent hydrocarbyl group typically having 2-4 carbon atoms in the bridge.
• Such a ligand mixture is typically present in a quantity of 0.5 - 2 mole per gram atom of palladium, and may be used in the catalyst system which is in addition based on an anion of an acid having a pKa of less than 4, typically in a quantity of 0.5 - 50 equivalents per gram atom palladium.
• Bidentate ligands of the general formula (I) are preferably applied as the sole ligands.
• the invention relates to a process for the preparation of copolymers of carbon monoxide and an ethylenically unsaturated compound by reacting the monomers in the presence of a catalyst system according to this invention.
• a palladium salt As source of palladium cations, i.e. component (a) of the catalyst system, conveniently a palladium salt is used. Suitable salts include salts of mineral acids such as sulphuric acid, nitric acid, phosphoric acid and sulphonic acids. Preferably, a palladium 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 represents a particularly preferred source of palladium cations.
• R represents a phenyl group substituted with one or more polar groups.
• the polar group(s) may be located at an ortho position with respect to the phosphorus atom to which ⁇ is linked, at the para-position, or, in the event of more than one polar group, - 5 - at both ortho-positions, or at an ortho- and the para-position.
• a single polar substituent, located at an ortho-position is preferred.
• Suitable polar groups include alkoxy groups and thio-alkyl groups such as a thiomethyl group.
• Alkoxy groups are preferred, in particular C1-C alkoxy groups,
• C1-C4 having its usual meaning, indicating methyl, ethyl, propyl, isopropyl, n-butyl, sec.butyl, isobutyl and tertiary butyl.
• R ⁇ The presence of a methoxy group in R ⁇ at an ortho-position with respect to the phosphorus atom, is most preferred. It is recommended to use a catalyst system comprising a ligand of formula (I) wherein each of R 2 , R 3 and R 4 represents an aryl group, typically having up to 10 carbon atoms, in particular a phenyl group.
• the aryl groups are preferably substituted with a polar group.
• R 2 , R 3 and R 4 all have the same meaning as R 1 .
• a particularly preferred bidentate ligand of formula (I) is 1,2-bis[di(2-methoxyphenyl)phoshino]ethane.
• the amount of bidentate ligand supplied to the catalyst system may vary, but is conveniently selected in the range from 0.5 to 2 moles of bidentate ligand per gram atom of palladium. Preferably, the amount is in the range of 0.75 to 1.5 moles of ligand per gramatom of palladium.
• the catalyst system may be based on an additional component which is generally thought to function during the copolymerization as a source of anions which are non- or only weakly co-ordinating with palladium.
• additional components are, for example, protic acids, salts of protic acids, Lewis acids, combinations of Lewis acids and protic acids, and salts derivable from such combinations.
• Suitable are strong acids, in particular having a pKa of less than 3, more in particular less than 2, when measured in aqueous solution at 18 °C.
• suitable acids are the above mentioned acids which may also participate in the palladium salts, e.g. trifluoroacetic acid.
• Suitable acids are adducts of boric acid and 1,2-diols, catechols or salicylic acids. Salts of. these acids may be used as well.
• Other suitable salts contain one or more hydrocarbylborate anions or carborate anions, such as sodium tetrakis[bis-3,5-(trifluoromethyl)phenyl]borate, lithium tetrakis- (perfluorophenyl)borate and cobalt carborate (Co i 2 -* ⁇
• Suitable Lewis acids are, for example, BF3, SnCl2, SnF 2 and Sn(CF3S03)2 and hydrocarbylboranes, such as triphenylborane, tris- (perfluorophenyl)borane and tris[bis-3,5-(trifluoromethyl)phenyl]- borane.
• Protic acids with which Lewis acids may be combined are for example sulphonic acids and hydrohalogenic acids, in particular HF.
• An example of a combination of a Lewis acid with a protic acid is tetrafluoboric acid (HBF4).
• HBF4 tetrafluoboric acid
• Other compounds which may be mentioned in this context are aluminoxanes, in particular methyl aluminoxanes and t-butyl aluminoxanes.
• the additional component on which the catalyst system is based contains boron. It is in particular a boron containing Lewis acid, protic acid or salt. Very good results can be obtained with an boron containing protic acid having a pKa of less than 2 which is tetrafluoboric acid.
• the amount of the additional component which is generally thought to function as an anion source is preferably selected in the range of 0.5 to 50 moles per gram atom of palladium, in particular in the range of 1 to 25 moles.
• the aluminoxanes may be used in such a quantity that the molar ratio of aluminium to palladium is in the range of 4000:1-10:1, preferably 2000:1-100:1.
• the activity of the catalyst system is such, that amounts in the range from 10 ⁇ ° to 10 ⁇ 1 gram atom of palladium per mole of ethylenically unsaturated compound to be copolymerized, are adequate. Preferably, the amount will be between 10 -7 to 10 -2 , on the same basis.
• olefins are preferred, in particular lower olefins, i.e. ethene and propene or mixtures thereof.
• Ethene is most preferred as monomer for the copoly ⁇ merization with carbon monoxide, in particular as the sole or substantially sole ethylenically unsaturated compound.
• the presence of a quantity of another ethylenically unsaturated compound may be tolerable, in particular such that the other ethylenically unsaturated compound is incorporated in the copolymer in a quantity of less than 2 %-mole, preferably less than 1 %-mole, calculated on the total of ethylenically unsaturated compounds incorporated.
• the starting materials are conveniently applied in ratios such that per mole of carbon monoxide 0.25 to 4 moles of ethylenically unsaturated compound(s) is (are) present.
• the molar ratio between the two monomers is in the range of 3:1 to 1:3, in particular in the range of 1.5:1 to 1:1.5.
• the process of the invention is conveniently carried out in the presence of a suitable diluent. Since the copolymers of the invention are insoluble or virtually insoluble in many conventional liquid solvents, a large number of these liquids may be used as diluent during the copolymerization reaction.
• Recommended diluents are polar organic liquids, such as ketones, ethers, esters or amides.
• protic liquids are used, such as monohydric and dihydric alcohols.
• a high LVN is indicative of a high molecular weight of the copolymer.
• a solid particulate material suspended in the diluent before the monomers are contacted with the catalyst system.
• Suitable solid particulate materials are silica, polyethene and a copolymer of carbon monoxide and an ethylenically unsaturated compound, preferably a copolymer which is based on the same monomers as the copolymer to be prepared.
• the quantity of the solid particulate material is preferably in the range of 0.1-20 g, particularly 0.5-10 g per 100 g diluent.
• a catalyst system is used which is supported on a solid carrier material.
• Suitable solid materials include organic compounds, such as polymers and resins, in particular ion exchanging resins, and inorganic compounds such as zeolites and inorganic oxides, e.g. silica, alumina, titania, zirconia and the like. Inorganic oxides are preferred carrier materials and among these, in particular silica, or a silica containing oxide-mixture.
• the amount of carrier material to be used for the supported catalysts may vary considerably. To a large extent the size of the carrier material determines the amount required for an optimal performance of the catalyst.
• the particle size is in the range of 0.001 to 5 microns, preferably in the range of 0.005 to 4 microns.
• the said particle sizes are usually indicated as D50 values, i.e. the size (in microns) whereby 50% of the particles has a particular diameter. If a particle size range is given, the diameters of substantially all particles are within the said range. Materials having a D50 of 0.01 are especially preferred.
• a catalyst system may be used, which additionally comprises an organic oxidant. Examples of suitable oxidants include quinones such as 1, -benzoquinone, 1,2-naphthoquinone and 1,4- naphthoquinone.
• the conditions under which the process of the invention is performed include the use of elevated temperatures and pressures, such as between 20 and 200 °C, in particular 30 and 130 °C and 1-200 bara, in particular 5-100 bara.
• Preferred reaction temperatures are in the range of 70 to 130 ⁇ C, temperatures in the range of 80 to 100 ⁇ C being most preferred.
• reaction pressure is preferably selected in the range of 40 to 80 bara, but pressures outside these limits are not precluded.
• EXAMPLE 1 A carbon onoxide/ethene copolymer was prepared as follows. A stirred 200 ml autoclave was charged with 90 ml of ethanol, 1.58 g of linear alternating carbon monoxide/ethene copolymer (obtained in a previous experiment) , and a catalyst solution consisting of 10 ml of methanol, 0.0094 mmol of palladium-II-acetate, 0.188 mmol of fluoboric acid (HBF 4 ) and 0.0104 mmol of 1,2-bis[di(2-methoxy- phenyl)phosphino]ethane.
• the air in the autoclave was displaced by nitrogen (1 bara) .
• the autoclave was then heated to 90 ⁇ C and pressurized with an equimolar mixture of carbon monoxide and ethene until a pressure of 50 bar was reached. Accordingly, the polymerization started. During the reaction the pressure was maintained by pressurizing with an equimolar carbon monoxide/ethene mixture. After 3 hours the polymerization was terminated by depressurization and subsequent cooling to ambient temperature.
• the yield was 26.5 g of copolymer having a bulk density of
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 1, with the difference that the reactor was pressurized with a mixture of carbon monoxide and ethene in a molar ratio of 0.40:1 instead of with an equimolar carbon monoxide/ethene mixture.
• the yield was 36.1 g of copolymer having a bulk density of 315 kg/m 3 .
• the polymerization rate was 11.5 kg of copolymer per gram of palladium and per hour.
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 1, with the difference that the reactor was pressurized with a mixture of carbon monoxide and ethene in a molar ratio of 1.42:1, instead of with an equimolar mixture.
• the yield was 25.6 g of copolymer having a bulk density of 230 kg/m 3 .
• the polymerization rate was 8.0 kg of copolymer per gram of palladium and per hour.
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 1 with the difference that a reaction temperature of 85 ⁇ C, instead of 90 C C was applied.
• the yield was 20.2 g of copolymer having a bulk density of 195 kg/m 3 .
• the polymerization rate was 6.2 kg of copolymer per gram of palladium and per hour.
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 1 with the difference that the reaction temperature was 95 ⁇ C, instead of 90 C C.
• the yield was 30.7 of copolymer having a bulk density of
• the polymerization rate was 9.7 kg of copolymer per gram of palladium and per hour.
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 1, with the difference that 0.188 mmol of trifluoroacetic acid was used, instead of fluo-boric acid.
• the yield was 16.9 g of copolymer having a bulk density of 107 kg/m 3 .
• the polymerization rate was 5.1 kg of copolymer per g of palladium and per hour.
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 6, with the difference that 0.104 mmol of
• the reaction had to be terminated after 1 h, because fluffy product was formed, hindering proper mixing of the reactor contents.
• the yield was 8.7 g of copolymer having a bulk density of 80 kg/m 3 .
• the polymerization rate was 8.1 kg of copolymer/g palladium and per hour.
• a carbon monoxide/ethene copolymer was prepared as follows. A stirred 300 ml autoclave was charged with 100 ml of methanol. Air was removed by pressurizing with carbon monoxide and subsequently the pressure was increased to 50 bar by pressurizing with a mixture of carbon monoxide and ethene in a molar ratio of 1.5:1.
• the temperature was raised to 96 ⁇ C and subsequently a catalyst solution was injected with the carbon monoxide stream at an additional pressure of 5 bar.
• the catalyst solution consisted of 0.01 mmol of palladium (II) acetate 0.012 mmol of 1,2-bis[di(2- methoxyphenyDphosphino]ethane and 0.2 mmol of fluoboric acid in 10 ml of methanol. Accordingly, the reaction started and was terminated after 1 hour.
• the yield of copolymer was 13 g.
• the polymerization rate was 13 kg of copolymer per gram of palladium and per hour.
• the Limiting Viscosity Number (LVN) of the copolymer was 0.7 ml/g.
• EXAMPLE 8 A carbon monoxide/ethene copolymer was prepared, substantially as described in Example 7, with the difference that a mixture of 50 ml of tertiary butanol and 50 ml of methanol was used, instead of 100 ml of methanol.
• the yield of copolymer was 10 g.
• the polymerization rate was still 10 kg of copolymer per gram of palladium and per hour.
• the LVN of the copolymer had increased to 4.5 dl/g.
• a copolymer of carbon monoxide and ethene was prepared, substantially as described in Example 7, with the difference that 0.012 mmol of 1,3-bis[di- (2-methoxyphenyl)phosphino]propane was used instead of 1,2-bis[di(2-methoxyphenyl)phosphino]ethane.
• the copolymer obtained had a LVN of 2.0 dl/g and was produced with a polymerization rate of 10 kg of copolymer per gram of palladium and per hour.
• a copolymer of carbon monoxide and ethene was prepared as follows. A 300 ml autoclave was charged with 5 g of CLA 27252 (a commercially available silica having a particle size (D50) of 3.5 micron), palladium-II-acetate(1.5 mg Pd) , 1,2-bis[di(2- methoxyphenyDphosphino]ethane and fluoboric acid-dimethylether such that the molar ratio palladium compound: bidentate ligand: acid anion was 1.0:1.1:5.0 and 150 ml of methanol.
• CLA 27252 a commercially available silica having a particle size (D50) of 3.5 micron
• palladium-II-acetate(1.5 mg Pd) 1,2-bis[di(2- methoxyphenyDphosphino]ethane and fluoboric acid-dimethylether
• the molar ratio palladium compound: bidentate ligand: acid anion
• the temperature of the contents of the autoclave was raised to 90 °C, whereupon the polymerization started.
• the reaction was terminated after a runtime of 5 hours.
• the polymerization rate was 2.1 kg of copolymer per g of palladium and per hour.
• the bulk density of the copolymer was
• a copolymer of carbon monoxide and ethene was prepared, substantially as described in Example 9, with the difference that 1,3-bis[di(2-methoxyphenyl)phosphino]propane was used instead of
• EXAMPLE 10 A copolymer of carbon monoxide and ethene was prepared, substantially as described in Example 9, with the difference that
• Organo-silicasol (a commercially available silica with a particle size (D50) of 0.01 micron) was used instead of CLA-27252.
• the polymerization rate was 5.8 kg of copolymer per g of palladium and per hour.
• the bulk density of the copolymer was
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 10, with the difference that 1,3-bis[di(2- methoxy-phenyl)phosphino]propane was used instead of 1,2-bis[di(2- methoxyphenyDphosphino]ethane.
• the polymerization rate was 9.6 kg of copolymer per g of palladium and per hour.
• the bulk density of the copolymer was 120 kg/m 3 .
• EXAMPLE 11 A carbon monoxide/ethene copolymer was prepared, substantially as described in Example 10, with the difference that trifluoro ⁇ acetic acid was used instead of fluoboric acid-dimethylether.
• the polymerization rate was 5.1 kg of copolymer per g of palladium and per hour.
• the bulk density of the copolymer was 370 kg/m 3 .
• EXAMPLE F (for comparison, not according to the invention)
• a carbon monoxide/ethene copolymer was prepared, substantially as described in Example 11, with the difference that 1,3-bis[di(2- methoxyphenyDphosphino]propane was used instead of 1,2-bis[di(2- methoxyphenyl)phosphino]ethane.
• the polymerization rate was 8.3 kg of copolymer per g of palladium and per hour.
• the bulk density of the copolymer was 127 kg/m 3 .

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• 1995
  • 1995-04-26 ZA ZA953387A patent/ZA953387B/xx unknown
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  • 1995-04-28 WO PCT/EP1995/001678 patent/WO1995029946A1/en not_active Application Discontinuation
  • 1995-04-28 CA CA002188921A patent/CA2188921A1/en not_active Abandoned
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