WO2000009521A1 - Compositions catalytiques et procede de preparation de polycetones - Google Patents

Compositions catalytiques et procede de preparation de polycetones Download PDF

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Publication number
WO2000009521A1
WO2000009521A1 PCT/EP1999/005986 EP9905986W WO0009521A1 WO 2000009521 A1 WO2000009521 A1 WO 2000009521A1 EP 9905986 W EP9905986 W EP 9905986W WO 0009521 A1 WO0009521 A1 WO 0009521A1
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group
catalyst composition
represent
atom
independently
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PCT/EP1999/005986
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English (en)
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Eit Drent
Alexander Willem Van Der Made
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Shell Internationale Research Maatschappij B.V.
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Priority to AU58522/99A priority Critical patent/AU5852299A/en
Publication of WO2000009521A1 publication Critical patent/WO2000009521A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • 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 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.
  • polymers of carbon monoxide hereafter referred to as "CO"
  • CO carbon monoxide
  • 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 (R 1 R 2 ) 1 -R-M 2 (R 3 R 4 ) , wherein M 1 and M 2 , independently, represent phosphorus, nitrogen, arsenic or antimony, R represents a divalent organic bridging group and R ⁇ -, R 2 ,
  • R 3 and R 4 are identical or different hydrocarbyl groups.
  • 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.
  • 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.
  • EP-A-489 473 also teaches that there is an exception.
  • CO is polymerised with an ⁇ -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.
  • 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.
  • 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.
  • 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
  • R R wherein Z represents a Group VIII metal selected from palladium, cobalt and nickel and (R-R 2 ) Mi-R-M 2 (R 3 R 4 ) represents the ligand, in which
  • M- and M independently, represent a phosphorus, nitrogen, arsenic or antimony atom;
  • R , R 2 , R 3 and R 4 independently, represent either identical or different, optionally polar substituted hydrocarbyl groups
  • R represents a divalent organic bridging group in which the bridge connecting M ⁇ and M 2 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 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.
  • 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.
  • the group VIII metal is selected from palladium and nickel.
  • the Group VIII metal is palladium.
  • the Group VIII metal is typically employed as a cationic species.
  • a Group VIII metal salt is used as the source of Group VIII metal cations. 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.
  • 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 ⁇ R 1 ⁇ ) Mi-R-M (R 3 R 4 ) represents a multidentate ligand, e.g. a bidentate, tridentate or tetradentate ligand.
  • a multidentate ligand e.g. a bidentate, tridentate or tetradentate ligand.
  • M ⁇ and M 2 independently, represent a phosphorus, nitrogen, arsenic or antimony atom.
  • one of M 1 or M 2 is a phosphorus atom, more preferably both M ⁇ and M 2 represent a phosphorus atom.
  • the ligand (R!R 2 ) i-R-M 2 (R 3 R 4 ) is a bisphosphine compound.
  • Ri, R 2 , R 3 and R independently, represent either identical or different hydrocarbyl groups such as alkyl, aryl, aralkyl or cycloalkyl groups.
  • aryl group includes
  • R 1 , R 2 , R 3 and R 4 contain not more than 15 carbon atoms, more typically not more than 10 carbon atoms.
  • at least one of R ⁇ -, R 2 , R 3 and R 4 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-, R 5 RgN-CO-, R5-O-CO-NH- and R5-O-CO-NR5-, wherein R 5 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-,
  • the present invention also relates to ligands represented by the general formula (R ⁇ -R 2 ) M!-R-M 2 (R 3 R 4 ) and which are capable of forming a complex of the formula I, wherein M 1 and M 2 , independently, represent a phosphorus, nitrogen, arsenic or antimony atom, R 1 -, R 2 ,
  • R 3 and R 4 independently, represent either identical or different aryl groups containing a polar substituent at an ortho position with respect to the M 1 and M 2 atom, and R represents a divalent organic bridging group in which the bridge connecting M ⁇ - and M 2 consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge.
  • the groups R ⁇ and R 2 and/or the groups R 3 and R 4 are alkyl groups which are interconnected by a chemical bond, additional to the connection via atom M ⁇ and/or the atom
  • (R 1 R 2 )M 1 and/or (R 3 R 4 )M 2 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 M 2 , respectively.
  • the particular cyclic structure is a 9-phosphabicyclononyl group.
  • both of (R 1 R 2 )M 1 and (R 3 R 4 )M 2 represent a cyclic structure, in particular a 9-phosphabicyclonyl 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 ⁇ -R 2 ) Mi-R-M (R 3 R 4 ) which are capable of forming a complex of the formula I and wherein (R-*-R 2 )M1 and
  • R 3 R )M 2 independently represent a bicyclononane group wherein one methylene group is replaced by an atom M ⁇ or an atom M 2 respectively, M 1 and M 2 independently represent a phosphorus, nitrogen, arsenic or antimony atom, and R represents a divalent organic bridging group in which the bridge connecting M ⁇ and M 2 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 M 2 consists of four atoms, and which bridging group contains a single cyclic structure sharing an unsaturated carbon-carbon bond with said bridge.
  • a "single cyclic structure” is understood to be one structure which is monocyclic or polycyclic.
  • “bridging group” is understood to be the complete moiety that connects the M 1 and M 2 atoms.
  • “Bridge”, being a part of the bridging group, is understood to consist of the shortest chain of atoms that connects M 1 and M 2 .
  • 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.
  • all four atoms of the bridge connecting M 1 and M 2 are carbon atoms .
  • the bridging group R may be represented by the general formula:
  • Y represents a bivalent cyclic hydrocarbon group comprising an unsaturated carbon-carbon bond, which bond is part of the bridge connecting M ⁇ and M 2 .
  • Y is an aromatic structure, which may or may not be fused, such as phenylene, naphthylene, phenantrylene .
  • Y is a 1, 2-phenylene group.
  • Y will contain from 4 to 20 carbon atoms, preferably from 6-20 carbon atoms, most preferably from 6-14 carbon atoms.
  • Y may optionally be substituted with e.g. alkyl groups or polar groups and may contain heteroatoms such as oxygen, nitrogen, phosphorus and sulphur.
  • R 7 and R 8 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.
  • R 7 and R 8 may be substituted with substituents, such as alkyl substituents having up to 4 carbon atoms.
  • substituents such as alkyl substituents having up to 4 carbon atoms.
  • 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.
  • ligands according to the invention with which very favourable results can be obtained are: l,2-bis ⁇ [bis (2-methoxyphenyl) phosphino] methyl ⁇ - benzene; and
  • 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.
  • suitable anions are those which are non- or only weakly co-ordinating with the Group VIII metal under the conditions of the copoly- merization.
  • 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.
  • protic acids examples include the above mentioned acids which may also participate in the Group VIII salts, e.g. trifluoroacetic acid and maleic acid.
  • 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 .
  • protic acids which may be combined with a Lewis acid are sulphonic acids and hydrohalogenic acids, in particular hydrogen fluoride.
  • tetrafluoroboric acid and hexafluorophos- phosphorus acid are tetrafluoroboric acid and hexafluorophos- phosphorus acid (HBF4 and HPFg) .
  • 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.
  • tetraarylborates such as tetraphenylborate, tetrakis [3, 5-bis ( trifluoromethyl) phenyl] borate and tetrakis (perfluorophenyl) borate, and carborate
  • 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 .
  • 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.
  • 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 .
  • 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
  • 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.
  • ethene and other ⁇ -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 ⁇ -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.
  • a diluent is used in which the admixed catalyst composition is soluble and in which the copolymer to be prepared forms a suspension.
  • a diluent may be selected in which the copolymer is insoluble or virtually insoluble.
  • 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.
  • 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.
  • the molar ratio of the olefinically unsaturated compounds relative to CO is preferably 10:1-1:10, and in particular 5:1-1:5.
  • 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.
  • 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.
  • 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.
  • 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.
  • a disadvantage of applying a higher temperature is that the stability of the catalyst composition may become a problem.
  • 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 ⁇ -R 4 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 .
  • the catalyst compositions according to the present invention are more effective in incorporating this ⁇ -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.
  • RI-R 4 represent alkyl groups
  • R 2 and/or the groups R 3 and R 4 are alkyl groups which are interconnected by a chemical bond, such that (R 1 R )M 1 and/or (R 3 R )M 2 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 materials.
  • 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 .
  • 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.
  • a catalyst solution which consisted of: 40 ml of a mixture of methanol/acetone, 0.1 mmol palladium acetate,
  • the autoclave was closed, and stirring was started.
  • the autoclave was purged with N 2 at 50 bar.
  • the autoclave was heated to 90 °C .
  • 24 bar CO and 24 bar ethene was forced in until a pressure of 50 bars was achieved.
  • an 1/1 (mol/mol) CO/ethene mixture was supplied continuously to the autoclave to maintain a pressure of 50 bar.
  • 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 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,
  • 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.
  • 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 .
  • a linear alternating terpolymer of CO with ethene and propene was prepared as follows .
  • the autoclave was closed, and stirring was started.
  • the autoclave were purged with N2 at 50 bar.
  • the autoclave is flushed three times with CO and 72 gram propene are added.
  • 10 bars of CO were introduced and the autoclave is heated to 76 °C .
  • the polymerisation temperature is reached the autoclave is pressurised with ethene to reach a final pressure of 46.
  • 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 .
  • Example 5 (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.
  • the autoclave was closed, and stirring was started.
  • the autoclave was evacuated, flushed three times with CO and subsequently 30 ml propene was added.
  • 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 .
  • 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 was 0.06.
  • 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 13 C-NMR) was 0.11.

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Abstract

L'invention porte sur des compositions catalytiques basées sur un métal du groupe VIII et sur un ligand formant ensemble un complexe de formule (I) dans laquelle Z représente un métal du groupe VIII choisi parmi le palladium, le cobalt et le nickel, et (R?1R2)M1-R-M2(R3R4¿) représente le ligand dans la formule duquel: M?1 and M2¿ représentent indépendamment un atome de phosphore, d'azote, d'arsenic ou d'antimoine; R?1, R2, R3 et R4¿ représentent indépendamment des groupes hydrocarbyle identiques ou différents à substitution polaire facultative; et R représente un groupe bivalent de pontage dont le pont reliant M1 et M2, qui consiste en quatre atomes, comporte une unique structure cyclique partageant une liaison carbone-carbone non saturée avec ledit pont. L'invention porte également sur un procédé de préparation de polymères de CO et d'un ou plusieurs composés non saturés en oléfines par mise en contact desdits monomères avec ladite composition catalytique.
PCT/EP1999/005986 1998-08-13 1999-08-11 Compositions catalytiques et procede de preparation de polycetones WO2000009521A1 (fr)

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WO2003040065A3 (fr) * 2001-11-09 2004-01-22 Shell Int Research Procede de telomerisation d'un diene conjugue, et catalyseur et ligand bidente utiles dans ce procede
US6794553B2 (en) 2001-11-09 2004-09-21 Shell Oil Company Process for the telomerization of a conjugated diene, catalyst and bidentate ligand useful therein
US7057082B2 (en) 2001-11-09 2006-06-06 Shell Oil Company Process for the telomerization of a conjugated diene, catalyst and bidentate ligand useful therein
US7491859B2 (en) 2001-11-09 2009-02-17 Shell Oil Company Process for the telomerization of a conjugated diene, catalyst and bidentate ligand useful therein

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