EP1192205A1 - Katalysator zusammensetzung und ihre verwendung - Google Patents

Katalysator zusammensetzung und ihre verwendung

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Publication number
EP1192205A1
EP1192205A1 EP00945888A EP00945888A EP1192205A1 EP 1192205 A1 EP1192205 A1 EP 1192205A1 EP 00945888 A EP00945888 A EP 00945888A EP 00945888 A EP00945888 A EP 00945888A EP 1192205 A1 EP1192205 A1 EP 1192205A1
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EP
European Patent Office
Prior art keywords
group
groups
catalyst composition
carbon
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00945888A
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English (en)
French (fr)
Inventor
Roelof Van Ginkel
Alexander Willem Van Der Made
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to EP00945888A priority Critical patent/EP1192205A1/de
Publication of EP1192205A1 publication Critical patent/EP1192205A1/de
Withdrawn legal-status Critical Current

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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
    • B01J31/24—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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
    • C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
    • 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
    • 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
    • B01J31/1895—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 the ligands containing arsenic or antimony
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper

Definitions

  • the present invention relates to catalyst compositions and their use as catalyst in the preparation of polyketone polymers .
  • Catalyst compositions for preparing polyketone polymers are known in the art. Typically, such catalyst compositions are based on a Group VIII metal compound, a bidentate ligand and an anion of an acid having a pKa of 6 or less .
  • Bidentate ligands frequently used have the general formula R.2M-R'- R2, wherein each R independently represents an optionally substituted hydrocarbyl group, each M represents a chelating atom selected from arsenic, antimony, phosphorus and nitrogen and R 1 represents a bivalent bridging group, typically comprising from 1 to 4 atoms in the bridge, which atoms may or may not carry substituents . Carbon and silicon atoms often form the bridge, while the substituents, if any, normally consist of carbon and hydrogen and optionally oxygen.
  • Such a catalyst composition has many variables which could have an impact on the performance of the catalyst when preparing polyketones .
  • Important variables in this respect are the Group VIII metal compound used, the type of anion used and in respect of the bidentate ligand: the groups attached to the chelating atoms and the bridging group.
  • Important parameters defining the performance of the catalyst are bulk density of the polymer prepared and activity defined in terms of polymerization rate.
  • other effects of using particular catalysts like fouling and building in of higher olefins into the polyketone polymer chain could be important.
  • a general purpose of the present invention is to provide a catalyst composition having an excellent performance in terms of both bulk density of the polymer formed and polymerization rate, but also in terms of reduced fouling, while the economics in relation to the catalyst composition should also be advantageous.
  • Such economics include the synthesis of the ligand and the costs associated therewith in terms of the number of synthesis steps required and the availability and prices of the various reactants.
  • this overall purpose was best realised by using a specific ligand having a novel type of bridging group.
  • the bidentate ligand comprises a bivalent bridging group in which the bridge consists of three carbon atoms, the middle of which forms part of a group -CR 7 R 8 - in which R 7 and R 8 are similar or different monovalent substituents exclusively comprising carbon, hydrogen and optionally oxygen.
  • the most preferred bridging group clearly is the 2, 2-dimethylpropylene group, which is used in all working examples of EP-A-0, 296, 687, as part of a phosphorus bidentate ligand containing phenyl or polar-substituted phenyl groups attached to the phosphorus atoms.
  • the present invention aims to provide catalyst compositions which also have an excellent polymerization rate, but moreover also result in polyketone polymers having a high bulk density without significant fouling occurring. Furthermore, the present invention aims to provide a catalyst composition which is attractive from an economic perspective and can thus be obtained at relatively low cost.
  • the present invention relates to a catalyst composition based on
  • R 2 , R3 and R 4 represent similar or different hydrocarbyl groups, which may optionally be substituted, M ⁇ and M 2 represent similar or different elements selected from arsenic, antimony, phosphorus and nitrogen and R ⁇ represents a bivalent bridging group in which the bridge consists of three atoms, the outer two of which are carbon atoms and the middle one (X) of which forms part of a group Y ⁇ O
  • X represents carbon or silicon
  • R 6 and R 7 represent similar or different groups, oligomeric chains or polymeric chains exclusively comprising carbon, hydrogen and optionally one or more heteroatoms; or together with the carbon or silicon atom to which they are bonded form a cyclic aliphatic structure exclusively comprising carbon, hydrogen and optionally oxygen and/or silicon with the proviso that R° and R 7 are not methyl groups if X is a carbon atom and the acid from which the anion is derived is para-toluenesulphonic acid or trifluoroacetic acid; and
  • R 8 represents hydrogen or an alkyl group having from 1 to 5 carbon atoms.
  • the Group VIII metal compound used as component (a) may be a platinum, cobalt, nickel or palladium compound, preferably a palladium compound. This compound may take the form of a salt of a carboxylic acid, with an acetate being preferred. The most preferred Group VIII metal compound is palladium acetate.
  • Suitable anions are anions of protic acids, including 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 those acids which have a pKa of less than 6, in particular less than 4, more in particular less than 2, when measured in an aqueous solution at 18 °C.
  • acids examples include sulphuric acid, perchloric acid, sulphonic acids, such as methane sulphonic acid and para-toluenesulphonic acid, and carboxylic acids, such as 2, 6-dihydroxybenzoic acid, maleic acid, trichloroacetic acid, difluoroacetic acid and trifluoroacetic acid.
  • sulphuric acid perchloric acid
  • sulphonic acids such as methane sulphonic acid and para-toluenesulphonic acid
  • carboxylic acids such as 2, 6-dihydroxybenzoic acid, maleic acid, trichloroacetic acid, difluoroacetic acid and trifluoroacetic acid.
  • BF3 Lewis acid
  • HF protic acid
  • HBF4 boron
  • suitable anions are borate anions comprising the same or different hydrocarbyl groups attached to boron, such as tetraarylborates and carborates .
  • Hydrocarbylboranes such as e.g. triphenylborane, or aluminoxanes, such as methyl aluminoxanes and tert. -butyl aluminoxanes, may also be applied as compounds functioning as a source of anions. More examples of suitable anions are given in EP-A- 0,743,336.
  • the anion most preferably originates from a protic acid selected from para-toluenesulphonic acid, trifluoroacetic acid, maleic acid and mixtures of two or more of these.
  • a protic acid selected from para-toluenesulphonic acid, trifluoroacetic acid, maleic acid and mixtures of two or more of these.
  • particularly maleic acid had a beneficial effect on various properties, such as the oxidative stability and whiteness of the polyketone polymers prepared.
  • This beneficial effect was found not to be limited to the specific ligands which are the subject of the present application, but to extend beyond these ligands to other ligands as well. Hence, said beneficial effects were concluded to be attributable to the use of maleic acid as the anion source.
  • the quantity of the source of anions is suitably selected such that it provides in the range of from 0.1 to 50, preferably from 0.5 to 25, equivalents of anions per mole of Group VIII metal.
  • 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 groups R1, R 2 , R3 and R 4 preferably represent similar or different aryl groups, which may optionally be substituted with one or more substantially apolar and/or one or more polar groups .
  • R ⁇ , R , R 3 and R 4 independently represent a phenyl group or a substituted phenyl group, wherein in the latter case one or more substituents selected from C1-C4 alkoxy groups, most suitably a methoxy group, aryloxy groups, most suitably a phenyloxy group, and C1-C4 alkyl groups, most suitably a methyl group, are present.
  • substituted groups examples include 2-methoxyphenyl, 2,4- dimethoxyphenyl, 4-methoxyphenyl, 2, 6-dimethoxyphenyl, 2- methoxy-5-methylphenyl and 2, 4 , 6-trimethoxyphenyl .
  • R ⁇ , R 2 , R 3 and R 4 are identical and are selected from phenyl, 2-methoxyphenyl and 2-methoxy- 5-methylphenyl .
  • the central atom X of the ligand 's bridge can be either a carbon atom or a silicon atom, but preferably it is a carbon atom.
  • Chelating atoms ⁇ and M 2 preferably both are phosphorus atoms.
  • the central atom X of the bridging group forms part of a cyclic structure as indicated in formula (I) .
  • This cyclic structure is completed by the group Y.
  • the group Y present in the ligand may represent a variety of different groups, which are able to form two stable bonds with both oxygen atoms indicated in formula (I), so that a stable cyclic structure can be formed. Accordingly, the group Y may represent the groups indicated above. First of all, Y may represent a group -C(R ⁇ ) (R 7 )- or
  • R ⁇ and R 7 either represent similar or different groups or chains exclusively comprising carbon, hydrogen and optionally one or more heteroatoms, or together with the carbon atom to which they are bonded form a cyclic aliphatic structure exclusively comprising carbon, hydrogen and optionally oxygen with the proviso that R ⁇ and R 7 are not methyl groups if X is a carbon atom and the acid from which the anion (component (b) ) is derived is para-toluenesulphonic acid or trifluoroacetic acid.
  • R° and R 7 independently represent alkyl groups or polymeric chains comprising carbon, hydrogen and optionally one or more heteroatoms, such as oxygen, nitrogen, sulphur and phosphorus.
  • C1-C4 alkyl groups such as methyl or ethyl, or polyketone polymeric chains, i.e. polymeric chains comprising one or more carbonyl groups either in an alternating fashion with the olefinic comonomer(s) or in a random distribution across the polymer chain.
  • the length of these polymeric chains may vary within broad limits and includes both oligomers and polymers. If R ⁇ and R 7 are polyketone polymeric chains, these chains may serve as a carrier to which the ligand is covalently bonded.
  • a catalyst supported on a carrier can be obtained.
  • Such catalysts are specifically of interest for gas phase polymerization processes, although they may also be useful in liquid phase (or slurry) polymerization processes for preparing linear alternating polyketone polymers .
  • R" and R 7 are polyketone polymeric chains more than one ligand may be bonded to a single polymer chain.
  • one polymeric chain may serve as a "backbone" from which two or more ligands of formula (I) are pending.
  • these ligands are bonded to the polyketone backbone polymer via the keto group:
  • Y in formula (I) is the carbon atom of the original keto group in the polymer chain.
  • R ⁇ and R 7 together with the carbon atom to which they are bonded form a cycloalkyl group, which may optionally be substituted with one or more substantially apolar or polar groups.
  • Substantially apolar substituents include alkyl groups, preferably C1-C4 alkyl groups, of which methyl and ethyl are most preferred.
  • Suitable polar substituents include inter alia alkoxy groups (suitably C1-C4 alkoxy groups like methoxy and ethoxy) , oxo groups, hydroxy groups and carboxyl groups.
  • R ⁇ and R 7 together with the carbon atom to which they are bonded form a cycloalkyl group, most preferably a cyclopentyl or cyclohexyl group.
  • ligands with X being a carbon atom and Y representing -C(R ⁇ ) (R 7 )- as discussed above can be prepared by a process comprising the steps of:
  • Step (a) can be carried out by methods known in the art. For instance, in Example 1 of US-4,851,461 this reaction is exemplified for cyclohexanone .
  • Process conditions typically include a temperature of 10 to 160 °C and a pressure of from essentially zero to 10 bar.
  • step (a) is carried out at an elevated temperature of at least 60 °C at atmospheric pressure.
  • Step (b) can, for instance, be effectively carried out in accordance with the process disclosed in European patent application No. 98203587 disclosing both the preparation of compounds of the type Li-M ⁇ R ⁇ R 2 and the reaction of halogen-containing compounds with these lithium compounds, thereby producing dentate ligands useful as catalyst component in catalyst compositions for producing polyketone polymers.
  • step (b) is carried out at a temperature not exceeding 55 °C, preferably not exceeding 40 °C, and especially not exceeding 30 °C .
  • the process is carried out at a temperature of at least -50 °C, preferably at least -15 °C and most preferably at least 0 °C . Cooling is generally required for such a process, whereby the temperature of the reaction mixture is preferably between 0 and 25 °C .
  • the pressure is not particularly critical and may vary from essentially zero to 10 bar.
  • this process step is carried out at a pressure of from 0.5 to 1.5 bar.
  • ligands with X being a carbon atom and Y representing -C(R°) (R 7 )- as discussed above can be prepared by a process (Method II) comprising the steps of:
  • step (b) reacting the product of step (a) with the chelating atom-containing compounds, such as Li-M ⁇ R ⁇ R 2 and/or Li-M 2 R 3 R 4 ; (c) removing the protective agent from the hydroxyl groups; and
  • the chelating atom-containing compounds such as Li-M ⁇ R ⁇ R 2 and/or Li-M 2 R 3 R 4 ;
  • step (d) reacting the product of step (c) with a compound
  • Suitable protective agents include, for instance, ketones (thus forming a ketal) and aldehydes (thus forming an acetal) .
  • suitable protective agents are propanone, formaldehyde and ethanal .
  • Removal of the protective agents after step (b) can e.g. suitably be effected by adding acid. Such methods are also well known in the art. Steps (b) and (d) can be carried out under the same conditions as outlined herein before.
  • ligands with Y representing -Si (R ⁇ ) (R 7 )- as discussed above can be prepared by Method I or
  • Ligands of formula I with Y representing -P(O) (R 8 )-; or -P(S) (R 8 )-; -S0 2 -; -SO- or -A1(R 8 )- are most suitably prepared by Method II using respectively a dihalophosphinoxide (e.g. R 8 -POCl2 or R 8 -POBr2) a dihalophosphine sulphide (e.g.
  • R 8 -PSCl2 or R 8 -PSBr2 instead of
  • Y may represent the group indicated by formula (II).
  • a tetradentate ligand is obtained.
  • a compound of formula (II) may suitably be obtained via Method I by reacting two moles of 1, 3-dibromo-2, 2-dihydroxymethylene-propane with one mole of 1, 4-cyclohexanedione followed by the reaction with the chelating atom-containing compounds .
  • the ligands are suitably used in the catalyst composition in a quantity of from 0.5 to 2 and in particular of from 0.75 to 1.5 mole per mole of Group VIII metal.
  • Organic oxidant promoters may be incorporated into the catalyst composition in order to enhance their performance.
  • suitable promoters are quinones, such as benzoquinone, naphthoquinone and anthraquinone .
  • the amount of promoter used is suitably in the range of from 1 to 250, preferably 1 to 100, mole per mole of Group VIII metal.
  • the catalyst composition of the present invention is suitably used in the form of a solution in a liquid.
  • suitable liquids include polar liquids, such as C -C4 alcohols, for example methanol and ethanol, C2 _ Cg ethers such as diethylether, tetrahydrofuran or the dimethylether of diethylene glycol (diglyme) , C2-C5 ketones such as acetone and methylethylketone and aromatic solvents such as toluene.
  • polar liquids such as C -C4 alcohols, for example methanol and ethanol
  • C2 _ Cg ethers such as diethylether, tetrahydrofuran or the dimethylether of diethylene glycol (diglyme)
  • C2-C5 ketones such as acetone and methylethylketone
  • aromatic solvents such as toluene.
  • the present invention also relates to a solution of the catalyst composition described above.
  • the present invention also relates to novel compounds of the formula
  • R 1 R 2 M 1 -R 5 -M 2 R 3 R 4 wherein R 1 , R 2 , R 3 , R , M 1 , M 2 and R 5 have the same meaning as indicated above with the proviso that R ⁇ and R 7 are not methyl groups if X is a carbon atom.
  • R ⁇ and R 7 represent similar or different C -C alkyl groups, preferably methyl or ethyl, or polyketone polymer chains or together with the carbon atom to which they are bonded form a cyclopentyl or cyclohexyl group.
  • the invention also relates to a process for the preparation of polymers, wherein a mixture of carbon monoxide and one or more olefinically unsaturated compounds is polymerised in the presence of a catalyst composition as defined above.
  • Olefinically unsaturated compounds which can be used as monomers in the said process include compounds consisting exclusively of carbon and hydrogen and compounds which in addition comprise heteroatoms, such as unsaturated esters, ethers and amides. Unsaturated hydrocarbons are preferred.
  • suitable olefinic monomers are olefins, such as ethene, propene, butene-1, octene-1, decene-1 and dodecene-1, cyclic olefins such as cyclopentene, aromatic compounds, such as styrene and ⁇ - methylstyrene and vinyl esters, such as vinyl acetate and vinyl propionate.
  • ethene and mixtures of ethene with another olefinically unsaturated compound in particular an ⁇ -olefin, such as propene, butene-1, octene-1, decene-1 and dodecene-1.
  • ⁇ -olefin such as propene, butene-1, octene-1, decene-1 and dodecene-1.
  • the molar ratio of on the one hand carbon monoxide and on the other hand the olefinically unsaturated compound (s) used as monomer is selected in the range of 1:5 to 5:1.
  • the molar ration is in the range of 1:2 to 2:1, substantially equimolar rations being preferred most.
  • the process according to the invention is suitably carried out at an overall pressure of from 20 to 150 bar. However, for economic reasons overall pressures between 20 and 75 bar are usually preferred.
  • the polymerization is usually carried out at a temperature in the range of from 20 to 200 °C, preferably 40 to 150 °C .
  • the present process may be carried out as a gas phase polymerization, as a super critical phase polymerization and as a liquid phase or slurry polymerization.
  • the catalyst composition is suitably supported on a carrier. Suitable carrier materials and methods and means for impregnating a carrier with catalyst solution are well known in the art.
  • suitable diluents would be ethene or carbon dioxide.
  • the diluent used should be a liquid in which the polyketone polymers formed are essentially insoluble such that they form a suspension.
  • Suitable diluents are ketones (e.g. acetone), chlorinated hydrocarbons (e.g.
  • aromatics e.g. toluene, benzene, chlorobenzene
  • protic diluents such as C1-C4 alcohols (e.g. methanol and ethanol).
  • C1-C4 alcohols e.g. methanol and ethanol.
  • protic diluents may comprise an aprotic diluent.
  • the C1-C4 alcohols, and in particular methanol are preferred.
  • the quantity of catalyst composition used in the process of the present invention suitably is such that per mole of olefinically unsaturated compound to be copolymerized IO -7 to IO -3 and particularly 10 ⁇ to IO -4 mole of Group VIII metal is present.
  • the polymerization process according to the present invention may be carried out either batchwise or continuously.
  • the Limited Viscosity Number (LVN) of polymers is reported.
  • the concept of LVN is well known in the art and is extensively explained in e.g. EP-A-0, 246, 674 and EP-A-0, 319, 083.
  • the LVN referred to in the present application corresponds with the LVN as explained in EP-A-0, 319, 083, i.e. an LVN on the basis of the viscosities determined at 60 °C of four solutions of the polymer prepared by dissolving the polymer in four different concentrations at 60 °C in m-cresol.
  • Example 1 (for comparison)
  • a 100 ml reaction vessel under argon atmosphere and equipped with a mechanical stirrer and a reflux condensor is charged with 40 ml of THF, 3.17 g (10 mmole) of N, N-diethylamino-bis (2-anisyl) phosphine and 486 mg (21 mmole) of a 30 % lithium dispersion under argon atmosphere at 0 °C.
  • the reaction mixture was stirred for 16 hours after which time a precipitate had been formed.
  • 5 ml of DMSO were added, followed by slow addition of 1.15 g (5 mmole) of 1, 3-dibromo-2, 2- dimethylpropane .
  • a 100 ml reaction vessel equipped with a mechanical stirrer and a reflux condensor was charged with 40 ml of THF, 3.17 g (10 mmole) of N, N-diethylamino-bis (2-anisyl) - phosphine and 486 g (21 mmole) of a 30% lithium dispersion under argon atmosphere at 0 °C.
  • the reaction mixture was stirred for 16 hours after which time a thick precipitate had formed.
  • Lithium diethylamide was quenched by addition of 535 mg (10 mmole) of ammoniumchloride, which caused a temperature rise to 6 °C.
  • the mixture was cooled again to 0 °C, stirred for 30 more minutes and 1.71 g (5 mmole) of the compound (a) in 5 ml of THF was added over a period of 10 minutes.
  • the mixture was stirred for two more hours while the temperature was slowly raised to 20 °C.
  • 10 ml of methanol were added, the solvent was removed under vacuum and 40 ml of toluene and 40 ml of water were added.
  • the organic phase was separated off and washed with 20 ml of water.
  • the toluene phase was concentrated to 10 ml, 30 ml of methanol were added and the mixture was refluxed until a white precipitate appeared. The mixture was allowed to crystallize overnight. Hereafter it was filtrated over a P3 glass frit, rinsed with methanol and dried. The desired diphosphine was obtained in a yield of
  • Example 3 was repeated except that maleic acid was added instead of trifluoroacetic acid. Accordingly, a catalyst solution was prepared on the basis of: 16.9 mg (0.0752 mmole) palladium acetate, 53.1 mg (0.0789 mmole) of the ligand of Example 2, 175 mg (1.50 mmole) maleic acid and 20 ml acetone.
  • Seed powder (5.4 g, ethene/propene/CO terpolymer, 2 wt% propene) was weighed directly into in a 0.5 1 autoclave followed by 270 g (334 ml) of methanol.
  • Catalyst Solution I was introduced via a polyethene syringe. The autoclave was closed, the stirrer was turned on and the system was pressurized to 50 bar nitrogen to leak-test the reactor and to remove the greater part of oxygen. After 5 minutes the pressure was carefully released.
  • the heating mantle was switched on, and when the temperature reached 88 °C 24 bar ethene was added, followed by 24 bar carbon monoxide, so that the total pressure was 50 bara (autogeneous pressure of methanol is 2 bar) .
  • a 1:1 (mole/mole) gas mixture of CO/ethene was introduced to keep the pressure at 50 bar throughout the polymerization.
  • the polymerization proceeded at 90° C for 1 hour.
  • Catalyst Solution I a catalyst solution was added based on : 0.0752 mmole palladium acetate,
  • the mass of polymer obtained was determined and corrected for the seed powder, and the bulk density and
  • Seed powder (33.6 g ethene/propene/CO terpolymer, 6 wt% propene) was weighed directly into a 1.25 1 autoclave the autoclave followed by 560 g (693 ml) methanol and 11.2 g water.
  • Catalyst Solution I was introduced via a polyethene syringe. The autoclave was closed, the stirrer was turned on and the system was pressurized to 50 bar nitrogen to leak-test the reactor and to remove most of the oxygen present. After 5 minutes the pressure was carefully released and the reactor was flushed three times with CO. Subsequently, 72 g of liquid propene were added followed by 10 bars of CO.
  • the heating mantle was switched on, and when the temperature reached 76 °C ethene was added to arrive at a final pressure of 46 bar. This resulted in a CO/olefin molar ratio of 0.7 and an ethene/propene molar ratio of 0.4 (autogenous pressure of methanol is 2 bar) .
  • a 1:1 (mole/mole) gas mixture of CO/ethene was introduced to keep the pressure at 46 bar throughout the polymerization. The polymerization was considered to have begun when the CO was introduced.
  • Example 8 was repeated except that Catalyst Solution II was used instead of Catalyst Solution I. The results are indicated in Table I .
  • Example 10 (for comparison)
  • Example 6 was repeated except that instead of Catalyst Solution I a catalyst solution was added based on :

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EP00945888A 1999-07-06 2000-07-05 Katalysator zusammensetzung und ihre verwendung Withdrawn EP1192205A1 (de)

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AU2002354267A1 (en) 2001-12-26 2003-07-15 Asahi Kasei Fibers Corporation Polyketone and process for producing the same
KR100721450B1 (ko) * 2006-08-31 2007-05-23 주식회사 효성 폴리케톤의 제조방법
KR100721448B1 (ko) * 2006-08-31 2007-05-23 주식회사 효성 폴리케톤의 제조방법
KR101546034B1 (ko) 2013-07-17 2015-08-25 주식회사 효성 폴리케톤 중합촉매
KR101630679B1 (ko) * 2014-04-22 2016-06-16 주식회사 효성 저융점 폴리케톤 중합방법 및 이를 이용하여 제조된 저융점 폴리케톤
KR101647685B1 (ko) * 2014-08-19 2016-08-11 주식회사 효성 폴리케톤 중합용 고체상 촉매, 이의 제조방법 및 이를 이용한 폴리케톤의 제조방법
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KR101746030B1 (ko) 2016-02-04 2017-06-27 주식회사 효성 폴리케톤 중합촉매 및 이의 제조방법

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US4851461A (en) * 1987-05-15 1989-07-25 Ici Americas Inc. Tetraalkyl piperidylated stabilizers for plastics
CA1333619C (en) * 1987-06-24 1994-12-20 Johannes Adrianus Van Doorn Catalyst compositions
KR0128998B1 (ko) * 1987-07-23 1998-04-07 오노 알버어스 신규 촉매 조성물 및 이를 이용하여 중합체를 제조하는 방법
EP0743336A3 (de) * 1995-05-18 1997-04-23 Shell Int Research Verfahren zur Herstellung linearer, alternierender Copolymere aus Kohlenmonoxid mit Ethen und einer anderen olefinisch ungesätigten Verbindung

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