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
• • 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
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/10—Complexes comprising metals of Group I (IA or IB) 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
  • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) 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
• • 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

Definitions

• the present invention relates to a process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated compounds in an aqueous medium.
• Linear, alternating copolymers of carbon monoxide and olefinically unsaturated compounds also referred to briefly as carbon monoxide copolymers or polyketones
• carbon monoxide copolymers or polyketones are known.
• high molecular weight, partially crystalline polyketones with a strictly alternating sequence of monomers in the main chain are generally distinguished by high melting points, good heat resistance, good chemical resistance, good barrier properties against water and air, and advantageous mechanical and rheological properties.
• polyketones made from carbon monoxide and two olefins generally ⁇ -olefins, such as, for example, carbon monoxide-ethylene-propylene, carbon monoxide-ethylene-butene-1, carbon monoxide-ethylene-hexene-1, carbon monoxide- Propylene-butene-1 or carbon monoxide-propylene-hexene-1 copolymers.
• ⁇ -olefins such as, for example, carbon monoxide-ethylene-propylene, carbon monoxide-ethylene-butene-1, carbon monoxide-ethylene-hexene-1, carbon monoxide- Propylene-butene-1 or carbon monoxide-propylene-hexene-1 copolymers.
• the carbon monoxide copolymerization can be carried out in suspension, as described in EP-A 0 305 011, or in the gas phase, for example according to EP-A 0 702 045.
• suspension media are, on the one hand, low molecular weight alcohols, in particular methanol (see also EP-A 0 428 228), and on the other hand non-polar or polar aprotic liquids such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460 743 and EP-A 0 590 942 ).
• Complex compounds with bisphosphine chelate ligands whose residues on the phosphorus represent aryl or substituted aryl groups have proven to be particularly suitable for the polymerization processes mentioned.
• 1,3-bis (diphenylphosphino) propane or 1,3-bis [di- (o-ethoxyphenyl) phosphino)] propane are particularly frequently used as chelating ligands used (see also Drent et al., Chem. Rev., 1996, 96, pp. 663-681).
• the carbon monoxide copolymerization is usually carried out in the presence of acids.
• the carbon monoxide copolymerization in low molecular weight alcohols such as methanol has the disadvantage that the carbon monoxide copolymer which forms has a high absorption capacity for these liquids and up to 80% by volume of e.g. Methanol are bound or taken up by the carbon monoxide copolymer. As a result, a large amount of energy is required to dry and isolate the carbon monoxide copolymers.
• Another disadvantage is that even after an intensive drying process, residual amounts of alcohol still remain in the carbon monoxide copolymer. Use as a packaging material for food is therefore ruled out from the outset for molding compositions produced in this way.
• EP-A 0 485 035 proposes the use of additions of water in proportions of 2.5 to 15% by weight to the alcoholic suspending agent in order to eliminate the residual amounts of low molecular weight alcohol in the carbon monoxide copolymer.
• this procedure also does not lead to methanol-free copolymers.
• halogenated hydrocarbons or aromatics such as dichloromethane or chlorobenzene or toluene poses problems, particularly in handling and disposal.
• the object of the present invention was to provide a process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated
• the invention was based on the object that the polyketones obtained in this way have high molecular weights and good physical properties, e.g. high bulk densities.
• R a independently of one another C ⁇ to C o-alkyl, C 3 - to
• R b as R a , additionally hydrogen or Si (R c ) 3 ,
• Z is a non-metallic element from group VA of the periodic table of the elements
• M is a metal selected from Groups VIIIB, IB or IIB of the Periodic Table of the Elements
• E 1 , E 2 a non-metallic element from group VA of the periodic table of the elements
• R 1 to R 4 are linear or branched C 2 - to C 28 -alkyl, C 3 - to -C 4 -cycloalkyl, C ß- cis-aryl or alkylaryl with 1 to 28 C-atoms in the alkyl part and 6 to 15 C-atoms in the aryl part, where at least one of the radicals R 1 to R 4 has at least one hydroxyl, amino or acid group or contains an ionically functional group,
• water-soluble transition metal complexes and solubilizers were therefore simultaneously used to increase the concentrations of the olefins in solution and to stabilize the water-insoluble polyketones.
• the invention also relates to a method in which the metal complex a1) is not presented in the form of a defined compound, but is formed in situ from the individual components during the copolymerization.
• the invention further relates to a process for the preparation of linear, alternating copolymers of carbon monoxide and an olefinically unsaturated compound having three to twenty carbon atoms or of carbon monoxide and at least two different olefinically unsaturated compounds in aqueous medium. diu, in which, in addition to the components al) and b) or al.l), al.2) 'and b) mentioned, an acid and, if appropriate, a hydroxy compound is used.
• the designations for the groups in the Periodic Table of the Elements are based on the nomenclature used by the Chemical Abstracts Service until 1986 (for example, the VA group contains the elements N, P, As, Sb, Bi; the IB group contains Cu, Ag, Au).
• the copolymerization is carried out in the presence of
• R b hydrogen f, C ⁇ ⁇ to Cio-alkyl or C 6 - bis
• R 5 is hydrogen, C 1 to C 0 alkyl, C 3 to C 0 cycloalkyl, 0 to cis aryl, with functional groups which atoms of groups IVA, VA, VIA or VIIA of the periodic table Contain elements, substituted C ⁇ to Cio-alkyl, C- to Cirj-cycloalkyl or C 6 - to Cis-aryl,
• E 1 , E 2 phosphorus, R 1 to R 4 are linear, branched or carbocycle-containing C - to C 28 -alkyl units, C 3 - to -CC 4 cycloalkyl units, C ⁇ - cis-aryl units or alkylaryl - groups with 1 to 20 C atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, at least one of the radicals R 1 to R 4 having at least one terminal, internal or hydroxy, amino, carboxylic acid, phosphoric acid, ammonium or sulfonic acid group,
• L 1 , L 2 acetate, trifluoroacetate, tosylate or halides
• the metal complex al has at least one radical among the substituents R 1 to R 4 which is substituted by at least one free carboxylic acid or sulfonic acid group, C 2 -C 28 -alkyl, C 3 -C to -C cycloalkyl, C 6 -C 5 aryl or alkylaryl having 1 to 28 carbon atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, completely dispensing with the presence of external acids a2).
• the metal complex a1) is not prepared beforehand and used in a defined form in the copolymerization, but only by adding the metal component a1) and the chelate ligand a1.2) to the starting materials of the copolymerization. generated in situ.
• bidentate chelate ligands of the general formula (R 1 ) (R 2 ) E x -GE 2 (R 3 ) (R 4 ) (III) are suitable as constituents of the metal complexes al) or as chelate ligand al.2) in the process according to the invention, in which the substituents and indices have the aforementioned meaning.
• the bridging structural unit G in the metal complexes al) or the chelate ligands al.2) of the process according to the invention generally consists of mono- or polyatomic bridge segments.
• a bridging structural unit is basically understood to mean a grouping which connects the elements E 1 and E 2 to one another.
• Such structural units include, for example, substituted or unsubstituted alkylene chains or those alkylene chains in which an alkylene unit has been replaced by a silylene group, an amino or phosphino group or by an ether oxygen.
• the bridging structural unit G can furthermore be a 5-, 6- or 7-atom carbocyclic ring system without or with one or more heteroatoms.
• the ring system can be aliphatic or aromatic. 5- or 6-atomic ring systems with 0, 1 or 2 heteroatoms selected from N, 0 or S are preferred.
• bonds to the atoms E 1 and E 2 can take any position relative to one another.
• Preferred positions relative to one another are the 1,2, 1,3 and 1,4 positions.
• Preferred embodiments for cyclic structural units G are the following (binding sites to E 1 and E 2 are identified):
• the monatomic bridged structural units are those with a bridging atom from group IVA of the periodic table of the elements such as -C (R b ) - or -Si (R a ) 2 -, wherein R a independently of one another in particular for linear or branched C ⁇ ⁇ to Cio-alkyl, for example methyl, ethyl, i-propyl or t-butyl, C 3 - to C ⁇ -cycloalkyl, such as cyclopropyl or cyclohexyl, C ⁇ - to Cio-aryl, such as phenyl or naphthyl, with functional groups, which are non-metallic elements of groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements contain substituted C ⁇ - to Cio-aryl, for example tolyl, (trifluoromethyl) phenyl, dirnethylaminophenyl, p-methoxyphenyl or partially or perhalogen
• R a represents in particular a methyl group
• R b represents in particular hydrogen
• the two-, three- and four-atom bridged structural units should be emphasized, with the tri-atomic bridged systems generally being used with preference.
• Suitable three-atom bridged structural units are generally based on a chain of carbon atoms, for example propylene (-CH 2 CHCH-), or on a bridge unit with a heteroatom from group IVA, VA or VIA of the periodic table of the elements, such as silicon, Nitrogen, phosphorus or oxygen in the chain structure.
• the bridging carbon atoms can generally with C ⁇ ⁇ to C ⁇ -alkyl such as methyl, ethyl or t-butyl, C 6 - to Cio-aryl such as phenyl or by functional groups, which elements of groups IVA, VA, VIA or VIIA of the periodic table of the elements contain, for example, triorganosilyl, dialkylamino, alkoxy, hydroxy or halogen.
• Suitable substituted propylene bridges are, for example, those with a methyl, phenyl, hydroxy, trifluoromethyl, ⁇ -hydroxyalkyl or methoxy group in the 2-position.
• Heteroatoms in the chain structure are advantageously used in which Z is nitrogen or phosphorus, in particular nitrogen (see also formula (I)).
• the substituent R 5 on Z can in particular mean: hydrogen, linear or branched C 1 to C 28 "alkyl, in particular C 1 to C 2 o alkyl such as methyl, ethyl, i-propyl, t-butyl, n-hexyl or ⁇ -Dodecyl, C - to C -cycloalkyl, in particular C 3 to Cs-cycloalkyl such as cyclopropyl or cyclohexyl, C ß - to cis-aryl, in particular C ⁇ - to Cio-aryl, for example phenyl, or alkylaryl with I to 20 C atoms in the alkyl radical and 6 to 10 C atoms in the aryl radical, for example benzyl.
• alkyl and aryl radicals mentioned can be unsubstituted or substituted.
• suitable substituents are functional groups which contain atoms from groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements. Suitable are inter alia triorganosilyl groups such as trimethylsilyl or t-butyldiphenylsilyl, the carboxylic acid group or carboxylic acid derivatives such as esters or amides, primary, secondary or tertiary amino groups such as dimethylamino or methylphenylamino, the nitro and the hydroxyl group, and further alkoxy groups such as methoxy or ethoxy, the sulfon and also halide atoms such as fluorine, chlorine or bromine.
• aryl also means substituted and unsubstituted heteroaryl, for example pyridyl or pyrrolyl.
• Alkyl radicals R 5 also include long-chain alkylene groups with 12 to 22 carbon atoms in the chain, which also have functionalities such as the sulfonic acid, carboxylic acid, phosphoric acid, hydroxy, amino or ammonium group, for example in the terminal position, can dispose of.
• Preferred radicals R 5 are also those compounds which represent an electron-withdrawing substituent.
• Suitable electron-withdrawing substituents are, for example, alkyl groups with one or more electron-withdrawing radicals such as fluorine, chlorine, nitrile or nitro in the ⁇ or ⁇ position to Z.
• Aryl groups with the electron-withdrawing radicals mentioned and also as radicals bonded directly to Z are also suitable, too the nitrile, sulfonate and nitro group.
• suitable electron-withdrawing alkyl radicals are the trifluoromethyl, trichloroethyl, difluoromethyl, 2, 2, 2-trifluoroethyl, nitromethyl and the cyanomethyl group.
• Suitable electron-withdrawing aryl radicals are: m-, p-, o-fluorophen or chlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,4,6-trifluorophenyl, 3,5-bis (tri-fluoromethyl) ) phenyl, nitrophenyl, 2-chloro-5-nitrophenyl and 2-bromo-5-nitrophenyl.
• carbonyl units are also suitable as radicals R 5 , so that when Z is nitrogen, Z and R 5 form a carboxylic acid amide functionality.
• the acetyl or trifluoroacetyl group may be mentioned as such a suitable radical.
• radicals R 5 t-butyl, phenyl, p-fluorophenyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, pentafluorophenyl, 3, 5-bis (trifluoromethyl) phenyl and ortho-, for example 3,4- , meta, for example 2,4-, or para, for example 2, 5-difluorophenyl.
• units A and B according to formulas (I) to (IV) are C 1 -C 4 -alkylene units in substituted or unsubstituted form, for example methylene, ethylene, propylene or ethylidene, propylidene and benzylidene.
• Methylene, ethylene, ethylidene or benzylidene are preferably used, particularly preferably methylene.
• a and B can also be a one, two, three or four atom component of an aliphatic or aromatic ring system.
• a and B can be a methylene or ethylene unit of a cyclopropyl, cyclopentyl or cyclohexyl ring.
• Aliphatic and aromatic heterocycles are also suitable as ring systems.
• a and B can furthermore be constituents of a heterocycle which is formed from the components AZ (R 5 ) -B, AZR 5 and BZR 5 , respectively.
• AZR 5 or BZR 5 can, for example, form a substituted or unsubstituted pyrrolidine or piperidine ring.
• the chelating atoms E 1 and E 2 are, independently of one another, the non-metallic elements of group VA of the Periodic Table of the Elements, preference being given to nitrogen and phosphorus, in particular phosphorus.
• E 1 and E 2 in the compounds according to formulas (I) and (III) represent phosphorus.
• the radicals R 1 to R 4 represent substituted C 2 - to C 28 - »preferably C 3 - to C 2 o-alkyl, C 3 - to C ⁇ 4 -, preferably C 3 - to Cs-cycloalkyl, C ⁇ - cis, preferably Cg-Cio-aryl or alkylaryl having 1 to 28, preferably 3 to 20 C atoms in the alkyl part and 6 to 15, preferably 6 to 10 C atoms in the aryl part, at least one, preferably more, particularly preferably all of the radicals R 1 to R 4 have at least one hydroxyl, amino or acid group or contain an ionically functional group.
• Ionic functional groups are groups based on non-metallic elements from groups IVA to VIA of the periodic table of the elements, for example sulfonate, phosphate, ammonium, carboxylate.
• R 1 to R 4 are preferably linear, branched or carbocyclic-containing C 2 to C 8 ⁇ A1 alkyl units or C 3 to C 4 cycloalkyl units, or C 6 -C 5 aryl units or alkylaryl groups having 1 to 28 C- Atoms in the alkyl part and 6 to 15 carbon atoms in the aryl part, at least one, preferably several, particularly preferably all of the radicals containing at least one hydroxyl, carboxylic acid, phosphoric acid, ammonium, amine or sulfonic acid group.
• salts of carboxylic, phosphoric, amino or sulfonic acids can also be used.
• Suitable salts are, for example, ammonium, alkylammonium, arylammonium, alkali or alkaline earth metal salts such as sodium, potassium or magnesium carboxylates or sulfonates.
• Counterions for the ammonium radicals mentioned are, in particular, non-nucleophilic anions, as are also used for the metal complexes a1 (see anions X).
• non-nucleophilic anions as are also used for the metal complexes a1 (see anions X).
• p-toluenesulfonate, tetrafluoroborate, trifluoroacetate, trichloroacetate, hexafluorophosphate, hexafluoroantimonate or tetraarylborate are particularly suitable.
• Particularly suitable aryl radicals R 1 to R 4 are, for example, aryl units with or without one or more, for example 1 to 3, heteroatoms in the ring which are substituted by one or two hydroxyl, carboxylic acid, sulfonic acid or amino groups.
• the phenyl (en) radical is preferred among the aryl or arylene radicals R 1 to R 4 .
• the radicals R 1 to R 4 can also have more than two polar groups and, for example, have four or six hydroxyl, ammonium or carboxylic acid groups.
• the cyclopentyl and cyclohexyl radicals are preferred as cycloaliphatic radicals R 1 to R 4 .
• Particularly suitable alkyl radicals R 1 to R 4 are, for example, alkylene units with one or two terminal hydroxyl, carboxylic acid, sulfonic acid or ammonium groups.
• the radicals R 1 to R 4 can have more than two polar groups and, for example, have four or six hydroxyl, ammonium or carboxylic acid groups.
• the radicals R 1 to R 4 can each also have different functional groups.
• the radicals R 1 to R 4 can also have functional groups in different numbers from one another. Suitable functional groups include, for example, the hydroxyl, amine, carboxylic acid, phosphoric acid, ammonium and sulfonic acid groups.
• Suitable propylene-bridged chelate ligand compounds can be prepared, for example, from the commercially available 1,3-dibromopropane.
• a double Arbuzov reaction for example with triethyl phosphite, leads to 1,3-bisphosphonic acid derivatives which are reductive, as described in "Methods of Organic Chemistry (Houben-Weyl)", 4th edition, Volume XII / 1 , Part 1, Georg Thieme Verlag, 1963, p. 62, can be converted into 1, 3-diphosphinopropane.
• 1,3-diphosphinopropane opens up flexible access to substituted bisphosphines via a hydrophosphination reaction with functionalized olefins.
• Hydrophosphination generally proceeds via a radical mechanism and can be carried out thermally, can be initiated chemically or with the help of a radical starter. Temperatures in the range from 20 to 100 ° C. and pressures from 0.1 to 5 bar are generally required for thermal initiation. Suitable radical initiators are, for example, di-t-butyl peroxide or azo-bis- [isobutyronitrile]. For photochemical initiation, UV radiation with a high pressure mercury lamp over a period of 2 to 48 hours is usually sufficient for quantitative hydrophosphination. Anti-Markovnikov products are generally obtained by means of radical-initiated processes in the hydrophosphination.
• suitable chelate ligand compounds can also be prepared under acid-catalyzed conditions.
• the products obtained by this process are often obtained as a mixture under the acidic reaction conditions due to the isomerization of the olefinic double bond.
• the process step of hydrophosphination is found e.g. in "Methods of Organic Chemistry (Houben-Weyl)", 4th edition, Volume XII / 1, Part 1, Georg Thieme Verlag, 1963, pp. 25 to 28.
• all olefins which fall under this class of compounds are suitable for the hydrophosphination reaction mentioned, provided that they have appropriate functional groups, such as, for example, hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium and sulfonic acid groups.
• appropriate functional groups such as, for example, hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium and sulfonic acid groups.
• propenyl radicals and C 4 - to C 28 -alkenes with at least one internal or terminal double bond which have at least one hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium or sulfonic acid group.
• olefinic compounds with aromatic radicals where the functional group can be present both on the aliphatic and on the aromatic radical, for example 4- (1-pentene) -benzoic acid or 3-phenylpent-5-ene-carboxylic acid .
• olefinic compounds with aliphatic carbocycles in the alkylene chain are suitable as a substituent.
• Cyclic olefins such as cyclohexen-3-ol or cycloocten-4-ol can also be used.
• Naturally carboxylic acid can also olefins with a plurality of functional groups selected from 'hydroxy, amino, resorted phosphoric acid, ammonium and sulphonic acid groups become.
• Suitable alkenes with an ⁇ -olefinic double bond are preferably used in the hydrophosphination reaction of the ⁇ , ⁇ -bisphosphines.
• heteroatom-containing ⁇ -olefins such as (meth) acrylic acid esters or amides, and homoallyl or allyl alcohols are also suitable.
• chelate ligands containing sulfonic acid groups can be prepared by reacting non-sulfonic acid-containing chelate ligands with SO 3 , chlorosulfonic acid, fuming sulfuric acid or oleum, as described in Jiang et al., Macromolecules 21 (1994 ) 7215-7216 or Verspui et al. , Chem. Commun., 1998, 401-402 or in J. March "Advanced Organic Chemistry", John Wiley & Sons (NY), 1985, 3 ⁇ & Edition pp. 473-475.
• radicals R 1 to R 4 in which the hydrophilicity induced by functional groups, for example hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium or sulfonic acid groups, is sufficient for the metal complex a1) to be completely water-soluble close.
• functional groups for example hydroxyl, amino, carboxylic acid, phosphoric acid, ammonium or sulfonic acid groups
• the greater the number of functional groups on the radicals R 1 to R 4 the greater the lipophilic aliphatic, aromatic or aliphatic-aromatic component.
• preferred radicals R 1 to R 4 each having a hydroxyl group, are those having 2 to 15 C atoms in the alkyl unit or 6-15 C atoms in the aryl unit.
• the radicals R 1 to R 4 have aryl substituents with a hydroxyl group having 6 to 12, in particular 6 to 10, carbon atoms, and aryl substituents with a carboxylic acid group have 6 to 15, in particular 6 to 10, carbon atoms , as aryl substituents with a sulfonic acid group over 6 to 15, and as aryl substituents with an ammonium group over 6 to 15 C atoms.
• Suitable chelating ligands are, for example, 1,3-bis [di- (hydroxyphenyl) phosphino] propane,
• Particularly preferred among the chelate ligand compounds mentioned are those in which the radicals R 1 to R 4 represent a phenyl radical substituted by one or more, for example 1 to 3, hydroxyl, sulfonic acid or carboxylic acid groups.
• the radicals R 1 to R 4 have alkyl substituents with a hydroxyl group of 4 to 12, in particular 4 to 7, carbon atoms, and alkyl substituents with a carboxylic acid group have 4 to 15, in particular 5 to 12, carbon atoms , as alkyl substituents with a sulfonic acid group over 4 to 18, in particular 5 to 15 C atoms and as alkyl substituents with an ammonium group over 4 to 22, in particular 5 to 20 C atoms.
• Particularly preferred among the chelating ligand compounds mentioned are those in which the radicals R 1 to R 4 represent a hexyl, 4-methylpentyl, octyl, cyclopentyl or cyclohexyl radical substituted by a hydroxyl or carboxylic acid group.
• Suitable metals M of the process according to the invention are the metals from groups VIIIB, IB and IIB of the Periodic Table of the Elements, that is, in addition to iron, cobalt and nickel, primarily the platinum metals such as ruthenium, rhodium, osmium, iridium and platinum and very particularly preferably palladium.
• the metals in the complexes according to formula (I) can be formally uncharged, formally single positively charged or preferably formally double positively charged.
• Suitable formally charged anionic ligands L 1 , L 2 are hydride, halides, sulfates, phosphates or nitrates.
• Carboxylates or salts of organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate or p-toluenesulfonate are also suitable.
• p-toluenesulfonate is preferred.
• the formally charged ligands L 1 , L 2 are carboxylates, preferably Ci to C o ⁇ carboxylates and in particular C 1 ⁇ to C 7 carboxylates, ie, for example, acetate, trifluoroacetate, propionate, oxalate, citrate or benzoate. Acetate is particularly preferred.
• Suitable formally charged organic ligands L 1 , L 2 are also -C ⁇ to Co ⁇ aliphatic radicals, C 3 - to C 3 o-cycloaliphatic radicals, C - to C 2 o-aralkyl radicals with Cg to -C aryl radicals and C ⁇ ⁇ bis
• Lewis bases ie compounds with at least one lone pair of electrons, are generally suitable as formally uncharged ligands L 1 , L 2 .
• Lewis bases whose free electron pair or whose free electron pairs are located on a nitrogen or oxygen atom for example nitriles, R-CN, ketones, ethers, alcohols or water, are particularly suitable.
• C ⁇ to C ⁇ o-nitriles such as acetonitrile, propionitrile, benzonitrile or C - to Cio-ketones such as acetone, acetylacetone or C - to Cio-ethers such as methyl ether, diethyl ether, tetrahydrofuran.
• acetonitrile, tetrahydrofuran or water are used.
• the ligands L 1 and L 2 can be in any ligand combination, ie the metal complex (I) can, for example, contain a nitrate and an acetate residue, a p-toluenesulfonate and an acetate residue or a nitrate and a formally charged organic Contain ligands such as methyl.
• L 1 and L 2 are preferably present as identical ligands in the metal complexes.
• the metal complexes Depending on the formal charge of the complex fragment containing the metal M, the metal complexes contain anions X. If the M-containing complex fragment is formally uncharged, the complex according to the invention according to formula (I) does not contain any anion X. Anions X which are as little nucleophilic as possible, ie have as little tendency as possible to interact strongly with the central metal M, whether ionic, coordinative or covalent.
• Suitable anions X are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids such as, for example, methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, and furthermore Tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
• organosulfonic acids such as, for example, methyl sulfonate, tri
• palladium (II) acetate complexes are suitable as defined metal complexes: [1, 3-bis (di-hydroxyphenyl) phosphinopropane] -, [1, 3-bis (di -4-hydroxybutyl) phosphinopropane] -,
• transition metal complexes described are soluble in water, at least in small parts. As a rule, these metal complexes are readily or very readily soluble in water.
• defined metal complexes according to formula (I) can be produced by the following processes.
• weakly coordinating ligands such as 1, 5-cyclooctadiene, benzonitrile or tetramethylethylenediamine
• the reaction is generally carried out in a polar solvent, such as, for example, acetonitrile, acetone, ethanol, diethyl ether, dichloromethane or tetrahydrofuran or mixtures thereof, at temperatures in the range from -78 to + 90.degree.
• a polar solvent such as, for example, acetonitrile, acetone, ethanol, diethyl ether, dichloromethane or tetrahydrofuran or mixtures thereof, at temperatures in the range from -78 to + 90.degree.
• neutral metal complexes of the formula (I) in which L 1 and L 2 are carboxylate, for example acetate can be reacted with transition metal salts such as Pd (OAc) with the described chelate ligands (III) in acetonitrile, acetone, ethanol, Diethyl ether, dichloromethane, tetrahydrofuran or water can be prepared at room temperature. Mixtures of solvents can also be used.
• a further synthesis method is the reaction of the metal complexes of the general formula (I) with organometallic compounds from groups IA, IIA, IVA and IIB, for example Ci to C ⁇ alkyls of the metals lithium, aluminum, magnesium, tin, zinc, wherein formally charged inorganic ligands L 1 , L 2, as previously defined, are exchanged for formally charged aliphatic, cycloaliphatic or aromatic ligands L 1 , L 2, as also previously defined.
• the reaction is generally carried out in a solvent such as diethyl ether or tetrahydrofuran at temperatures in the range from -78 to 65 ° C.
• the reactions are generally carried out in coordinating solvents, for example acetonitrile, benzonitrile, tetrahydrofuran or ether, at temperatures in the range from -78 to 65 ° C.
• metal salts M'X meet the following criteria.
• the metal M ' should preferably form poorly soluble metal chlorides, such as silver chloride.
• the salt anion should preferably be a non-nucleophilic anion X, as previously defined.
• Well-suited salts for the formation of cationic complexes are e.g. Silver tetrafluoroborate, silver hexafluorophosphate, silver trifluoromethanesulfonate, silver perchlorate, silver paratoluene sulfonate, silver trifluoroacetate and silver hexafluoroantimonate, sodium tetraphenylborate, sodium tetrakis (pentafluorophenyDborate, silver trifluorodisorbate (3), sodium trifluorodisorbate (also sodium trifluorodisorbate), also sodium trifluoroacetate (3), also sodium trifluorodisorbate (3), also sodium trifluorodisorbate (3), also sodium trifluorodisorbate (3), also sodium trifluorodisorbate (3), also sodium trifluoroacetate (5), also sodium trifluorodisorbate (3), also sodium trifluorodisorbate (3).
• a further process for the preparation of the dicationic complexes of the formula (I) is the reaction of [Q 4 M] X with the chelate ligands of the general formula (III) defined at the outset.
• Q means the same or different black ligands such as acetonitrile, benzonitrile or 1,5-cyclooctadiene, M and X have the previously defined meaning.
• a preferred method for producing the metal complexes of the general formula (I) is the reaction of the dihalometal precursor complexes with silver salts containing non-coordinating anions.
• the solubilizers b) used by the process according to the invention are emulsifiers or protective colloids.
• emulsifiers or protective colloids emulsifiers or protective colloids.
• a mixture of one or more emulsifiers and one or more protective colloids can also be used.
• the emulsifier is preferably anionic, cationic, amphoteric or nonionic, in particular cationic or anionic soaps can be used. These are for example in
• alkyl sulfates and alkyl or alkylarylsulfonates with 8-30 C atoms, preferably 12-18 C atoms can be used as anionic emulsifiers.
• Particularly suitable compounds are alkali dodecyl sulfates, for example sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali metal salts of C 2 -C 6 -P raffinsulfonic acids.
• Sodium dodecylbenzenesulfonate and sodium dioctylsulfonic succinate are also suitable.
• Suitable cationic emulsifiers are salts of amines or diamines, quaternary ammonium salts, such as, for example, hexadecyltrimethylammonium bromide, and salts of long-chain substituted cyclic amines, such as pyridine, morpholine, piperidine.
• quaternary ammonium salts such as, for example, hexadecyltrimethylammonium bromide, of trialkylamines are used.
• the alkyl radicals preferably have 1 to 20 carbon atoms.
• Suitable nonionic emulsifiers are, for example, polyethylene oxide- or polypropylene oxide-based substances such as Pluronic® or Tetronic® from BASF Aktiengesellschaft.
• Protective colloids are generally water-soluble polymers which envelop the monomer droplets and the polymer particles formed therefrom and in this way protect them from coagulation.
• Protective colloids are cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymers such as polyacrylic acid and cationic polymers such as poly-N-vinyl imidazole. Further suitable protective colloids are described in the above book "Emulsion Polymerization and Emulsion Polymers", pages 226-227.
• Suitable hydroxy compounds c) are all substances which have one or more hydroxyl groups.
• Lower alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n- or iso-propanol, n-butanol, sec-butanol or tert are preferred.
• Butanol In addition, aromatic hydroxy compounds, e.g. Phenol.
• e.g. Sugar such as fructose, glucose, lactose.
• polyalcohols such as ethylene glycol, glycerin or polyvinyl alcohol. Mixtures of several coactivators can of course also be used.
• the copolymerization according to the invention of carbon monoxide and olefinically unsaturated compounds in the presence of the metal complexes or their individual components and the solubilizer is carried out in an aqueous medium.
• the polymerization mixture is preferably mixed vigorously to achieve reproducibly good productivity.
• Suitable stirring tools such as anchor or spiral stirrers can be used for this.
• Suitable stirring speeds are in the range from 100 to 1100 rpm, preferably above 150 rpm.
• the carbon monoxide copolymers can in principle be obtained by two different procedures.
• the aforementioned defined metal complexes a1) are used. These complexes are prepared separately and added as such to the reaction mixture or placed in the reaction container.
• the constituents forming the catalytically active species are added individually to the reaction mixture.
• the metal M is generally fed to the reaction vessel in salt form or as a complex salt.
• the chelating ligand compound al.2) is also added. Given Otherwise, an acid a2) and / or a hydroxy compound c) can be added as activator compound in both procedures. The addition of the activator species can be omitted if the chelating ligand al.2) has residues R 1 to R 4 which have at least one free sulfonic or carboxylic acid group.
• Suitable olefinically unsaturated monomer compounds in the processes mentioned for the preparation of the carbon monoxide copolymers are both pure hydrocarbon compounds and heteroatom-containing ⁇ -olefins, such as (meth) acrylic acid esters or amides, and homoallyl or allyl alcohols, ethers or halides.
• ⁇ -olefins such as (meth) acrylic acid esters or amides, and homoallyl or allyl alcohols, ethers or halides.
• C 3 -C 2 ol-alkenes are suitable.
• the low molecular weight ⁇ -olefins for example ⁇ -olefins with 3 to 8 carbon atoms such as propene, 1-butene, 1-pentene, 1-hexene or 1-octene
• Cyclic olefins for example cyclopentene, norbornene, aromatic olefin compounds such as styrene or .alpha.-methylstyrene or vinyl esters such as vinyl acetate can of course also be used.
• Propene is particularly preferred.
• C 1 -C 2 ol alkenes are suitable.
• the low molecular weight ⁇ -olefins for example ⁇ -olefins with 2 to 8 carbon atoms such as ethylene, propene, 1-butene, 1-pentene, 1-hexene or 1-octene, are to be emphasized.
• Cyclic olefins for example cyclopentene, norbornene, aromatic olefin compounds such as styrene or .alpha.-methylstyrene or vinyl esters such as vinyl acetate can of course also be used.
• Mixtures of ethene with low molecular weight ⁇ -olefins such as propene, 1-butene, 1-hexene, 1-octene or 1-decene are particularly preferably used. Mixtures of ethene and propene, and ethene and hexene are very particularly preferred.
• the molar ratio of carbon monoxide to ⁇ -olefin or to a mixture of ⁇ -olefins is generally in the range from 5: 1 to 1: 5, values in the range from 2: 1 to 1: 2 are usually used.
• the amount of metal complex al) or its individual components al.l) and al.2) usually used is in the range from 10 ⁇ 7 to 10 ⁇ 3 mol per mol of olefinically unsaturated monomers, an amount of 10 ⁇ 6 to 10 " 4 is preferred If the metal compound al.l) and chelate ligand al.2) are used separately, a stoichiometric composition is advantageous but not necessary.
• the copolymerization temperature is generally set in a range from 0 to 200.degree. C., preferably at temperatures in the range from 20 to 130.degree.
• the pressure is generally in the range from 2 to 300 bar and in particular in the range from 20 to 220 bar.
• Suitable catalysts a2) can be used as activator compounds for catalyst activation. Both mineral protonic acids and Lewis acids can be used as activator compounds.
• Suitable protic acids are, for example, sulfuric acid, nitric acid, boric acid, tetrafluoroboric acid, perchloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid or methanesulfonic acid.
• p-toluenesulfonic acid and tetrafluoroboric acid are used.
• Lewis acids a2) are boron compounds such as triphenylborane, tris (pentafluorophenyl) borane, tris (p-chlorophenyl) borane or tris (3,5-bis (trifluoromethyl) phenyl) borane or aluminum, zinc, antimony - or titanium compounds with a Lewis acidic character in question.
• boron compounds such as triphenylborane, tris (pentafluorophenyl) borane, tris (p-chlorophenyl) borane or tris (3,5-bis (trifluoromethyl) phenyl) borane or aluminum, zinc, antimony - or titanium compounds with a Lewis acidic character in question.
• Protonic acids or Lewis acids as well as protonic and Lewis acids are used in a mixture.
• the molar ratio of activator to metal complex a1), based on the amount of metal M, is generally in the range from 60: 1 to 1: 1, preferably from 25: 1 to 2: 1 and particularly preferably from 12: 1 to 3: 1 for the cases in which the functional groups of the radicals R 1 to R 4 are not sulfonic or carboxylic acid functionalities.
• activator compound a2) it is of course also possible to add activator compound a2) to the polymerization mixture.
• the emulsifier used as solubilizer is advantageously used in an amount of 0.005 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.1 to 2.5% by weight, based on the total mass of the monomers, used.
• the amount of protective colloids additionally or instead used as solubilizers is preferably 0.1 to 5
• the molar ratio of hydroxy compound c) to metal complex a1), based on the amount of metal M, is generally in the range from 100,000 to 0, preferably 50,000 to 500 and particularly preferably 10,000 to 1,000. 5
• the carbon monoxide copolymerization can be carried out batchwise, e.g. in stirred autoclaves, as well as continuously, e.g. in tubular reactors, loop reactors or cascade stirred tanks.
• average catalyst activities are obtained which are generally greater than 0.17 kg polymer per g (metal) per hour, in the case of CO / ethene / olefin copolymerizations greater than 0.5 kg polymer per
• the method according to the invention consequently opens up an economical, ecological, preparative simple and, in terms of safety, largely harmless access to linear, alternating carbon monoxide copolymers.
• the process according to the invention is particularly effective with regard to achievable catalyst activities, polymer bulk densities, molecular weights and their distribution and, in the presence of several different olefins, with regard to the achievable incorporation rates of higher olefins.
• Example 14 When the test was otherwise the same as in Example 12, 11.5 g of 5-hexen-l-ol were used instead of 20 ml of hexene. The activity was 2.339 kg polyketone / g (Pd) / h.
• Example 14

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