Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
  • C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals

Definitions

• the invention relates to a process for the copolymerization of polar and nonpolar monomers, a suitable catalyst system containing one or more transition metal compounds from group 5-10 of the periodic table, one or more radical formers and optionally one or more cocatalysts, the polymers obtainable therefrom, and the use thereof the polymers that can be produced in the process for the production of moldings of all kinds.
• the copolymerization of polar and nonpolar monomers under high pressure by radical polymerization is known.
• An example is the production of ethylene-acrylate copolymers (M. Buback et.al., Macromol. Chem. Phys. 1997, 198, 3627), which runs between 130 and 225 ° C at pressures between 1500 and 2500 bar.
• ethylene-vinyl acetate copolymers are typically produced at 2380 bar and 280 ° C. This high pressure of generally 500 to 3000 bar is not only technically but also economically problematic.
• the production of ethylene-vinyl acetate-CO terpolymers is similar.
• the alternating radical copolymerization of acrylic derivatives and ethene at lower pressure is known and is described, for example, in DE-A-19 49 370 and in DE-A-44 04 320.
• a disadvantage of the processes described is that the copolymerization is only successful in the presence of an acid or complexing agent which is equimolar to the polar monomer and only leads to alternating products, and that these complexing agents are only removed with great effort after the end of the polymerization.
• EP-A-558 143 describes a nickel-based catalyst by means of which ethylene and methyl methacrylate can be copolymerized.
• a disadvantage of the process described is that only insufficient amounts of the polar comonomer are also incorporated.
• WO-A-98/27124 describes a process for the polymerization of non-polar monomers (ethylene) by means Bisiminopyridylcobalt- or -eisenk 'omplexen the general formula (I) and cocatalysts, as well as the supporting of such catalyst systems in the liquid phase or in a fluidized bed process.
• WO-A-98/30612 describes a process for the polymerization of non-polar monomers (propylene) using the catalysts disclosed in WO-A-98/27124.
• WO-A-99/02472 writes bisiminopyridyl complexes of iron and a process for the oligo- and polymerization of ethylene.
• WO-A-99/12981 describes a catalyst system composed of bisiminopyridyl complexes of iron, cobalt, ruthenium or manganese for the homo- and copolymerization of ethylene and ⁇ -olefins and claims the use of ethene, propene, butene, hexene, methyl methacrylate, methyl acrylate, butyl acrylate, Acrylonitrile, vinyl acetate and styrene.
• a disadvantage of the process described is that the activation of the bisiminopyridyl complexes has to use organoaluminum compounds which, as any person skilled in the art can easily understand, can react with the polar monomers claimed and are therefore no longer available for activating the catalyst.
• the object was therefore to provide a process for the copolymerization of polar and non-polar monomers and a catalyst system suitable for this.
• a further object was to avoid disadvantages of the copolymerization processes described in the prior art.
• the invention thus relates to a process for the copolymerization of polar and non-polar monomers, characterized in that at least one polar and at least one non-polar monomer are present in the presence of one or more transition metal compounds from group 5-10 of the Periodic Table according to IUPAC 1985, one or more radical formers and optionally polymerized one or more co-catalysts.
• polar monomers are understood as meaning monomers which can be polymerized by free radicals and have a more or less pronounced partial charge distribution in the molecule.
• examples include chloroprene, styrene, acrylonitrile, vinyl chloride, acrylic acid, acrylic acid esters, cyanoacrylic esters, methacrylic acid, methacrylic acid esters, acrylamide, methacrylonitrile, vinyl acetate, propene oxide, ethene oxide, vinyl carbazole, vinyl pyrrolidone, vinyl esters, and the compounds based on these basic molecules.
• Acrylonitrile, acrylic acid ester, methacrylic acid ester and styrene are preferred.
• Nonpolar monomers in the sense of the invention are understood to mean polymerizable monomers by means of coordinative polymerization without any particular charge separation in the molecule.
• examples of these are olefins, in particular ethylene, propylene, butenes, pentenes, hexenes, heptenes, octenes and their higher homologues, diolefins, in particular butadiene, isoprene, pentadienes, hexadienes, heptadienes, octadienes, methyloctadienes, ethylidene norbornene, vinylnorbornene, norbornadienes and their cyclooctadienes higher homologues and triene.
• Suitable transition metal compounds for the purposes of the invention are compounds which correspond to the general formula (II)
• M is a metal from group 5-10 of the periodic table according to IUPAC 1985, preferably a metal selected from the group vanadium, chromium, manganese, iron, cobalt, nickel, ruthenium, rhodium and palladium,
• L represents a 2-, 3- or 4-toothed chelating ligand, preferably a 3-toothed chelating ligand
• bidentate chelating ligands are diamines, such as, for example, ethylenediamine, propylenediamine and butylenediamine, diimines, dipyridyls, dioximes, dioximates, 1,3-diketones, such as, for example, acetylacetonate and hexafluoroacetylacetonate, carboxylates, dichinones, semiquinone, bisquinoline, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquinone, bisquino
• Preferred bidentate chelating ligands are ethylenediamine, propylenediamine, bipyridyl, diimines, 2-pyridylamines, 2-pydridylimines, ethylenediphosphine, 1,3-diphosphinopropane and phosphorylide ligands.
• tridentate chelating ligands examples include tyridine, triamines, 2,6-diaminopyridyls, 2,6-bisiminopyridyls, 2,6-biscyclopentadienylpyridines, bis (2,6-hydrazonyl) pyridines, trispyrazolylborates, trispyrazolylalkanes, trispyrazolyl ketones or triphosphines.
• Preferred tridentate chelating ligands are triamines, trispyrazolylborates, 2,6-diaminopyridyls, triphosphines and bisiminopyridyl ligands of the general formula (III),
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, optionally substituted Ci-Cio-alkyl group, optionally substituted C ⁇ -Cu aryl radical or parts of a ring system.
• R 1 and R 2 are particularly preferably, independently of one another, an optionally substituted aryl radical and
• R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, optionally substituted Ci-Cio-alkyl group, optionally substituted C 6 -C] 4 - aryl radical or parts of a ring system.
• 4-tooth chelating ligands are tetraamines, tetrapyridines, tetraphosphines, salen, bis (pyridylimino) isoindolines and porphyrins.
• Preferred 4-tooth chelating ligands are trialkyl tetraamines, triaryl tetraamines, tetraphosphines and salen.
• Examples of mono- or non-ionic ligands Q is halide, hydride, C ⁇ - 0 to C ⁇ alkyl or alkenyl, C 6 -C 10 cycloalkyl, C 6 - to C ⁇ 4 -aryl, alkylaryl with C ⁇ - to Cio grouping in the alkyl group and C 6 - to Ci 4 grouping in the aryl group, -OR 8 , OR 8 R 9 , -NR 10 R ⁇ , NR 10 R n R 12 , -N (SiR 10 R ⁇ R 12 ) 2 , N (SiR , 0 R u R 12 ) 3 , -PR 10 R H , PR 10 R n R 12 , CO, tetrahydrofuran, pyridine, acetonitrile, mean, where Q can be the same or different, one or more of the two Groupings Q can also be bridged, and wherein R 8 to R 12 from H, d-
• Halogen is understood by the person skilled in the art to be fluorine, chlorine, bromine or iodine; chlorine and bromine are preferred.
• C 1 -C 0 alkyl means all linear or branched alkyl radicals with 1 to 10 C atoms known to the person skilled in the art, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neo-pentyl and hexyl, heptyl, octyl, nonyl and decyl, which in turn can in turn be substituted.
• Halogen, nitro, hydroxyl, or also C] -C 10 alkyl, and also C 6 -C 4 cycloalkyl or aryl are possible as substituents, such as benzoyl, trimethylphenyl, ethylphenyl, chloromethyl, chloroethyl and nitromethyl.
• C 6 -C 4 - cycloalkyl means all mono- or polynuclear cycloalkyl radicals having 6 to 14 carbon atoms known to the person skilled in the art, such as cyclohexyl, cycloheptyl, cyclooctyl and cyclononyl or also partially or fully hydrogenated fluorenyl, which in turn are substituted can.
• Halogen, nitro, Ci-C j o-alkoxy or also -CC-alkyl, as well as C 6 -C 2 cycloalkyl or aryl, such as methylcyclohexyl, chlorocyclohexyl and nitrocyclohexyl, are suitable as substituents.
• C 6 -C 4 aryl is understood to mean all mono- or polynuclear aryl radicals having 6 to 14 carbon atoms known to the person skilled in the art, such as phenyl, naphthyl, fluorenyl, which in turn can in turn be substituted.
• Suitable substituents here are halogen, nitro, C 1 -C alkoxy or also C 1 -C 4 alkyl, and C 6 -C 14 cycloalkyl or aryl, such as bromophenyl, chlorophenyl, toloyl and nitrophenyl.
• Q is preferably selected from halide, especially chloride and bromide, hydride, methyl, ethyl, butyl, tetrahydrofuran, CO and pyridine.
• a particularly preferred transition metal compound is the general formula (IV)
• M is selected from iron, cobalt, nickel or palladium,
• Q is a mono-anionic or non-anionic ligand, in particular chlorine,
• R 1 and R 2 independently of one another represent an optionally substituted aryl radical, in particular dialkylphenyl
• R 3 and R 4 are selected independently of one another from hydrogen, optionally substituted C 1 -C 0 -alkyl group, optionally substituted C 6 -C ] 4 aryl radical or parts of a ring system,
• n an integer in the range from 1 to 3, in particular 2,
• the transition metal compound is preferably selected so that the transition metal compound, optionally in the presence of a cocatalyst, can reversibly form a complex with the radical-growing polymer chain and nonpolar in the bond formed between transition metal and polymer chain Monomers, especially olefins, can be inserted.
• a cocatalyst can reversibly form a complex with the radical-growing polymer chain and nonpolar in the bond formed between transition metal and polymer chain Monomers, especially olefins, can be inserted.
• Suitable radical formers are all radical formers known to the person skilled in the art which are able to initiate the radical polymerization of the polar monomer and at the same time do not react disadvantageously with the transition metal compound.
• radical generator can be selected from the large number of available radical generators using a few preliminary tests. To enumerate them all would contribute nothing further to the understanding of the invention.
• An overview of radical formers suitable in principle can be found in G. Allen J.C. Bevington (ed.), Comprehensive Polymer Science, Pergamon Press, 1989, 123ff, to which reference is expressly made here.
• peroxides such as potassium or sodium peroxodisulfate, dibenzoyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, diisobutyryl peroxide, dilauryl peroxide, dilauryl peroxide, dilauryl peroxide, dilauryl peroxide, dilauryl peroxide Dibutyl peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxy-isononate, tert-butyl peroxydiethylacetate or tert-butyl peroxyacetate, and diazo compounds, such as
• the choice of the suitable radical generator is also influenced by the reaction medium and the polymerization temperature.
• the radical generator is selected such that it initiates the radical polymerization of the polar monomer under the given conditions (temperature, pressure, type of monomer, any solvent present, etc.) and at the same time not disadvantageously with the transition metal compound or the active compound formed therefrom Transition metal species reacts. For this reason, molecular oxygen, for example, is generally not suitable as a radical generator.
• coordination complex compounds selected from the group of strong, neutral Lewis acids, ionic compounds with Lewis acid cations or Bronsted acid cations and non-coordinating anions can be used as the cocatalyst.
• Compounds of the general formula V are preferred as strong neutral Lewis acids which can form stable salts or coordination complexes with Q.
• M 2 represents an element of group 3, in particular B, Al or Ga, preferably B, X 1 , X 2 and X 3 for H, - to C 10 alkyl, C to C 4 cycloalkyl, C 6 - to C 4 aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl, haloalkylaryl or haloarylalkyl, each with Ci to C 0 alkyl, C 6 to C 14 cycloalkyl and C 6 to C 4 aryl radicals and / or fluorine, chlorine, bromine or iodine, in particular for halogen aryls, preferably perfluoro-substituted.
• Lewis acidic cation is a Lewis acidic cation according to the Lewis acid base theory, preferably carbonium, oxonium, or / and sulfonium cations and cationic transition metal complexes, in particular triphenylmethyl cation, silver cation or ferrocenyl cation, or L is a Brönstedt acidic cation according to the Brönstedt acid -Base theory means, preferably trialkylammonium, dialkylarylammonium or / and alkyldiarylammonium, in particular N, N-dimethylanilinium,
• M 2 represents an element of group 3, in particular B, Al or Ga, preferably B,
• Ai to A n are singly negatively charged radicals, such as hydride, C ⁇ - C 28 alkyl, C 6 - to C cycloalkyl, C 6 - to C) -aryl, alkylaryl, arylalkyl, haloalkyl, Haloaryl, haloalkylaryl or Halogenarylalkyl each Ci- to C 28 - alkyl, C ⁇ - to C 14 cycloalkyl, and C 6 - to C ⁇ 4 -aryl, or halogen, alkoxide, aryloxide or organometalloid, and A ⁇ and A n are the same or different,
• n stands for integers from 2 to 8
• n 1 to 6.
• Preferred anions [(M 2 ) m + A ⁇ A 2 ... A n ] d "of the general formula VI are those in which Ai to A n are space-filling aromatic hydrocarbon radicals and M 2 is boron or aluminum, in particular tetraphenylborate , Tetrakis (3,5- bis (trifluoromethyl) phenylborate) and tetrakis (pentafluorophenyl) borate.
• the radical generator (s) are generally present in (total) concentrations in the range from 0.01 mol% to 5 mol%, based on the total concentration of the polar monomer (s), preferably in the range from 0.01 to 1 mol% used.
• the cheapest concentration can easily be determined by a few preliminary tests.
• the transition metal compound or the transition metal compounds are used in the range from 0.005 to 10 mol%, based on the total concentration of the radical generator (s), preferably in the range from 0.01 to 0.1 mol%.
• the cheapest concentration can easily be determined by a few preliminary tests.
• the amount of cocatalyst or cocatalysts depends on the number of ligands Q to be abstracted of the transition metal compound. Theoretically, one to 1.2 cocatalyst molecules are used for each strongly coordinating ligand Q to be abstracted. This means that generally in the range from 0.01 to 20 mol%, based on the total concentration of the radical generator (s), preferably in the range from 0.01 to 0.5 mol%, are used.
• connection should preferably take place via the ligand L, so that the components of the catalyst system do not disadvantageously interact or react with the support.
• the support materials used are preferably particulate, organic or inorganic solids whose pore volume is between 0.1 and 15 ml / g, preferably between 0.25 and 5 ml / g, the specific surface area of which is greater than 1, preferably 10 to 1000 m 2 / g (BET), the grain size of which is between 10 and 2500 ⁇ m, preferably between 50 and 1000 ⁇ m, and which can be suitably modified on its surface.
• the specific surface is determined in the usual way according to Brunauer, Emmet and Teller, J. Anorg. Chem. Soc. 1938, 60, 309, the pore volume by the centrifugation method according to McDaniel, J. Colloid Interface Sei. 1980, 78, 31 and the particle size according to Cornillaut, Appl. Opt. 1972, 11, 265.
• Suitable inorganic solids may be mentioned, for example, without wishing to restrict the present invention: silica gels, precipitated silicas, clays, aluminosilicates, talc, zeolites, carbon black, inorganic oxides such as silicon dioxide, aluminum oxide, magnesium oxide, titanium dioxide, inorganic chlorides, such as magnesium chloride , Sodium chloride, lithium chloride, calcium chloride, zinc chloride, or calcium carbonate.
• the inorganic solids mentioned that meet the above specification and are therefore used for the are particularly suitable as carrier materials, are described in more detail, for example, in Ullmann's Encyclopedia of Industrial Chemistry, volume 21, pp. 439 ff (silica gel), volume 23, pp. 311 ff (clays), volume 14, pp. 633 ff (carbon black) and volume 24, pp. 575 ff (zeolites).
• Suitable organic solids are powdery, polymeric materials, preferably in the form of free-flowing powder, with the above-mentioned properties. Examples are mentioned without wishing to restrict the present invention: polyolefins, such as, for example, polyethene, polypropene, polystyrene, polystyrene-co-di-vinylbenzene, polybutadiene, polyethers, such as, for example, polyethyleneylene oxide, polyoxytetramethylene or polysulfides, such as, for example, / - phenylensulf ⁇ d. Particularly suitable materials are polypropylene, polystyrene or polystyrene-co-di-vinylbenzene.
• organic solids mentioned which meet the above-mentioned specification and are therefore particularly suitable for use as carrier materials, are described in more detail, for example, in Ullmann's Encyclopedia of Industrial Chemistry, volume 19, p. 195 ff (polypropylene), and volume 19, p. 265 ff (polystyrene).
• the supported catalyst system can be produced in a wide temperature range. Usually, temperatures from -80 to + 200 ° C, preferably -20 to 150 ° C, particularly preferably 20 to 100 ° C, work.
• the invention further relates to a composition of one or more transition metal compounds of group 5-10 of the periodic table according to IUPAC 1985, one or more radical formers and optionally one or more co-catalysts, and their use as a catalyst system in a process for the co-polymerization of polar and non-polar monomers.
• the polymerization is preferably carried out by dissolving the monomers with the composition according to the invention in suitable solvents, gaseous, liquid in finely divided form or suspended in liquid diluent.
• Additional gases or finely divided liquids can be mixed into the gaseous, liquid or sprayed monomers, which serve either for dilution, for spraying or for heat dissipation.
• Suitable diluents or solvents are liquids or liquefied gases known to those skilled in the art which do not adversely affect the polymerization and the catalyst system, in particular saturated hydrocarbons such as pentane, hexane, cyclohexane, gasoline and petroleum ether.
• the polymerization can be carried out at pressures from 0.01 bar to 1000 bar, preferably 0.1 to 500 bar, particularly preferably 1 to 100 bar, very particularly preferably 1 to 10 bar.
• the polymerization is carried out at temperatures from -20 to 250 ° C., preferably at 0 to 200 ° C., particularly preferably at 20 to 160 ° C.
• the temperature must trivially be coordinated with the radical generator used so that the radical generator also disintegrates at the temperature.
• the transition metal compound is generally oxygen and water sensitive, it is advantageous to exclude oxygen and water.
• the order in which the individual components of the composition are combined is arbitrary. As a rule, the finished composition is brought into contact with the monomer mixture and then the temperature is raised above the decomposition temperature of the radical generator.
• Another object of the invention is the use of the polymers obtainable according to the invention for the production of moldings of all kinds, in particular foils, plates, tubes, profiles, jackets, extrudates and injection molded articles.
• Said polymers are statistical copolymers at the molecular level and are not AB block copolymers.
• Another preferred use is the use as a starting material for adhesives and additives, in particular oil additives.
• the composition can be varied over a wide range depending on the set conditions, the catalytically active composition and the monomer composition and concentrations.
• the mole fraction from built-in polar monomers to built-in non-polar monomers is in the range from 0.05 to 0.95.
• the polymers prepared according to the invention may contain homopolymers of the individual monomers as impurities.
• suitable measures such as fractional precipitation or extraction processes.
• the polymerization reactions were carried out in a 1 liter Büchi glass autoclave at 60 ° C. and the amount of ethene was measured by mass flow meters.
• the polymers were isolated by precipitation in ethanol, cleaned by washing with ethanol and dried in vacuo.
• the content of ethene in the polymer was determined by means of NMR spectroscopy in d 6 -dimethylsulfoxide, the glass temperature T g was determined by DSC and the weight-average molecular weight Mw and the polydispersity M W / M N were determined by means of GPC against polystyrene. Standard in dimethylacetamide. complex synthesis
• anhydrous cobalt (II) 0.07 g (0.5 mmol) of anhydrous cobalt (II) are added to a solution of 0.28 (0.5 mmol) of 2,6-dibenzoylbis (2,6-dimethylphenylimino) pyridine in 20 ml of dry THF at room temperature. added chloride and the mixture was stirred at RT for 48 h. The solution is then concentrated to half its volume and 100 ml of hexane are added. The bisiminopyridyl cobalt complex precipitates as a light brown powder and is dried in vacuo after filtering off. Yield: 0.15 g.
• DMAc dimethylacetamide

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