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WO2004087772A1 - Procede de production d'une dispersion polymerique aqueuse a l'aide d'un catalyseur de polymerisation insoluble dans l'eau - Google Patents

Procede de production d'une dispersion polymerique aqueuse a l'aide d'un catalyseur de polymerisation insoluble dans l'eau Download PDF

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WO2004087772A1
WO2004087772A1 PCT/EP2004/003344 EP2004003344W WO2004087772A1 WO 2004087772 A1 WO2004087772 A1 WO 2004087772A1 EP 2004003344 W EP2004003344 W EP 2004003344W WO 2004087772 A1 WO2004087772 A1 WO 2004087772A1
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water
aqueous
ethylenically unsaturated
bis
alkyl
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English (en)
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Markus Schmid
Mubarik Mahmood Chowdhry
Peter PREISHUBER-PFLÜGL
Xavier Sava
Horst Weiss
Stefan Mecking
Ludmila Kolb
Martin Zuideveld
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BASF SE
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BASF SE
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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
    • 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

Definitions

  • the present invention relates to a process for the preparation of an aqueous polymer dispersion by polymerizing at least one ethylenically unsaturated compound (monomer) using at least one water-insoluble polymerization catalyst and at least one dispersant in an aqueous medium, which is characterized in that a solution of a dispersant in water is first prepared , then introduces the water-insoluble polymerization catalyst either in solid form or mixed with a water-miscible solvent or mixed with a self-dispersing ethylenically unsaturated compound in the aqueous solution of the dispersant, then disperses the water-insoluble polymerization catalyst by mechanical energy input and with the aid of this Aqueous dispersion thus obtained is then subjected to polymerization of at least one ethylenically unsaturated compound leads.
  • the present invention further relates to the aqueous polymer dispersions obtainable by the process according to the invention and to their use for paper applications, paint coatings, adhesive raw materials, molded foams, textile or leather applications, carpet backing coatings or pharmaceutical applications.
  • Aqueous dispersions of polymers are used commercially in numerous very different applications. Until now it has been difficult to produce aqueous dispersions of polyolefins and polyketones, since these polymers are usually only poorly water-soluble. In order nevertheless to arrive at polymer dispersions based on polyolefins or polyketones starting from inexpensive monomers such as olefins or carbon monoxide, suitable, water-soluble polymerization catalysts are used, which have to be prepared in a synthetically complex manner. It is also possible to produce aqueous dispersions of polyolefins or polyketones by a so-called miniemulsion polymerization, in which the polymerization catalyst is dissolved and emulsified in an organic solvent. Such a miniemulsion polymerization, however, requires an additional manufacturing step and is relatively expensive in terms of equipment.
  • the carbon monoxide copolymerization can be carried out in suspension, as described in EP-A 0305 011, or in the gas phase, for example in accordance with EP-A 0702 045.
  • suspending agents are, on the one hand, low molecular weight alcohols, in particular methanol (see also EP-A 0428228), and on the other hand non-polar or polar aprotic liquids such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460743 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 copolymerization processes mentioned.
  • 1,3-bis (diphenylphosphino) propane or 1,3-bis [di- (o-methoxyphenyl) phosphino)] propane are particularly frequently used as chelating ligands (see also Drent et al., Chem. Rev., 1996, 96, Pp. 663 to 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, for example, methanol is bound or absorbed by the carbon monoxide copolymer. As a result, a large amount of energy is required to dry and isolate the carbon monoxide copolymers.
  • a further disadvantage is that even after an intensive drying process, residual amounts of alcohol still remain in the carbon monoxide copolymer.
  • EP-A 0485035 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.
  • copolymers carbon monoxide copolymers formed (hereinafter referred to as "copolymers") precipitate in the organic suspension media, are separated from the organic suspension media by filtration and are further processed in bulk.
  • copolymers are not in bulk but in the form of aqueous copolymer dispersions. This is particularly the case when the copolymers are to be used, for example, as binders in adhesives, sealants, plastic plasters or paints.
  • aqueous copolymer dispersions can be prepared by appropriate suspension polymerization in organic solvents, filtration, drying, grinding and dispersing the ground copolymer particles in an aqueous medium (so-called secondary dispersions).
  • secondary dispersions The disadvantage of this step concept is that it is very complex overall and the copolymers, particularly owing to the high solvent content, are difficult to grind (adhesive bonding of the mills), and the copolymer particles obtained by grinding, if at all, are dispersed in an aqueous medium, if at all, using large amounts of emulsifier can and these aqueous secondary dispersions are unstable due to their very wide particle size distribution and tend to form coagulate or sedimentation.
  • Aqueous copolymer dispersions which are directly accessible by copolymerization of carbon monoxide and olefinically unsaturated compounds in an aqueous medium can be assumed from the following prior art.
  • DE-A 10125238 discloses stable aqueous copolymer dispersions whose preparation is carried out by copolymerizing carbon monoxide and olefinically unsaturated compounds in aqueous medium using the water-soluble metal catalysts mentioned in the abovementioned application and using special comonomers in the presence of so-called host compounds.
  • the document discloses that stable copolymer dispersions are accessible even without the use of special comonomers. This is particularly the case when the copolymerization of carbon monoxide and the olefinically unsaturated compounds is carried out in the presence of ethoxylated emulsifiers.
  • WO 97/18266 relates to secondary dispersions of polyketones which are obtained by first producing a low molecular weight polyketone in an organic solvent and then dispersing it in water with emulsifiers.
  • a disadvantage of the manufacturing process described is the additional emulsification step.
  • secondary dispersions are characterized by a broad particle size distribution, which is unfavorable for some areas of application.
  • P.W. Mul et al., Inorg. Chim. Acta 2002, 327, 147-159 describes the catalyzed terpolymerization of ethylene, propylene and carbon monoxide in mixtures of water, alcohol and other solvents.
  • the dissolved terpolymer can be separated from the aqueous phase in which the catalyst is also by phase separation.
  • the catalyst is a sulfonated diphos-palladium (II) acetate complex that is activated with strong acids.
  • II diphos-palladium
  • the present invention was therefore based on the object, the described
  • a process for the preparation of an aqueous polymer dispersion by polymerizing at least one ethylenically unsaturated compound (monomer) has been found using at least one water-insoluble polymerization catalyst and at least one dispersant in an aqueous medium, which is characterized in that firstly a solution of a dispersant in Water, then introduces the water-insoluble polymerization catalyst either in solid form or mixed with a water-miscible solvent or mixed with a self-dispersing ethylenically unsaturated compound in the aqueous solution of the dispersant, then the water-insoluble polymerization catalyst by mechanical energy input dispersed and then with the aid of the aqueous dispersion obtained in this way a polymerization of at least one ethylenically unsaturated compound.
  • the aqueous polymer dispersions are obtained by polymerizing at least one ethylenically unsaturated compound (monomer) using a water-insoluble polymerization catalyst.
  • Suitable ethylenically unsaturated compounds 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.
  • C 2 - to C ao -1 -alkenes are suitable among the pure hydrocarbons.
  • the low molecular weight olefins for example ethene or ⁇ -olefins having 3 to 20 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, are to be emphasized.
  • cyclic olefins for example cyclopentene, cyclohexene, norbornene, aromatic olefin compounds, such as styrene or a-methylstyrene, or vinyl esters, such as vinyl acetate, can also be used.
  • aromatic olefin compounds such as styrene or a-methylstyrene
  • vinyl esters such as vinyl acetate
  • the C 2 - to C 2 o-1 alkenes are particularly suitable.
  • Q is a non-polar organic group selected from the group comprising linear or branched C to C 2 o -alkyl, often C 2 to C 18 alkyl and often C 3 to C 14 alkyl, for example methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -heptyl, -octyl, -nonyl, -decyl, -undecyl, -dodecyl, -tridecyl or - Tetradecyl, C 3 - to C -cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, C 6 - to Cu-aryl, for example phenyl, naphthyl or phenanthryl and alkylaryl
  • Pol is a polar radical which is selected from the group comprising carboxyl (- C0 2 H), sulfonyl (-S0 3 H), sulfate (-OSO 3 H), phosphonyl (-PO 3 H), phosphate (-OPO 3 H 2 ) and their alkali metal salts, in particular sodium or potassium salts, alkaline earth metal salts, for example magnesium or calcium salts and / or ammonium salts.
  • Pol also includes the alkanolammonium, pyridinium, imidazolinium, oxazolinium, morpholinium, thiazoline, quinolinium, isoquinolinium, tropylium, sulfonium, guanidinium and phosphonium compounds, and especially ammonium compounds, which are accessible by protonation or alkylation of the general formula (V)
  • R 6 , R 7 and R 8 independently of one another represent hydrogen and linear or branched d- to C 20 -alkyl, frequently C to Cio-alkyl and often d- to C 5 -alkyl, alkyl being for example methyl, ethyl, n - or i-propyl, n-, i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -heptyl, -octyl, -nonyl, -decyl, -undecyl, -dodecyl, -tridecyl or - is tetradecyl.
  • the corresponding anions of the abovementioned compounds are non-nucleophilic anions, such as, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, for example Methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexatluafluoroarsenate.
  • organosulfonic acids for example Methyl sul
  • the polar radical Pol can also be a group of the general formula (VI), (VII) or (VIII)
  • PO stands for a -CH 2 -CH (CH 3 ) -O- or a -CH (CH 3 ) -CH 2 -O group
  • k and I for numerical values from 0 to 50, often from 0 to 30 and often from 0 to 15, but k and I are not 0 at the same time.
  • (EO) k is a block of k -CH 2 -CH 2 -0 groups
  • (PO) is a block of I -CH 2 -CH (CH 3 ) -O- or -CH (CH 3 ) -CH 2 -O groups
  • R * stands for hydrogen, linear or branched C to C 2 o-alkyl, often C r to C ⁇ 0 - alkyl and often d- to C 6 -alkyl or -SO 3 H and its corresponding alkali metal, alkaline earth metal and / or ammonium salt.
  • alkyl is, for example, methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -
  • the compounds containing the structural element of the general formula (IV) are, in particular, ⁇ -olefins of the general formula (IX)
  • Preferred olefins (IX) are 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and styrene-4-sulfonic acid.
  • the proportion of the amount of the ethylenically unsaturated compound (s) containing the structural element of the general formula (IV) in the monomer mixture to be polymerized, consisting of at least one ethylenically unsaturated compound containing the structural element of the general formula (IV) and at least one of the aforementioned ethylenically unsaturated compound is 0 to 100% by weight, often 0.5 to 80% by weight and often 1.0 to 60% by weight or 2.0 to 40% by weight.
  • the ethylenically unsaturated compounds according to the invention are, in particular, ethene, propene, 1-butene, i-butene, 1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene and / or norbornene or these in a mixture with 10-undecenoic acid, 3-butenoic acid , 4-pentenoic acid, 5-hexenoic acid and / or styrene-4-sulfonic acid.
  • carbon monoxide can also be used according to the invention, which ultimately results in polymer dispersions based on polyketones, which generally consist of alternating structural elements based on suitable ethylenically unsaturated compounds on the one hand and carbon monoxide on the other. It is advisable to set the quantitative ratio between the ethylenically unsaturated compound or compounds on the one hand and the carbon monoxide on the other hand to 80 mol% to 20 mol%, in particular to 60 mol% to 40 mol%.
  • Particularly suitable ethylenically unsaturated compounds for the production of polyketones are nonpolar ethylenically unsaturated compounds, for example ethylene or ⁇ -olefins having 3 to 20 carbon atoms.
  • water-insoluble polymerization catalysts means in particular those polymerization catalysts which have a water solubility of less than 10 "4 g catalyst per 100 g water, preferably less than 10 " 5 g catalyst per 100 g water.
  • polymer dispersions based on polyketones are to be produced using the process according to the invention, it is advisable to carry out the reaction of the ethylenically unsaturated compounds and carbon monoxide in the aqueous medium using the following polymerization catalyst:
  • R is hydrogen, linear or branched d to C 20 alkyl, C 3 to Cio-cycloalkyl, C 6 to C 1 aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des Periodic table-substituted C 6 to C 14 aryl, aralkyl with 1 to 20 C atoms in the alkyl radical and 6 to 14
  • R a independently linear or branched C to C 20 alkyl, C 3 - to Cio-cycloalkyl, C 6 - to C 14 -aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des accrual Systems substituted C 6 to C 14 aryl, aralkyl with 1 to 20 C atoms in the alkyl part and 6 to 14 C atoms in the aryl part,
  • R b as R a and additionally hydrogen and -Si (R c ) 3 ,
  • R c linear or branched d to C 20 alkyl, C 3 to Cio-cycloalkyl, C 6 to C 14 aryl or aralkyl having 1 to 20 C atoms in the alkyl part and 6 to 14 C atoms in the aryl part,
  • Z is an element from the VA group 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 is a non-metallic element from group VA of the periodic table of the elements
  • R 1 to R 4 independently of one another are linear or branched d- to C 20 -alkyl, C 3 - to Cio-cycloalkyl, C 6 - to C 14 -aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted C 6 to C 1 aryl, aralkyl with 1 to 20 C atoms in the alkyl radical and 6 to 14 C atoms in the aryl radical or heteroaryl,
  • R f , R 9 independently of one another for hydrogen, linear or branched d- to C 6 -alkyl or
  • R e and R f together represent a five- or six-membered carbo- or heterocycle
  • 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; group IB contains Cu, Ag, Au).
  • Suitable metals M of the metal complexes to be used according to the invention are the metals from groups VIIIB, IB and IIB of the Periodic Table of the Elements, i.e. in addition to copper, silver or zinc, also iron, cobalt and nickel and the platinum metals such as ruthenium, rhodium, osmium, iridium and Platinum, with nickel and palladium being very particularly preferred.
  • the elements E and E 2 of the chelating ligands are the non-metallic elements of the 5th main group of the periodic table of the elements, for example nitrogen, phosphorus or arsenic. Nitrogen or phosphorus are particularly suitable, especially phosphorus.
  • the chelating ligands can contain different elements E 1 and E 2 , for example nitrogen and phosphorus.
  • the structural unit G in the metal complex (I) is a single or multi-atom bridging structural unit.
  • a bridging structural unit is basically understood to mean a grouping which connects the elements E 1 and E 2 in structure (I) to one another.
  • 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 ) 2 - or - Si (R a ) 2 -, in which R a independently of one another in particular for linear or branched d- to Cio-alkyl, for example methyl, ethyl, i-propyl or t-butyl, C 3 - to C 6 - cycloalkyl, such as cyclopropyl or cyclohexyl, C B - to Cio-aryl, such as phenyl or naphthyl, with functional Groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted C 6 - to Cio-aryl, for example tolyl, (trifluoromethyl) phenyl, dimethylaminophenyl, p-methoxyphenyl or partially or perhalogen
  • the two- and three-atom bridged structural units should be emphasized, the latter generally being preferred.
  • R f , R 9 independently of one another are hydrogen, straight-chain or branched C to C 6 alkyl, such as methyl, ethyl or i-propyl, or
  • R e and R f together represent a five- or six-membered carbo- or heterocycle
  • chelate ligands such as 1, 10-phenanthroline, 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine or their substituted derivatives can be traced back to diatomically bridged structural units.
  • Suitable three-atom bridged structural units are generally based on a chain of carbon atoms, for example propylene (-CH 2 CH 2 CH 2 -), or on a bridging 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 free valences can be substituted by d- to C 6 -alkyl, such as methyl, ethyl or tert-butyl, C 6 - to cio-aryl, such as phenyl, or by functional groups such as triorganosilyl, dialkylamino or halogen ,
  • Suitable substituted propylene bridges are, for example, those with a methyl, phenyl or methoxy group in the 2-position.
  • the radical R 5 on Z can in particular mean: hydrogen, linear or branched C to C 10 alkyl, such as methyl, ethyl, i-propyl or t-butyl, C 3 to C 6 cycloalkyl, such as cyclopropyl or cyclohexyl , C 6 - to C 10 -aryl, for example phenyl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table, substituted C 6 - to cio-aryl, such as tolyl, mesityl, aralkyl with 1 to 6 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical, pyridyl, long-chain radicals with 12 to 22 carbon atoms in the chain, which have polar
  • R a independently of one another hydrogen, linear or branched Cr to C ⁇ 0 - alkyl, such as methyl, ethyl, i-propyl or t-butyl, C 3 - to C 6 -cycloalkyl, for example
  • Aryl part for example benzyl
  • R as R and additionally hydrogen and -Si (R c ) 3 ,
  • R c is linear or branched Cr to C 10 -alkyl such as methyl or ethyl, C 3 - to C 6 - cycloalkyl, for example cyclohexyl, C 6 - to C ⁇ 0 aryl, for example phenyl, or aralkyl with 1 to 6 C- Atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl, which, for example, trimethyl-, triethyl-, triphenyl- or t-butyldiphenylsilyl fall under the formula -Si (R c ) 3
  • the metal complexes (I) chelated with monatomic ligands those are preferred, for example, in which M is palladium positively charged as divalent is present, the elements E 1 and E 2 are phosphorus and the bridging structural unit G is methylene, ethylidene, 2-propylidene, dimethylsilylene or diphenylsilylene, in particular methylene.
  • the monatomically bridged metal complexes advantageously have radicals R1 to R4, at least one of which is a non-aromatic radical.
  • aromatic radicals phenyl and tolyl and o-, m- or p-anisyl are particularly noteworthy, among the aliphatic radicals are methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, n -, i- or neo-pentyl, -hexyl, -heptyl, -ctyl, -nonyl, -decyl, -undecyl, -dodecyl, -tridecyl or -tetradecyl.
  • Metal complexes (I) which have a three-atom bridge are particularly preferred. This includes, for example, compounds in which the elements E1 and E2 are connected by a propylene unit (-CH 2 CH 2 CH 2 -) and the further substituents in formula (I) have the following meaning:
  • E 1 , E 2 phosphorus or nitrogen, in particular phosphorus
  • R 1 to R 4 independently of one another are linear or branched d- to C 20 -alkyl, frequently Cr to Cio-alkyl and often d- to C 5 -alkyl, where alkyl is, for example, methyl,
  • substituted C 6 to C 10 aryl such as linear or branched d to C 6 alkyl, for example methyl, ethyl, i-propyl, t-butyl, partially or perhaogenized d to C 6 alkyl, for example trifluoromethyl or 2,2,2-trifiuorethyl, triorganosilyl such as trimethylsilyl, triethylsilyl or t
  • Butyldiphenylsilyl amino, for example dimethylamino, diethylamino or di-i-propylamino, alkoxy, for example methoxy, ethoxy or t-butoxy, or halogen, such as fluorine, chlorine, bromine or iodine, aralkyl with 1 to 3 carbon atoms in the alkyl radical and 6 up to 10 carbon atoms in the aryl radical, for example benzyl, or heteroaryl, such as pyridyl,
  • L 1 , L 2 acetonitrile, acetylacetone, trifluoroacetate, benzonitrile, tetrahydrofuran, diethyl ether, acetate, tosylate or water, and also methyl, ethyl, propyl, butyl, phenyl or benzyl, X tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, pentafluorobenzoate, trifluoromethanesulfonate, trifluoroacetate, perchlorate, p-toluenesulfonate or tetraaryl borates such as tetrakis (pentafluorophenyl) borate or tetrakis (3,5-bis) trifluoromethyl
  • Further preferred metal complexes have bidentate ligands which contain bipyridine structures.
  • E 1 , E 2 phosphorus or nitrogen, in particular phosphorus
  • R 1 to R 4 independently of one another are linear or branched Cr to C 20 alkyl, frequently d- to do-alkyl and often C to C 5 alkyl, alkyl being for example methyl, ethyl, n- or i-propyl, n- , i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -heptyl,
  • C 3 - to C 6 -cycloalkyl such as cyclopropyl, cyclohexyl or 1-methylcylohexyl, especially cyclohexyl, C 6 - bis Cio-aryl, such as phenyl or naphthyl, especially phenyl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des
  • Periodic table substituted C 6 - to Cio-aryl such as linear or branched d to C 6 alkyl, for example methyl, ethyl, i-propyl, t-butyl, partially or perhalogenated d to C 6 alkyl, for example trifluoromethyl or 2 , 2,2-trifluoroethyl, triorganosilyl, such as trimethylsilyl, triethylsilyl or t-butyldiphenylsilyl, amino, for example dimethylamino, diethylamino or di-i-propylamino, alkoxy, for example methoxy, ethoxy or t-butoxy, or halogen, such as fluorine, chlorine, Bromine or iodine, aralkyl with 1 to 3 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical, for example benzyl, or heteroaryl, such as pyridy
  • L 1 , L 2 acetonitrile, benzonitrile, acetone, acetylacetone, diethyl ether, tetrahydrofuran, acetate, trifluoroacetate or benzoate, and also methyl, ethyl, propyl, butyl, phenyl or benzyl,
  • metal complexes used are positively charged, in particular BF 4 " , SO 4 2" , trifluoroacetate, nitrate, perchlorate, tosylate, trifluoromethanesulfonate or methanesulfonate are suitable as non-coordinating counterions.
  • the aforementioned metal complexes are used in the presence of acids, which are also referred to as activators.
  • Both mineral protonic acids and Lewis acids are suitable as activator compounds.
  • suitable protic acids are 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 preferably used.
  • Lewis acids examples include 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 acid character in question. Mixtures of protonic acids or Lewis acids and protonic and Lewis acids in a mixture can also be used.
  • the molar ratio of optionally used acid to metal complex, based on the amount of metal M, is generally in the range from 60: 1 to 1: 1, frequently from 25: 1 to 2: 1 and often from 12: 1 to 3: 1.
  • the aforementioned metal complexes are used together with the acids in the presence of organic hydroxy compound.
  • Suitable organic hydroxy compounds are all low molecular weight organic substances (M w ⁇ 500) which have one or more hydroxyl groups.
  • Lower alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n- or i-propanol, n-butanol, s-butanol or t-butanol, are preferred.
  • Aromatic hydroxy compounds such as phenol, can also be used.
  • Sugars such as fructose, glucose or lactose are also suitable.
  • polyalcohols such as ethylene glycol, glycerin or polyvinyl alcohol. Mixtures of several hydroxy compounds can of course also be used.
  • the molar ratio of optionally used hydroxy compound to metal complex, based on the amount of metal M is generally in the range from 0 to 100,000, often from 500 to 50,000 and often from 1,000 to 10,000.
  • the metals M can be present in the complexes in a formally uncharged, formally single positive or preferably formally double positive.
  • Suitable formally charged anionic ligands L 1 , L 2 are hydride, sulfates, phosphates or nitrates.
  • Carboxylates or salts of organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate or p-toluenesulfonate are also suitable.
  • the salts of organic sulfonic acids p-toluenesulfonate is preferred.
  • Preferred formally charged ligands L 1 , L 2 are carboxylates, preferably d to C 20 carboxylates and in particular Cr to C 7 carboxylates, that is to say, 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 C 20 aliphatic radicals, C 3 to C 4 cycloaliphatic radicals, C 7 to C 20 arylalkyl radicals with C 6 to C aryl radicals and d to C 6 alkyl radicals and C 6 - to -C 4 aromatic radicals, for example methyl, ethyl, propyl, i-propyl, t-butyl, n-, i-pentyl, cyclohexyl, benzyl, phenyl and aliphatic or aromatic substituted phenyl radicals.
  • Lewis bases ie compounds with at least one lone pair of electrons, are generally suitable as formally uncharged ligands L 1 , L 2 .
  • d- to C 10 -nitriles such as acetonitrile, propionitrile, benzonitrile or C 2 - to -C- 0 ketones such as acetone, acetylacetone or C 2 - to cioethers such as dimethyl ether, diethyl ether, tetrahydrofuran.
  • acetonitrile, tetrahydrofuran or water are used.
  • the ligands L 1 and L 2 can be present in any ligand combination, ie the metal complexes (I) or (III) or the rest according to formula (II) can be, for example, a nitrate and an acetate residue, a p-toluenesulfonate and contain an acetate residue or a nitrate and a formally charged organic ligand 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. However, if the M-containing complex fragment is formally uncharged, the complex according to the invention according to formula (I) or (III) contains none Anion X. Anions X are advantageously used which are as little nucleophilic as possible, ie which 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, methylsulfonate, trifluoromethylsulfonate and p-toluene tetronate, Tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • organosulfonic acids such as, for example, methylsulfonate, trifluoromethylsulfonate and p-to
  • Perchlorate, trifluoroacetate, sulfonates such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate, tetrafluoroborate or hexafluorophosphate and in particular trifluoromethyl sulfonate, trifluoroacetate, perchlorate or p-toluenesulfonate are preferably used.
  • polymer dispersions based on polyolefins are to be produced using the process according to the invention, it is advisable to carry out the polymerization of the ethylenically unsaturated compounds in an aqueous medium using the following polymerization catalyst:
  • M d is a transition metal from groups 7 to 10 of the Periodic Table of the Elements (according to the nomenclature used from 1987), preferably manganese, iron, cobalt, nickel or palladium,
  • Aryl anions where L 1 d and L 2 d are covalent to one another
  • Bonds can be linked, E d nitrogen, phosphorus, arsenic or antimony, X d -SO 3 -, -O-PO 3 2 -, NH (R 15 d ) 2 + , N (R 15 d ) 3 + or - ( OCH 2 CH 2 ) n OH, n is an integer from 0 to 15,
  • R 1 d hydrogen, CrC ⁇ 2 alkyl groups, C 7 -C ⁇ 3 aralkyl radicals and C 6 -C ⁇ -
  • Aryl groups unsubstituted or substituted with a hydrophilic group X d , R 2 d and R 3 d hydrogen, hydrophilic groups X d ,
  • Halogens or amino groups NR 13 d R 14 d where the radicals R 2 d and R 3 d can form a saturated or unsaturated 5- to 8-membered ring with one another, and at least one radical R 1 d , R 2 d or R 3 d bears a hydrophilic group X d ;
  • R 4 d to R 7 d are hydrogen, hydrophilic groups X d , d -CC 2 alkyl, where the alkyl groups can be branched or unbranched, CC 12 alkyl, substituted one or more times identically or differently by C C 2 alkyl groups, halogens, hydrophilic groups X d , CrC 12 alkoxy groups or the d C 1 -C 2 thioether groups, C 7 -C 3 aralkyl, C 3 -C 2 cycloalkyl,
  • R 8 d and R 9 d are hydrogen, dC 6 alkyl groups, C 7 -Ci 3 aralkyl groups and C 6 -d 4 -
  • Aryl groups unsubstituted or substituted with a hydrophilic group X d , R 10 d to R 15 d hydrogen, dC 20 alkyl groups, which in turn can be substituted with O (dC 6 alkyl) or N (CrC 6 alkylI) 2 groups , C 3 -C 2 cycloalkyl groups, C 7 -C 3 aralkyl radicals and C 6 -C aryl groups;
  • R 6 is hydrogen, dC 20 -alkyl groups, which in turn can be substituted by O (CrC 6 -alkyl) or N (d-C 6 -alkyl) 2 groups,
  • L 1 d and L 2 d are linked to one another by one or more covalent bonds.
  • ligands are 1,5-cyclooctadienyl ligands (“COD”), 1,6-cyclodecenyl ligands or 1,5,9-all-trans-cyclododecatrienyl ligands.
  • Such complex compounds of the general formula A or B, their preparation, their special configurations and particularly suitable representatives of these complex compounds are described in detail in WO 01/44325, the disclosure content of which is hereby incorporated in its entirety.
  • the compounds A and B can be used in a ratio of 0: 100 to 100: 0 mol%. Preferred embodiments are 0: 100 mol%, 10: 90 mol%, 50: 50 mol%, 90: 10 mol% and 100: 0 mol%.
  • the activator can be olefin complexes of rhodium or nickel.
  • Ni (C 2 H 4 ) 3 Ni (1, 5-cyclooctadiene) 2 "Ni (COD) 2 ", Ni (1, 6-cyclodecadiene) 2 , or Ni (1, 5,9-all-trans-cyclododecatriene ) 2 .
  • Ni (COD) 2 is particularly preferred.
  • Some complexes of the general formula A or B can be activated by ethylene.
  • the ease of the activation reaction depends crucially on the nature of the ligand L 1 d. It could be shown that in the case that L 1 d is a tetramethylethylenediamine ligand, no activator is required.
  • the dispersants used in the process according to the invention can be emulsifiers or protective colloids.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, copolymers containing vinyl-2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid and their alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, as well as their alkali metal nitrate, as well N- vinyl carbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acryl
  • emulsifiers can of course also be used. Often only emulsifiers are used as dispersants, whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They can be of anionic, cationic or nonionic nature. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked in the case of doubt using a few preliminary tests. In general, anionic emulsifiers are compatible with one another and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually not compatible with one another.
  • anionic, cationic and / or nonionic emulsifiers are used in particular as dispersants.
  • Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri- alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 to C ⁇ 2 ) and ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C 8 to C 36 ).
  • Lutensol® A brands C 12 C fatty alcohol ethoxylates, EO grade: 3 to 8
  • Lutensol® AO brands C ⁇ 3 Ci 5 oxo alcohol ethoxylates, EO grade: 3 to 30
  • Lutensol® AT Brands C 16 d 8 - fatty alcohol ethoxylates, EO grade: 11 to 80
  • Lutensol® ON brands C 10 -
  • Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 2 ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 2 to C 8 ) and ethoxylated alkyl phenols (EO- Degree: 3 to 50, alkyl radical: C to C 2 ), of alkyl sulfonic acids (alkyl radical: C 2 to C ⁇ 8 ) and of alkylarylsulfonic acids (alkyl radical: C 9 to C ⁇ 8 ).
  • Compounds of the general formula (X) have also proven to be further anionic emulsifiers:
  • R y and R z represent H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms
  • D 1 and D 2 can be alkali metal ions and / or ammonium ions.
  • R y and R E are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R y and R z are not both H Atoms are.
  • D 1 and D 2 are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • Suitable cationic emulsifiers are usually a C 6 - to -C 8 alkyl, - alkylaryl or heterocyclic radical having primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts and thiazolinium salts Amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinic acid esters, N-cetylpyridinium sulfate, N-laurylpyridinium sulfate and N-cetyl-N, N, N-trimethylammonium sulfate, N- Dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethlyammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate as well as the gemini surfactant N, N'- (lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl -N-methylammonium sulfate and
  • the anionic countergroups are as possible are low nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as white acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as, for example, methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate (tetrakis), tetrakis (tetrakis), tetrakis (tetrakis, tetrakis (tetrakis, 5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • the emulsifiers which are preferably used as dispersants are advantageously used in a total amount of 0.005 to 10 parts by weight, preferably 0.01 to 7 parts by weight, in particular 0.1 to 5 parts by weight, based in each case on 100 parts by weight of the olefinically unsaturated compounds.
  • the amount of emulsifier is frequently chosen so that the critical micelle formation concentration of the emulsifiers used is essentially not exceeded within the aqueous phase.
  • the total amount of protective colloids additionally or instead used as dispersants is often 0.1 to 10 parts by weight and often 0.2 to 7 parts by weight, based in each case on 100 parts by weight of the olefinically unsaturated compounds.
  • Organic solvents which are only slightly soluble in water can optionally be used in the process according to the invention.
  • Suitable solvents are liquid aliphatic and aromatic hydrocarbons with 5 to 30 carbon atoms, such as n-pentane and isomers, cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers, n- Nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, eicosane, benzene, toluene, ethylbenzene, cumene, o-, m- or p-xylene, mesitylene, and generally hydrocarbon mixtures in the boiling range
  • Hydroxy compounds such as saturated and unsaturated fatty alcohols having 10 to 32 carbon atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol and their isomers or cetyl alcohol, ceryl alcohol or myricyl alcohol (mixture of C 30 and C 3 alcohols) can also be used.
  • Esters such as fatty acid esters with 10 to 32 C atoms in the acid part and 1 to 10 C atoms in the alcohol part or esters from carboxylic acids and fatty alcohols with 1 to 10 C atoms in the carboxylic acid part and 10 to 32 C atoms in the alcohol part.
  • Esters such as fatty acid esters with 10 to 32 C atoms in the acid part and 1 to 10 C atoms in the alcohol part or esters from carboxylic acids and fatty alcohols with 1 to 10 C atoms in the carboxylic acid part and 10 to 32 C atoms in the alcohol part.
  • the total amount of solvent is up to 15 parts by weight, preferably 0.001 to 10 parts by weight and particularly preferably 0.01 to 5 parts by weight, in each case based on 100 parts by weight of water.
  • Solvents are used in particular when the olefinically unsaturated compounds are gaseous under reaction conditions (pressure / temperature), as is the case, for example, with ethene, propene, 1-butene and / or i-butene.
  • the process according to the invention is characterized in that a solution of one or more of the dispersing agents described above is first prepared in water and then the water-insoluble polymerization catalyst is introduced into the aqueous solution of the dispersing agent.
  • the water-insoluble polymerization catalyst can be introduced into the aqueous solution of the dispersant either in solid form or mixed with a water-miscible solvent or mixed with a self-dispersing ethylenically unsaturated compound.
  • the water-insoluble polymerization catalyst is introduced as a solid or oily metal complex into the aqueous solution of the dispersant, it is advisable to do this at temperatures from 0 to 100 ° C., in particular from 20 to 80 ° C. and particularly preferably at 40 to 60 ° C.
  • the water-insoluble polymerization catalyst can be mixed with a water-miscible solvent and introduced into the aqueous solution of the dispersant.
  • Solvents suitable for this have a solubility in the aqueous reaction medium of at least 50% by weight, in particular at least 60% by weight, particularly preferably at least 70% by weight, in particular at least 80% by weight, in each case based on the total amount of solvent , on.
  • Suitable water-miscible solvents include: Alcohols such as methanol, ethanol, n- or iso-propanol, butanol or polyethylene glycols, acetone or tetrahydrofuran.
  • the water-insoluble polymerization catalyst can also be mixed with a self-dispersing, ethylenically unsaturated compound in the aqueous solution of the dispersant.
  • Suitable self-dispersing, ethylenically unsaturated compounds include 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid or styrene-4-sulfonic acid, or 1-butenol, 1-pentenol, 1-hexenol or with 1-20 Eo units ethoxylated 1-butenol, 1-pentenol, 1-hexenol.
  • the water-insoluble polymerization catalyst is dispersed by mechanical energy input, preferably at temperatures from 0 to 100 ° C., in particular from 20 to 80 ° C., using the process according to the invention.
  • the mechanical energy input is preferably carried out with the aid of suitable shearers, homogenizers, ultrasonic units (sonotrodes) or stirring devices. It is also possible here to use suitable homogenizers, ultrasound units or other shearing devices to produce an aqueous mini-emulsion from the aqueous macroemulsion initially present.
  • High-pressure homogenizers for example, can be used for this purpose.
  • the fine distribution of the components in these machines is achieved through a high local energy input.
  • Two variants have proven particularly useful in this regard.
  • the aqueous macroemulsion is compressed to over 1000 bar using a piston pump and then expanded through a narrow gap.
  • the effect here is based on an interaction of high shear and pressure gradients and cavitation in the gap.
  • An example of a high-pressure homogenizer that works on this principle is the Niro-Soavi high-pressure homogenizer type NS1001 L Panda.
  • the compressed aqueous macroemulsion is expanded into a mixing chamber via two opposing nozzles.
  • the fine distribution effect depends above all on the hydrodynamic conditions in the mixing chamber.
  • An example of this type of homogenizer is the M 120 E microfluidizer from Microfluidics Corp.
  • the aqueous macroemulsion is compressed to a pressure of up to 1200 atm by means of a pneumatically operated piston pump and expanded via a so-called "interaction chamber".
  • the emulsion jet is divided into two jets in a microchannel system, which are brought together at an angle of 180 °.
  • homogenizer working according to this type of homogenization is the Nanojet type Expo from Nanojet Engineering GmbH.
  • two homogenizing valves are installed in the Nanojet, which can be adjusted mechanically.
  • homogenization can also be carried out, for example, by using ultrasound (eg Branson Sonifier II 450). The fine distribution here is based on cavitation mechanisms.
  • the devices described in GB-A 2250 930 and US-A 5,108,654 are in principle also suitable for homogenization by means of ultrasound.
  • the quality of the aqueous miniemulsion generated in the sound field depends not only on the sound power introduced, but also on other factors such as e.g. B.
  • the intensity distribution of ultrasound in the mixing chamber depends, inter alia, on the concentration of the emulsifier and on the energy introduced during the homogenization and can therefore be set in a targeted manner, for example by changing the homogenization pressure or the corresponding ultrasound energy.
  • the device described in DE-A 19756874 has proven particularly useful for producing an aqueous miniemulsion from conventional macroemulsions by means of ultrasound.
  • This is a device which has a reaction space or a flow-through reaction channel and at least one means for transmitting ultrasound waves to the reaction space or the flow-through reaction channel, the means for transmitting ultrasound waves being designed in such a way that the entire reaction space or the flow-through reaction channel can be irradiated uniformly with ultrasonic waves in one section.
  • the radiation surface of the means for transmitting ultrasound waves is designed such that it substantially corresponds to the surface of the reaction space or, if the reaction space is a section of a flow-through reaction channel, extends essentially over the entire width of the channel, and that the depth of the reaction space, which is essentially perpendicular to the radiation surface, is less than the maximum depth of action of the ultrasound transmission means.
  • depth of the reaction space essentially means the distance between the radiation surface of the ultrasound transmission means and the bottom of the reaction space.
  • Reaction chamber depths of up to 100 mm are preferred.
  • the depth of the reaction space should advantageously not be more than 70 mm and particularly advantageously not more than 50 mm.
  • the reaction spaces can in principle also have a very small depth, but in view of the lowest possible risk of clogging and easy cleanability and a high product throughput, reaction space depths are preferred which are considerably larger than, for example, the usual gap heights at high pressure are homogenizers and are usually over 10 mm.
  • the depth of the reaction space can advantageously be changed, for example by means of ultrasound transmission means immersed in the housing at different depths.
  • the radiation area of the means for transmitting ultrasound corresponds essentially to the surface of the reaction space.
  • This embodiment is used for batch production of mini emulsions.
  • ultrasound can act on the entire reaction space.
  • a turbulent flow is generated in the reaction space by the axial sound radiation pressure, which causes intensive cross-mixing.
  • such a device has a flow cell.
  • the housing is designed as a flow-through reaction channel, which has an inflow and an outflow, the reaction space being a partial section of the flow-through reaction channel.
  • the width of the channel is the channel extension which is essentially perpendicular to the direction of flow.
  • the radiation area covers the entire width of the flow channel transverse to the direction of flow.
  • the length of the radiation surface perpendicular to this width that is to say the length of the radiation surface in the direction of flow, defines the effective range of the ultrasound.
  • the flow-through reaction channel has an essentially rectangular cross section.
  • a likewise rectangular ultrasound transmission medium with corresponding dimensions is installed in one side of the rectangle, a particularly effective and uniform sound system is guaranteed. Due to the turbulent flow conditions prevailing in the ultrasonic field, however, a round transmission means can also be used without disadvantages, for example.
  • a plurality of separate transmission means can be arranged, which are connected in series as seen in the flow direction. Both the radiation surfaces and the depth of the reaction space, that is to say the distance between the radiation surface and the bottom of the flow channel, can vary.
  • the means for transmitting ultrasound waves is particularly advantageously designed as a sonotrode, whose end facing away from the free radiation surface is coupled to an ultrasound transducer.
  • the ultrasonic waves can be generated, for example, by utilizing the reverse piezoelectric effect.
  • high-frequency electrical vibrations (usually in the range from 10 to 100 kHz, preferably between 20 and 40 kHz) are generated by means of a piezoelectric transducer into mechanical vibrations of the same frequency converted and coupled with the sonotrode as a transmission element in the medium to be sonicated.
  • the sonotrode is particularly preferably designed as a rod-shaped, axially radiating ⁇ / 2 (or multiple of ⁇ / 2) longitudinal oscillators.
  • baffles are provided in the reaction space to improve the flow and mixing behavior.
  • These internals can be, for example, simple deflection plates or a wide variety of porous bodies.
  • the mixing can also be further intensified by an additional agitator.
  • the reaction space can advantageously be temperature-controlled.
  • polymerization of one or more ethylenically unsaturated compounds is carried out by the process according to the invention. If the polymerization should lead to polyketone dispersions, it is necessary to polymerize the ethylenically unsaturated compound together with carbon monoxide.
  • the partial pressure of carbon monoxide should generally be in the range from 1 to 300 bar, in particular in the range from 1 to 80 bar.
  • the polymerization reactor is usually rendered inert before being pressed on with carbon monoxide by flushing with carbon monoxide, ethylenically unsaturated compounds or inert gas, for example nitrogen or argon.
  • the polymerization temperature is generally set in a range from 0 to 120 ° C., in particular in a range from 20 to 100 ° C. and particularly preferably in a range from 40 to 80 ° C.
  • the process according to the invention can be carried out in the customary polymerization apparatus used in industry, preferably in stirred reactors, autoclaves, in particular high-pressure autoclaves, and in continuous tubular reactors or in so-called bubble columns, which can also be connected as a cascade.
  • the polymers obtained by the process according to the invention have molar masses (weight average), determined by means of gel permeation chromatography and 1, 1, 1, 3,3,3-hexafluoro-2-propanol as solvent, which are in the range from 1000 to 1,000,000, frequently in the range from 1500 to 800000 and in particular in the range from 2000 to 600000.
  • the polyketones which are likewise accessible by the processes according to the invention are, as 13 C or 1 H NMR spectroscopic studies show, generally linear, alternating carbon monoxide copolymer compounds.
  • copolymer compounds in which in the polymer chain on each carbon monoxide unit a -CH 2 -CH 2 -, -CH 2 -CH- or -CH-CH unit originating from the olefinic double bond of the at least one olefinically unsaturated compound and on each -CH 2 -CH 2 -, -CH 2 -CH- or -CH-CH unit is followed by a carbon monoxide unit.
  • the ratio of carbon monoxide units to - CH 2 -CH 2 -, -CH 2 -CH- or -CH-CH units is generally from 0.9 to 1 to 1 to 0.9, frequently from 0.95 to 1 to 1 to 0.95 and often from 0.98 to 1 to 1 to 0.98.
  • the glass transition temperature T g means the limit value of the glass transition temperature which, according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymer, Vol. 190, p. 1, equation 1), strives with increasing molecular weight.
  • the glass transition temperature is determined using the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).
  • T g 1 , T g 2 , .... T g n are the glass transition temperatures of only one of the Monomers 1, 2, .... n built up polymers in degrees Kelvin.
  • the T g values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, p. 169, VCH Weinheim, 1992; further sources for glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 st Ed., J. Wiley, New York 1966, 2 nd Ed. J. Wiley, New York 1975, and 3 rd Ed. J. Wiley, New York 1989).
  • the polymer dispersions likewise according to the invention frequently have minimum film-forming temperatures MFT ⁇ 80 ° C., often ⁇ 50 ° C. or ⁇ 30 ° C. Since the MFT is below 0 ° C is no longer measurable, the lower limit of the MFT can only be given by the T g values.
  • the MFT is determined in accordance with DIN 53787.
  • the process according to the invention makes it possible to obtain aqueous polymer dispersions whose solids content is 0.1 to 70% by weight, often 1 to 65% by weight and often 5 to 60% by weight and all values in between.
  • the residual monomers remaining in the aqueous polymer system after completion of the main polymerization reaction can be removed by steam and / or inert gas stripping without adversely affecting the polymer properties of the copolymers present in the aqueous medium.
  • aqueous polymer dispersions which are also accessible with the aid of the process according to the invention can contain, in addition to the polymer, as further components, for example formulation auxiliaries, antioxidants, light stabilizers, dyes, pigments, and waxes or else rheology modifiers or other polymer dispersions.
  • aqueous polymer dispersions which are likewise according to the invention are frequently stable over several weeks or months and generally show virtually no phase separation, deposition or coagulum formation during this time. They are particularly suitable as binders for paper applications such as paper coating or surface sizing, for paint varnishes, adhesive raw materials, molded foams such as mattresses, textile and leather applications, carpet backing or pharmaceutical applications, and as additives in polymer blends or in building materials.
  • aqueous polymer dispersions can be prepared easily and with high productivity without great technical outlay.
  • the process according to the invention has the advantage that synthetically simple, water-soluble polymerization catalysts can also be used for the preparation of aqueous polymer dispersions.
  • TEM Transmission electron microscopy
  • DSC Differential scanning calorimetry
  • aqueous dispersions based on copolymers of ethylene and carbon monoxide (Examples 1 to 4) and aqueous dispersions based on terpolymers of ethylene, carbon monoxide and undecenoic acid (Example 5 to 13).
  • a solution of an emulsifier in water was first prepared, then the catalyst used was either in solid form (Examples 2-4) or solubilized in a water-miscible solvent (Examples 5) or mixed with a self-dispersing olefin (Examples 12-14) introduced into the aqueous solution of the emulsifier. This was followed by homogenization with ultrasound and then the actual polymerization.
  • the polymerization was carried out in a mechanically stirred 250 ml pressure reactor with a double jacket.
  • the reaction temperature was controlled by a thermal sensor immersed in the reaction mixture.
  • the volume of the reaction mixture was 100 ml.
  • palladium acetate and 1,3-bis (diphenylphosphino) propane (DPPP) were dissolved separately in a little toluene or in toluene / undecenoic acid and combined to form a yellow solution.
  • DPPP 1,3-bis (diphenylphosphino) propane palladium (II) diacetate
  • undecenoic acid 1,3-bis (diphenylphosphino) propane palladium (II) diacetate
  • the catalyst solution was added to the aqueous emulsifier solution containing p-toluenesulfonic acid.
  • the homogenization was carried out by ultrasound treatment (Bandelin HD2200 with KE76 tip; 2 min at 120 W).
  • the mini emulsions obtained were transferred to the reactor and a pressure of 40 bar (ethylene / carbon monoxide 1: 1) was applied.
  • heated (1000 rpm) either with a thermostat or with a polyethylene glycol bath.
  • the mixture was cooled and then ethene and carbon monoxide were discharged.
  • precipitated polymers these were filtered off and washed with water and methanol. If a latex was obtained, it was filtered through glass wool. A measured amount was precipitated in methanol to analyze and determine the yield.
  • the “solubilized” catalyst was prepared by homogenizing a mixture of catalyst precursor complex, one tenth of the total amount of emulsifier used and 10 ml of water by means of ultrasound (2 min, 120 W). This solution already became that The stirred and stirred aqueous emulsifier solution containing para-toluenesulfonic acid (p-TsOH) was injected through an O.45 ⁇ m micron filter, otherwise the procedure was as described in Section I.
  • p-TsOH para-toluenesulfonic acid
  • the catalyst precursor complex is dissolved in 1 ml of methanol and added dropwise in 10 ml of an emulsifier solution at 40 ° C. and stirred magnetically. Para-toluenesulfonic acid was added to the solution (10 equivalents based on Pd) and the mixture was filtered through a 0.45 ⁇ m filter.

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Abstract

L'invention concerne un procédé de production d'une dispersion polymérique aqueuse par polymérisation au moins d'un composé éthyléniquement insaturé (monomère) à l'aide au moins d'un catalyseur de polymérisation insoluble dans l'eau et au moins d'un dispersif dans une substance aqueuse. Selon ce procédé, on prépare une solution d'un agent dispersant dans l'eau puis on introduit dans cette solution aqueuse d'un agent dispersant le catalyseur de polymérisation insoluble dans l'eau sous forme solide, mélangé à un solvant miscible à l'eau ou encore mélangé à un composé éthyléniquement insaturé auto-dispersant. Ensuite, on disperse le catalyseur de polymérisation insoluble dans l'eau par un apport d'énergie mécanique et à l'aide de la dispersion ainsi obtenue. Finalement, on effectue une polymérisation au moins d'un composé éthyléniquement insaturé.
PCT/EP2004/003344 2003-04-02 2004-03-30 Procede de production d'une dispersion polymerique aqueuse a l'aide d'un catalyseur de polymerisation insoluble dans l'eau Ceased WO2004087772A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019036718A1 (fr) * 2017-08-18 2019-02-21 Rohm And Haas Company Catalyseur encapsulé et procédés de polymérisation d'oléfines
US11492424B2 (en) 2018-10-03 2022-11-08 The Board Of Trustees Of The University Of Illinois Method of preparing solubilized catalyst complex, the solubilized catalyst formulation, and method of catalytic olefin polymerization

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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WO2019036718A1 (fr) * 2017-08-18 2019-02-21 Rohm And Haas Company Catalyseur encapsulé et procédés de polymérisation d'oléfines
KR20200071064A (ko) * 2017-08-18 2020-06-18 롬 앤드 하아스 컴패니 캡슐화된 촉매 및 올레핀 중합 방법
US10947330B2 (en) 2017-08-18 2021-03-16 Rohm And Haas Company Encapsulated catalyst and methods of olefin polymerization
KR102638020B1 (ko) 2017-08-18 2024-02-19 롬 앤드 하아스 컴패니 캡슐화된 촉매 및 올레핀 중합 방법
US11492424B2 (en) 2018-10-03 2022-11-08 The Board Of Trustees Of The University Of Illinois Method of preparing solubilized catalyst complex, the solubilized catalyst formulation, and method of catalytic olefin polymerization

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