EP1560904A1 - Polymer dispersions with low viscosity and method for production thereof - Google Patents

Polymer dispersions with low viscosity and method for production thereof

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Publication number
EP1560904A1
EP1560904A1 EP03809259A EP03809259A EP1560904A1 EP 1560904 A1 EP1560904 A1 EP 1560904A1 EP 03809259 A EP03809259 A EP 03809259A EP 03809259 A EP03809259 A EP 03809259A EP 1560904 A1 EP1560904 A1 EP 1560904A1
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EP
European Patent Office
Prior art keywords
polymer dispersion
component
meth
dispersion according
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03809259A
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German (de)
French (fr)
Inventor
Markus Scherer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Oil Additives GmbH
Original Assignee
RohMax Additives GmbH
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Filing date
Publication date
Application filed by RohMax Additives GmbH filed Critical RohMax Additives GmbH
Publication of EP1560904A1 publication Critical patent/EP1560904A1/en
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to polymer dispersions with reduced viscosity, processes for the preparation and use of these polymer dispersions.
  • Viscosity index improvers for motor oils are mostly essentially hydrocarbon-based polymers. Typical additional rates in motor oils are around 0.5 - 6% by weight, depending on the thickening effect of the polymers.
  • Particularly inexpensive viscosity index improvers are olefin copolymers (OCP), which are mainly composed of ethylene and propylene, or hydrogenated copolymers (HSD) from diene and styrene.
  • the dispersion technology described allows the production of polymer solutions with more than 20% OCP or HSD content while maintaining kinematic viscosities, which allow easy incorporation into lubricating oil formulations.
  • the synthesis of such systems basically includes the use of a so-called emulsifier or a dispersing component.
  • Common dispersion components include OCP or HSD polymers, onto which mostly alkyl methacrylates or alkyl methacrylate / styrene mixtures have been grafted.
  • dispersions are known in which a solvent is used which dissolves the methacrylate component of the dispersion better and the OCP or HSD component more poorly. Such a solvent together with the methacrylate part of the product forms the main component of the continuous phase of the dispersion.
  • the OCP or HSD component formally represents the main component of the discontinuous or disperse phase.
  • No. 4,149,984 describes a process for producing lubricating oil additives by improving the compatibility between polyalkyl methacrylates, hereinafter referred to as PAMA, and polyolefins.
  • PAMA polyalkyl methacrylates
  • the proportion by weight of the PAMA is 50-80% by weight, that of the polyolefin 20-50%.
  • the total polymer content of the dispersion is 20-55%.
  • dispersing monomers such as N-vinyl pyrrolidone Grafting is also mentioned.
  • methacrylates can be polymerized onto a polyolefin by grafting (DT-AS 1 235 491).
  • EP-A-0 008 327 protects a process for the production of lubricating oil additives based on a hydrogenated block copolymer from conjugated dienes and styrene, styrene and alkyl methacrylates or exclusively alkyl methacrylates being grafted onto the hydrogenated block copolymer in the first stage and an additional grafting stage (for example N-vinyl pyrrolidone) is built up.
  • the proportion of the hydrogenated block copolymer in the total polymer content is 5-55% by weight, that of the first grafting stage consisting of PAMA / styrene is 49.5-85% and the second grafting stage is 0.5-10%.
  • Document DE 32 07 291 describes processes which enable an increased olefin copolymer introduction.
  • the olefin copolymer content should be 20-65% in relation to the total weight of the dispersion.
  • the object of the invention is that by using suitable solvents which poorly dissolve olefin copolymers and components which contain PAMA well, dispersions of a higher concentration are obtained.
  • DE 32 07 291 is to be understood as a process patent, which describes in particular the production of the dispersions.
  • DE 32 07292 corresponds essentially to DE 32 07 291, but is rather to be understood as protection of certain copolymer compositions. These compositions are prepared by a method analogous to that described in DE 32 07291.
  • Another object was to provide polymer dispersions which have a high content of polyolefins, in particular of olefin copolymers and / or of hydrogenated block copolymers.
  • polymer dispersions should be simple and inexpensive to produce, in particular using commercially available components. Production should be able to be carried out on an industrial scale without the need for new or structurally complex systems.
  • D) comprising at least one compound which has a dielectric constant greater than or equal to 9, it is possible to provide polymer dispersions which have a particularly low viscosity in a manner which is not readily predictable.
  • the polymer dispersions according to the invention can achieve a number of further advantages. These include:
  • the polymer dispersions according to the invention can comprise particularly high proportions of polyolefins which have a viscosity index improver or a thickening effect in lubricating oils.
  • the polymer dispersions of the present invention can be adjusted to a predetermined viscosity in a particularly simple manner.
  • the polymer dispersion comprises polyolefins which preferably have a viscosity-index-improving or thickening effect.
  • polyolefins have long been known and are described in the documents mentioned in the prior art.
  • polystyrene-diene copolymers examples include in particular polyolefin copolymers (OCP) and hydrogenated styrene-diene copolymers (HSD).
  • OCP polyolefin copolymers
  • HSD hydrogenated styrene-diene copolymers
  • the polyolefin copolymers (OCP) to be used according to the invention are known per se. These are primarily polymers composed of ethylene, propylene, isoprene, butylene and / or other olefins having 5 to 20 carbon atoms, as have already been recommended as VI improvers. Systems which are grafted with small amounts of oxygen- or nitrogen-containing monomers (e.g. 0.05 to 5% by weight of maleic anhydride) can also be used.
  • the copolymers containing diene components are generally hydrogenated to reduce the sensitivity to oxidation and the tendency to crosslink the viscosity index improvers.
  • the molecular weight Mw is generally from 10,000 to 300,000, preferably from 50,000 to 150,000.
  • Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037, DE -A 19 63 039 and DE-A 20 59 981.
  • Ethylene-propylene copolymers are particularly useful; terpolymers with the known ter components, such as ethylidene norbomene (cf. Macromolecular Reviews, Vol. 10 (1975)) are also possible however, to take into account their tendency to network in the aging process.
  • the distribution can be largely statistical, but sequence polymers with ethylene blocks can also be used with advantage.
  • the ratio of the monomers ethylene-propylene is variable within certain limits, which can be set as the upper limit at about 75% for ethylene and about 80% for propylene.
  • polypropylene is already less suitable than ethylene-propylene copolymers.
  • those with more pronounced iso- or syndiotactic propylene incorporation can also be used.
  • Such products are commercially available for example under the trade names Dutral CO 034 ®, ® Dutral CO 038, Dutral CO 043 ®, ® Dutral CO 058, Buna ® EPG 2050 or Buna ® EPG 5050th
  • the hydrogenated styrene-diene copolymers are also known, these polymers being described for example in DE 21 56 122. They are generally hydrogenated isoprene or butadiene-styrene copolymers.
  • the ratio of diene to styrene is preferably in the range from 2: 1 to 1: 2, particularly preferably around 55:45.
  • the molecular weight Mw is generally from 10,000 to 300,000, preferably between 50,000 and 150,000.
  • the proportion of double bonds after the hydrogenation is at most 15%, particularly preferably at most 5%, based on the number of Double bonds before hydrogenation.
  • Hydrogenated styrene-diene copolymers can be obtained commercially under the trade name ®SHELLVIS 50, 150, 200, 250 or 260.
  • the proportion of components A) is at least 20% by weight, preferably at least 30% by weight and particularly preferably at least 40% by weight, without any intention that this should impose a restriction.
  • Component B) is formed by at least one dispersing component, which component can often be regarded as block copolymers. At least one of these blocks preferably has a high compatibility with the previously described polyolefins of components A), at least one further of the blocks contained in the dispersing components having only a low compatibility with the previously described polyolefins.
  • dispersing component can often be regarded as block copolymers.
  • At least one of these blocks preferably has a high compatibility with the previously described polyolefins of components A), at least one further of the blocks contained in the dispersing components having only a low compatibility with the previously described polyolefins.
  • the residue compatible with component A) generally shows a non-polar character, whereas the incompatible residue is polar in nature.
  • preferred dispersing components can be regarded as block copolymers which comprise one or more blocks A and one or more blocks X, the block A being olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene / isoprene or hydrogenated Copolymers of butadiene / isoprene and styrene represents and Block X represents polyacrylate, polymethacrylate, styrene, methylstyrene or N-vinyl heterocyclic sequences or sequences from mixtures of polyacrylate, polymethacrylate, styrene, ⁇ -methylstyrene or N-vinyl heterocycles.
  • Preferred dispersion components can be prepared by graft polymerization, with polar monomers being grafted onto the polyolefins described above, in particular onto the OCP and HSD.
  • the polyolefins can be pretreated by mechanical or / and thermal degradation.
  • the polar monomers include in particular (meth) acrylates and styrene compounds.
  • (meth) acrylates encompasses methacrylates and acrylates and mixtures of the two.
  • a monomer composition comprising one or more (meth) acrylates of the formula (I) is used in the grafting reaction
  • R is hydrogen or methyl and R 1 is hydrogen, a linear or branched alkyl radical having 1 to 40 carbon atoms.
  • the preferred monomers according to formula (I) include, among others, (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth ) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth ) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate,
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate.
  • the monomer composition can have one or more (meth) acrylates of the formula (II)
  • R is hydrogen or methyl and R 2 is an alkyl group with 2 to 20 carbon atoms substituted by an OH group or an alkoxylated group of the formula (III) wherein R 3 and R 4 are independently hydrogen or methyl, R 5 is hydrogen or an alkyl radical having 1 to 40 carbon atoms and n is an integer from 1 to 90.
  • Polyoxyethylene and polyoxypropylene derivatives of (meth) acrylic acid such as
  • Tetrapropylengylcol (meth) acrylate Tetrapropylengylcol (meth) acrylate.
  • the (meth) acrylates with a long-chain alcohol residue can be obtained, for example, by reacting the corresponding acids and / or short-chain (meth) acrylates, in particular methyl (meth) acrylate or ethyl (meth) acrylate, with long-chain fatty alcohols, a mixture of Esters, such as (meth) acrylates with different long-chain alcohol residues.
  • These fatty alcohols include, among others, Oxo AlcoholO 7911 and Oxo AlcoholO 7900, Oxo AlcoholO 1100 from Monsanto; Alphanol® 79 from ICI; Nafol ⁇ 1620, Alfol ⁇ 610 and Alfol ⁇ 810 from Condea; Epalo 610 and Epalo 810 from Ethyl Corporation; Linevol ⁇ 79, Linevol ⁇ 911 and Dobanol ⁇ 25L from Shell AG; Lial 125 from Augusta ⁇ Milan; DehydadO and Lorol ⁇ from Henkel KGaA as well as Linopol ⁇ 7 - 11 and Acropol ⁇ 91 Ugine Kuhlmann.
  • R is hydrogen or methyl
  • X is oxygen or an amino group of the formula -NH- or -NR 7 -, wherein R 7 is an alkyl radical having 1 to 40 carbon atoms
  • R 6 is substituted by at least one -NR 8 R 9 - group linear or branched alkyl radical having 2 to 20, preferably 2 to 6 carbon atoms
  • R 8 and R 9 independently of one another are hydrogen, an alkyl radical having 1 to 20, preferably 1 to 6 or wherein R 8 and R 9 including the Nitrogen atom and optionally a further nitrogen or oxygen atom form a 5- or 6-membered ring which can optionally be substituted with Ci-C ö alkyl.
  • the (meth) acrylates or (meth) acrylamides according to formula (IV) include, among others
  • Aminoalkyl methacrylates such as tris (2-methacryloxyethyl) amine
  • heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate
  • the monomer composition can have styrene compounds. These include styrene, substituted styrenes with an alkyl substituent in the side chain, such as. B. ⁇ -methyl styrene and ⁇ -ethyl styrene, substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • styrene compounds include styrene, substituted styrenes with an alkyl substituent in the side chain, such as. B. ⁇ -methyl styrene and ⁇ -ethyl styrene, substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and
  • the monomer compositions can be heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole , 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinyl caprolactam, N-vinyl butyrolactam, vinyl oxolane, vinyl furan, vinyl thiophene, vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles.
  • heterocyclic vinyl compounds such as 2-vinylpyridine,
  • preferred monomers are in particular monomers which have dispersing effects, such as the heterocyclic vinyl compounds mentioned above. These monomers are also referred to as dispersing monomers.
  • the aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is furthermore possible to vary the monomer composition during the polymerization in order to obtain defined structures, such as block copolymers.
  • the weight ratio of the parts of the dispersing component, particularly blocks A, which are compatible with the polyolefins to the parts of the dispersing component, in particular blocks X, which are incompatible with the polyolefins can be within wide ranges. In general, this ratio is in the range from 50: 1 to 1:50, in particular 20: 1 to 1:20 and particularly preferably 10: 1 to 1:10.
  • the manufacture of the dispersing components shown above is known in the art. For example, it can be produced by polymerization in solution. Such processes are described, inter alia, in DE-A 12 35 491, BE-A 592 880, US-A 4 281 081, US-A 4 338 418 and US-A-4,290,025.
  • a mixture of the OCP and one or more of the monomers set out above can be placed in a suitable reaction vessel, suitably equipped with a stirrer, thermometer, reflux condenser and metering line. After loosening under an inert atmosphere, such as. B. nitrogen, with heating, for example to 110 ° C, a portion of a conventional radical initiator, for example from the group of peresters, is set, initially for example about 0.7 wt .-% based on the monomers.
  • a conventional radical initiator for example from the group of peresters
  • a mixture of the remaining monomers with the addition of further initiators for example about 1.3% by weight, based on the monomers, is metered in over a few hours, for example 3.5 hours. It is advisable to add some initiator some time after the end of the feed, for example after two hours. The total polymerization time can be taken as a guideline, for example, about 8 hours.
  • the mixture is expediently diluted with a suitable solvent, such as, for. B. a phthalate such as dibutyl phthalate. As a rule, an almost clear, viscous solution is obtained.
  • the polymer dispersions can be produced in a kneader, an extruder or in a static mixer.
  • the treatment in the device reduces the molecular weight of the polyolefin, in particular the OCP or HSD, under the influence of the shear forces, the temperature and the initiator concentration.
  • initiators suitable in the graft copolymerization are cumene hydroperoxide, diumyl peroxide, benzoyl peroxide, azodiisobutyric acid dinitrile, 2,2-bis (t-butyl peroxy) butane, diethyl peroxydicarbonate and tert-butyl peroxide.
  • the processing temperature is between 80 ° C and 350 ° C.
  • the residence time in the kneader or extruder is between 1 minute and 10 hours. The longer the dispersion is treated in the kneader or extruder, the lower the molecular weight.
  • the temperature and the concentration of free-radical initiators can be adjusted according to the desired molecular weight.
  • the solvent-free polymer-in-polymer dispersion can be converted into an easy-to-handle, liquid polymer / polymer emulsion by incorporation into suitable carrier media.
  • the proportion of components B) is generally up to 30% by weight, in particular this proportion is in the range from 5 to 15% by weight, without any intention that this should impose a restriction.
  • the use of larger amounts of component B) is often uneconomical. Smaller amounts often lead to a lower stability of the polymer dispersion.
  • Component C) is essential for the success of the present invention.
  • the solvents that can be used as the liquid carrier medium should be inert and, on the whole, harmless.
  • Carrier media that meet the conditions mentioned include, for. B. to the group of esters, ethers and / or to the group of higher alcohols.
  • the molecules of the types of compounds that can be used as carrier medium contain more than 8 carbon atoms per molecule.
  • mixtures of the solvents described above can also be used for the carrier medium.
  • esters phosphoric acid esters, esters of dicarboxylic acids, esters of monocarboxylic acids with diols or polyalkylene glycols, esters of neopentyl polyols Monocarboxylic acids. (See Ullmann's Encyclopedia of Technical Chemistry, 3rd ed., Vol. 15, pp. 287-292, Urban & Schwarzenber (1964)).
  • Suitable esters of dicarboxylic acids are the esters of phthalic acid, in particular the phthalic esters with C-4 to Cs alcohols, dibutyl phthalate and dioctyl phthalate being particularly mentioned, and then the esters of aliphatic dicarboxylic acids, especially the esters of straight-chain dicarboxylic acids with branched-chain primary alcohols. Particular emphasis is given to the esters of sebacic, adipic and azelaic acid, in particular the 2-ethylhexyl, isooctyl-3,5,5-trimethyl esters and the esters with the Cs, Cg and Cifj oxo alcohols should be.
  • esters of straight-chain primary alcohols with branched dicarboxylic acids are of particular importance.
  • examples include the alkyl-substituted adipic acid, for example 2,2,4-trimethyladipic acid.
  • esters of monocarboxylic acids with diols or polyalkylene glycols the di-esters with diethylene glycol, triethylene glycol, tetraethylene glycol to decamethylene glycol, and also with dipropylene glycol as alcohol components should be emphasized.
  • the monocarboxylic acids which are specifically mentioned are propionic acid, (iso) butyric acid and pelargonic acid - for example dipropylene glycol dipelargonate, diethylene glycol dipropionate - and diisobutyrate as well as the corresponding esters of triethylene glycol and the tetraethylene glycol di-2-ethylhexanoic acid ester.
  • Preferred carrier media are nonionic surfactants. These include, inter alia, fatty acid polyglycol esters, fatty amine polyglycol ethers, alkyl polyglycosides, fatty amine N-oxides and long-chain alkyl sulfoxides. Furthermore, the aforementioned esters with ethoxy groups belong to the group of nonionic surfactants.
  • Another group of particularly preferred carrier media which are nonionic surfactants are alcohols etherified with (oligo) oxyalkyl groups.
  • ethoxylated alcohols which particularly preferably have 1 to 20, in particular 2 to 8, ethoxy groups.
  • the hydrophobic radical of the ethoxylated alcohols preferably comprises 1 to 40, preferably 4 to 22 carbon atoms, it being possible to use both linear and branched alcohol radicals. Oxo alcohol ethoxylates can also be used.
  • ethers are the Lutensol ® A brands, especially Lutensol ® A 3 N, Lutensol ® A 4 N, Lutensol ® A 7 N and Lutensol ® A 8 IM, ethers of the Lutensol ® TO brands, in particular Lutensol ® TO 2, Lutensol ® TO 3, Lutensol ® TO 5, Lutensol ® TO 6, Lutensol ® TO 65, Lutensol ® TO 69, Lutensol ® TO 7, Lutensol ® TO 79, Lutensol ® 8 and Lutensol ® 89, ethers of the Lutensol ® AO brands, in particular Lutensol ® AO 3, Lutensol ® AO 4, Lutensol ® AO 5, Lutensol ® AO 6, Lutensol ® AO 7, Lutensol ® AO 79, Lutensol ® AO 8 and Lutensol ® AO 89,
  • Mixtures comprising alcohols etherified with (oligo) oxyalkyl groups and esters are particularly preferred. Such mixtures show an unexpectedly high stability. This applies in particular to dispersions which have hydrogenated styrene-diene copolymers (HSD).
  • HSD hydrogenated styrene-diene copolymers
  • the weight ratio of ester to alcohol etherified with (oligo) oxyalkyl groups can be in wide ranges. This ratio is particularly preferably in the range from 15: 1 to 1:15, in particular 5: 1 to 1: 5.
  • Mineral oils represent a further group of preferred carrier media. Surprisingly, it was found that the stability of the polymer dispersion can be increased considerably by the presence of mineral oil.
  • Mineral oils are known per se and are commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and upgrading processes, the term mineral oil in particular referring to the higher-boiling proportions of the crude or petroleum. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. It is also possible to produce by smoldering shale oil, coking hard coal, distilling with the exclusion of air from brown coal and hydrogenating hard coal or brown coal. To a small extent, mineral oils are also made from raw materials of vegetable (e.g. jojoba, rapeseed) or animal (e.g. claw oil) origin. Accordingly, mineral oils have different proportions of aromatic, cyclic, branched and linear hydrocarbons depending on their origin.
  • vegetable e.g. jojoba, rapeseed
  • animal e.g. claw oil
  • paraffin-based, naphthenic and aromatic components in crude oils or mineral oils, the terms paraffin-based component standing for longer-chain or strongly branched iso-alkanes and naphthenic component for cycloalkanes.
  • mineral oils have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are said to have limited polar properties .
  • the assignment is difficult, however, since individual alkane molecules can have long-chain branched groups as well as cycloalkane residues and aromatic components.
  • the assignment can be made, for example, in accordance with DIN 51 378.
  • Polar fractions can also be determined in accordance with ASTM D 2007.
  • n-alkanes in preferred mineral oils is less than 3% by weight, the proportion of O, N and / or S-containing compounds is less than 6% by weight.
  • the proportion of the aromatics and the monomethyl-branched paraffins is generally in each case in the range from 0 to 40% by weight.
  • mineral oil mainly comprises naphthenic and paraffin-based alkanes, which generally have more than 13, preferably more than 18 and very particularly preferably more than 20 carbon atoms.
  • the proportion of these compounds is in in general> 60% by weight, preferably> 80% by weight, without any intention that this should impose a restriction.
  • a preferred mineral oil contains 0.5 to 30% by weight of aromatic components, 15 to 40% by weight of naphthenic components, 35 to 80% by weight of paraffin-based components, up to 3% by weight of n-alkanes and 0.05 up to 5% by weight of polar compounds, in each case based on the total weight of the mineral oil.
  • Liquid chromatography on silica gel shows the following components, the percentages referring to the
  • Aromatics with 14 to 32 carbon atoms :
  • mixtures are used as carrier medium which comprise mineral oil and nonionic surfactants, in particular alcohols etherified with (oligo) oxyalkyl groups.
  • the weight ratio of mineral oil to nonionic surfactant, in particular to alcohol etherified with (oligo) oxyalkyl groups can be within wide ranges. This ratio is particularly preferably in the range from 15: 1 to 1:15, in particular 5: 1 to 1: 5.
  • the proportion of the carrier medium in the concentrated polymer dispersion can be in a wide range, this proportion being dependent in particular on the polyolefins and dispersion components used.
  • the proportion of the carrier medium is 79 to 25% by weight, preferably less than 70, especially 60 to 40% by weight, based on the total polymer dispersion.
  • Component D) is mandatory for the present polymer dispersion, this component comprising one or more compounds with a dielectric constant greater than or equal to 9, in particular greater than or equal to 20 and particularly preferably greater than or equal to 30.
  • the dielectric constant can be determined according to the methods given in the Handbook of Chemistry and Physics, David R. Lide, 79th Edition, CRS Press, the dielectric constant being measured at 20 ° C.
  • the particularly suitable compounds include water, glycols, in particular ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, polyethylene glycol; Alcohols, especially methanol, ethanol, butanol, glycerin; ethoxylated alcohols, for example 2-fold ethoxylated butanol, 10-fold ethoxylated methanol; Amines, especially ethanolamine, 1, 2 ethanediamine and propanolamine; halogenated hydrocarbons, especially 2-chloroethanol, 1, 2 dichloroethane, 1, 1 dichloroacetone; Ketones, especially acetone.
  • the proportion of components D) in the polymer dispersion can be in a wide range.
  • the polymer dispersion comprises 0.01-15% by weight, in particular 0.3 to 5% by weight, of compounds according to component D).
  • the polymer dispersion according to the invention can contain further additives.
  • the polymer dispersions can be prepared by known processes, these processes being set out in the aforementioned documents of the prior art.
  • the present polymer dispersions can be prepared by dispersing component A) in a solution of component B) using shear forces at a temperature in the range from 80 to 180 ° C.
  • Component B) generally comprises component C).
  • Component D) can be added to the dispersion before, during or after the dispersion of component A).
  • KV100 means the kinematic viscosity of a liquid measured at 100 ° C in a 150N oil.
  • the viscosity is determined in accordance with DIN 51 562 (Ubbelohde viscometer).
  • the concentration of the OCP in oil is 2.8% by weight.
  • ethylene glycol used was ethylene glycol for analysis (Merck)
  • polyethylene glycol used was polyethylene glycol 400 for synthesis (Merck-Schuchardt).
  • hydrophilic character 0.5 or 1.0% by weight was added to the respective dispersion heated to 90 to 110 ° C. in an 11-glass bottle and the resulting still warm mixture in the glass bottle on a roller bench (Speed: 160 rpm) homogenized over a period of half an hour to an hour.
  • BV20, BV40 and BV100 values were determined before and after the addition of the hydrophilic component.
  • initiators such as the perinitiators di (tert-butylperoxy) -3,3,5-trimethylcyclohexane and / or tert-butyl peroctoate were used as initiators for the preparation of the dispersions.
  • 670 g of the product can be weighed into a 2 liter Witt pot.
  • An InterMig stirrer with three blades (measuring stirrer with torque and speed display MR-D1 from Ika) and a NiCrNi thermocouple (temperature controller 810 from Eurotherm) are installed in the Witt pot.
  • the oil bath (silicone oil PN 200) is heated, the speed being set so that the power input is 1.3 watts.
  • the power input can be calculated via the viscosity.
  • the product is warmed up to 160 ° C and this internal temperature is then maintained for 2 hours.
  • the internal temperature in the reactor is then raised by 10 ° C. within 15 minutes and again held for 2 hours, this process being repeated several times until the internal temperature is 190 ° C. If the product is subject to phase separation beforehand, which can be recognized by a sudden increase in viscosity and thus a rapid increase in torque, the test is ended. Time and temperature up to this point in time are detected.
  • the temperature is set again to 100 ° C., after which 1.14 g of tert-butyl peroctoate are added and at the same time an inlet consisting of a mixture of 527.2 g of the C12-C16 alkyl methacrylate and 6.33 g of tert-butyl peroctoate is started.
  • the run-in time is 3.5 hours.
  • the feed rate is constant. 2 hours after the end of the feed, a further 1.15 g of tert-butyl peroctoate are added.
  • the mixture is diluted to 47.55% polymer content with 472.1 g of an ethoxylated fatty alcohol (eg Marlipal ® 013/20).
  • an ethoxylated fatty alcohol eg Marlipal ® 013/20.
  • the temperature is reduced to 100 ° C., 1.26 g of tert-butyl peroctoate are added and the mixture is stirred at 100 ° C. for a further 2 hours.
  • the temperature is therefore increased from 100 ° C. to 140 ° C. and stirring is continued at 150 rpm for 6 hours.
  • the mixture is then diluted to 55% polymer content by dilution with 136.6 g of an ethoxylated fatty alcohol (eg Marlipal ® 013/20) and the mixture is stirred at 100 ° C. for half an hour.
  • the polymer content of the dispersion is then reduced to 52% by weight by further adding Marlipal ® 013/20.
  • the BV40 of a dispersion produced in this way was 3834 mm 2 / s, the BV100 1623 mm 2 / s.
  • the addition of 1.0% by weight of water by the process described above led to a drop in the BV40 to 3169 mm 2 / s and to a lowering of the BV100 to 801 mm 2 / s.
  • the OCP dispersion is prepared in analogy to Example 2, with the difference that dioctyl adipate (eg Vestinol OA) is used instead of mineral oil and that the last dilution step from 55 to 52% by weight polymer content is not carried out.
  • the KV100 of the solution of 2.8% by weight of a dispersion thus obtained in a 150N oil was measured at 10.85 mm / s.
  • the BV40 was 3844 mm 2 / s, the BV100 1499 mm 2 / s.
  • a dispersion produced in analogy to Example 2 had a BV20 of 3450 mm 2 / s.
  • the addition of 4.5% by weight of 2-fold ethoxylated butanol led to a reduction in the BV20 to 2880 mm 2 / s.

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Abstract

The invention relates to polymer dispersions with low viscosity, comprising A) at least one dispersed polyolefin, B) at least one dispersing component, C) at least one support medium and D) at least one compound with a dielectric constant greater than or equal to 9.

Description

Polymerdispersionen mit geringer Viskosität und Verfahren zur HerstellungLow viscosity polymer dispersions and process for making them
Die vorliegende Erfindung betrifft Polymerdispersionen mit erniedrigter Viskosität, Verfahren zur Herstellung sowie die Verwendung dieser Polymerdispersionen.The present invention relates to polymer dispersions with reduced viscosity, processes for the preparation and use of these polymer dispersions.
Viskositätsindexverbesserer für Motorenöle sind zumeist im wesentlichen auf Kohlenwasserstoff basierende Polymere. Typische Zusatzraten in Motorenölen betragen je nach Verdickungswirkung der Polymere etwa 0,5 - 6 Gew.%. Besonders preisgünstige Viskositätsindexverbesserer stellen Olefincopolymere (OCP), die vorwiegend aus Ethylen- und Propylen aufgebaut sind, oder hydrierte Copolymere (HSD) aus Dienen und Styrol dar.Viscosity index improvers for motor oils are mostly essentially hydrocarbon-based polymers. Typical additional rates in motor oils are around 0.5 - 6% by weight, depending on the thickening effect of the polymers. Particularly inexpensive viscosity index improvers are olefin copolymers (OCP), which are mainly composed of ethylene and propylene, or hydrogenated copolymers (HSD) from diene and styrene.
Der ausgezeichneten Verdickungswirkung dieser Polymertypen steht eine mühsame Verarbeitbarkeit bei der Herstellung von Schmierölformulierungen gegenüber. Insbesondere die schlechte Löslichkeit in den Ölen, die den Formulierungen zugrunde liegen, bereitet Schwierigkeiten. Im Falle der Benutzung fester, nicht vorgelöster Polymere kommt es somit zu langen Einrührperioden, wobei man auf die Benutzung spezieller Rühr- und/oder Vormahlwerke angewiesen ist.The excellent thickening effect of these types of polymers contrasts with the tedious processability in the production of lubricating oil formulations. The poor solubility in the oils on which the formulations are based is particularly difficult. In the case of the use of solid, not pre-dissolved polymers, this results in long stirring-in periods, one having to rely on the use of special stirring and / or pre-grinding mechanisms.
Setzt man konzentrierte, in Öl bereits vorgelöste Polymere als übliche Handelsformen ein, so ist lediglich eine 10-15%-ige Lieferform der OCP's bzw. HSD's realisierbar. Höhere Konzentrationen gehen mit zu hohen aktuellen Viskositäten der Lösungen einher (> 15,000 mm2/s bei Raumtemperatur) und sind daher kaum noch handhabbar. Insbesondere mit diesem Hintergrund wurden hochkonzentrierte Dispersionen von Olefincopolymeren und hydrierten Dien/Styrol-Copolymeren entwickelt.If you use concentrated polymers that are already pre-dissolved in oil as usual commercial forms, only a 10-15% delivery form of the OCP's or HSD's can be realized. Higher concentrations go hand in hand with excessively high viscosities of the solutions (> 15,000 mm 2 / s at room temperature) and are therefore hardly manageable. With this background in particular, highly concentrated dispersions of Developed olefin copolymers and hydrogenated diene / styrene copolymers.
Die beschriebene Dispersionstechnologie erlaubt die Herstellung von Polymerlösungen mit mehr als 20% OCP- bzw. HSD-Gehalt unter Erhalt kinematischer Viskositäten, die eine bequeme Einarbeitung in Schmierölformulierungen erlauben. Grundsätzlich beinhaltet die Synthese solcher Systeme den Einsatz eines sog. Emulgators bzw. einer Dispergierkomponente. Gebräuchliche Dispergierkomponenten sind unter anderem OCP- bzw. HSD-Polymere, auf die zumeist Alkylmethacrylate bzw. Alkylmethacrylat/Styrol-Gemische gepfropft wurden. Darüber hinaus sind Dispersionen bekannt, bei denen ein Lösemittel eingesetzt wird, welches den Methacrylatbestandteil der Dispersion besser und den OCP- bzw. HSD-Anteil schlechter löst. Ein solches Lösemittel zusammen mit dem Methacrylatanteil des Produktes bildet den Hauptbestandteil der kontinuierlichen Phase der Dispersion. Der OCP- bzw. HSD-Anteil stellt formell gesehen den Hauptbestandteil der diskontinuierlichen oder dispersen Phase dar.The dispersion technology described allows the production of polymer solutions with more than 20% OCP or HSD content while maintaining kinematic viscosities, which allow easy incorporation into lubricating oil formulations. The synthesis of such systems basically includes the use of a so-called emulsifier or a dispersing component. Common dispersion components include OCP or HSD polymers, onto which mostly alkyl methacrylates or alkyl methacrylate / styrene mixtures have been grafted. In addition, dispersions are known in which a solvent is used which dissolves the methacrylate component of the dispersion better and the OCP or HSD component more poorly. Such a solvent together with the methacrylate part of the product forms the main component of the continuous phase of the dispersion. The OCP or HSD component formally represents the main component of the discontinuous or disperse phase.
Als Stand der Technik werden unter anderem die folgenden Dokumente angesehen:The following documents are regarded as state of the art:
US 4,149,984US 4,149,984
EP-A-0 008 327EP-A-0 008 327
DE 32 07 291DE 32 07 291
DE 32 07 292DE 32 07 292
US 4,149,984 beschreibt ein Verfahren zur Herstellung von Schmierölzusätzen durch Verbesserung der Kompatibilität zwischen Polyalkylmethacrylaten, im folgenden PAMA genannt, und Polyolefinen. Der Gewichtsanteil des PAMA's beträgt 50-80 Gew.%, der des Polyolefins 20-50%. Gesamtpolymergehalt der Dispersion ist 20-55%. Die Verwendung dispergierender Monomere wie N-Vinylpyrrolidon zur Pfropfung ist ebenso erwähnt. Vor dieser Anmeldung war bekannt, dass Methacrylate durch Pfropfung auf ein Polyolefin aufpolymerisiert werden können (DT-AS 1 235 491 ).No. 4,149,984 describes a process for producing lubricating oil additives by improving the compatibility between polyalkyl methacrylates, hereinafter referred to as PAMA, and polyolefins. The proportion by weight of the PAMA is 50-80% by weight, that of the polyolefin 20-50%. The total polymer content of the dispersion is 20-55%. The use of dispersing monomers such as N-vinyl pyrrolidone Grafting is also mentioned. Before this application it was known that methacrylates can be polymerized onto a polyolefin by grafting (DT-AS 1 235 491).
EP-A-0 008 327 schützt ein Verfahren zur Herstellung von Schmieröladditiven auf Basis eines hydrierten Blockcopolymerisats aus konjugierten Dienen und Styrol, wobei in erster Stufe Styrol und Alkylmethacrylate oder ausschließlich Alkylmethacrylate auf das hydrierte Blockcopolymer aufgepfropft werden und in zweiter Stufe eine zusätzliche Pfropfstufe (z.B. N-Vinylpyrrolidon) aufgebaut wird. Der Anteil des hydrierten Blockcopolymerisats am Gesamtpolymergehalt beträgt 5-55 Gew.%, der der ersten aus PAMA/Styrol bestehenden Pfropfstufe 49,5-85 % sowie der zweiten Pfropfstufe 0,5-10%.EP-A-0 008 327 protects a process for the production of lubricating oil additives based on a hydrogenated block copolymer from conjugated dienes and styrene, styrene and alkyl methacrylates or exclusively alkyl methacrylates being grafted onto the hydrogenated block copolymer in the first stage and an additional grafting stage (for example N-vinyl pyrrolidone) is built up. The proportion of the hydrogenated block copolymer in the total polymer content is 5-55% by weight, that of the first grafting stage consisting of PAMA / styrene is 49.5-85% and the second grafting stage is 0.5-10%.
Das Dokument DE 32 07 291 beschreibt Verfahren, welche einen erhöhten Olefincopolymereintrag ermöglichen. Der Olefincopolymergehalt soll 20-65% in Relation zum Gesamtgewicht der Dispersion betragen. Gegenstand der Erfindung ist, dass durch Einsatz geeigneter Lösemittel, welche Olefincopolymere schlecht und PAMA-haltige Komponenten gut lösen, höher konzentrierte Dispersionen erhalten werden. DE 32 07 291 ist als Verfahrenspatent zu verstehen, welches insbesondere die Herstellung der Dispersionen beschreibt.Document DE 32 07 291 describes processes which enable an increased olefin copolymer introduction. The olefin copolymer content should be 20-65% in relation to the total weight of the dispersion. The object of the invention is that by using suitable solvents which poorly dissolve olefin copolymers and components which contain PAMA well, dispersions of a higher concentration are obtained. DE 32 07 291 is to be understood as a process patent, which describes in particular the production of the dispersions.
DE 32 07292 entspricht im wesentlichen DE 32 07 291 , ist aber eher als Schutz bestimmter Copolymerzusammensetzungen zu verstehen. Diese Zusammensetzungen werden nach analogem Verfahren hergestellt wie in DE 32 07291 beschrieben.DE 32 07292 corresponds essentially to DE 32 07 291, but is rather to be understood as protection of certain copolymer compositions. These compositions are prepared by a method analogous to that described in DE 32 07291.
Die im Stand der Technik beschriebenen Polymerdispersionen zeigen bereits ein gutes Eigenschaftsprofil. Verbesserungswürdig ist jedoch insbesondere deren Viskosität. Je höher der Gehalt an OCP oder HSD, desto höher im allgemeinen die Viskosität der Dispersion. Andererseits ist ein hoher Gehalt an diesen Polymeren wünschenswert, um die Transportkosten zu senken. Hierbei ist zu bedenken, dass eine geringere Viskosität eine einfachere und schnellere Zumischung der Viskositätsindexverbesserer in das Grundöl erlaubt. Daher sollten Polymerdispersionen zur Verfügung gestellt werden, die eine besonders geringe Viskosität aufweisen.The polymer dispersions described in the prior art already show a good property profile. However, their viscosity needs improvement. The higher the OCP or HSD content, generally the higher the viscosity of the dispersion. On the other hand, a high content of these polymers is desirable in order to reduce the transportation costs. It should be borne in mind here that a lower viscosity permits easier and faster admixing of the viscosity index improvers into the base oil. Therefore polymer dispersions should be made available which have a particularly low viscosity.
Darüber hinaus sind die Verfahren zur Herstellung der zuvor genannten Polymerdispersionen relativ schwierig zu beherrschen, so dass bestimmte Spezifikationen nur sehr schwer eingehalten werden können. Dementsprechend sollten Polymerdispersionen geschaffen werden, deren Viskosität leicht auf vorgegebene Werte eingestellt werden können.In addition, the processes for producing the aforementioned polymer dispersions are relatively difficult to master, so that certain specifications are very difficult to meet. Accordingly, polymer dispersions should be created whose viscosity can easily be adjusted to predetermined values.
Eine weitere Aufgabe bestand darin, Polymerdispersionen anzugeben, welche einen hohen Gehalt an Polyolefinen, insbesondere an Olefincopolymeren und/oder an hydrierten Blockcopolymeren aufweisen.Another object was to provide polymer dispersions which have a high content of polyolefins, in particular of olefin copolymers and / or of hydrogenated block copolymers.
Des weiteren sollten die Polymerdispersionen einfach und kostengünstig hergestellt werden können, wobei insbesondere kommerziell erhältliche Komponenten eingesetzt werden sollten. Hierbei sollte die Produktion großtechnisch erfolgen können, ohne dass hierzu neue oder konstruktiv aufwendige Anlagen benötigt werden.Furthermore, the polymer dispersions should be simple and inexpensive to produce, in particular using commercially available components. Production should be able to be carried out on an industrial scale without the need for new or structurally complex systems.
Gelöst werden diese sowie weitere nicht explizit genannten Aufgaben, die jedoch aus den hierin einleitend diskutierten Zusammenhängen ohne weiteres ableitbar oder erschließbar sind, durch Polymerdispersionen mit allen Merkmalen des Patentanspruchs 1. Zweckmäßige Abwandlungen der erfindungsgemäßen Polymerdispersionen werden in den auf Anspruch 1 rückbezogenen Unteransprüchen unter Schutz gestellt. Hinsichtlich des Verfahrens zur Herstellung von Polymerdispersionen liefert Anspruch 18 eine Lösung der zugrunde liegenden Aufgabe, während Anspruch 19 eine bevorzugte Verwendung einer Polymerdispersionen der vorliegenden Erfindung schützt.These and other tasks which are not explicitly mentioned, but which can easily be derived or inferred from the contexts discussed at the outset, are achieved by polymer dispersions having all the features of claim 1. Appropriate modifications of the polymer dispersions according to the invention are protected in the subclaims relating to claim 1 , With regard to the method for producing polymer dispersions, claim 18 provides a solution to the underlying object, while claim 19 protects a preferred use of a polymer dispersion of the present invention.
Dadurch, dass Polymer-DispersionenBecause of polymer dispersions
A) mindestens ein dispergiertes Polyolefin,A) at least one dispersed polyolefin,
B) mindestens eine Dispergierkomponente,B) at least one dispersing component,
C) mindestens ein Trägermedium undC) at least one carrier medium and
D) mindestens eine Verbindung, die eine Dielektrizitätskonstante größer oder gleich 9 aufweist, umfassen, gelingt es auf nicht ohne weiteres vorhersehbare Weise Polymerdispersionen zur Verfügung zu stellen, die eine besonders geringe Viskosität aufweisen.D) comprising at least one compound which has a dielectric constant greater than or equal to 9, it is possible to provide polymer dispersions which have a particularly low viscosity in a manner which is not readily predictable.
Zugleich lassen sich durch die erfindungsgemäßen Polymerdispersionen eine Reihe weiterer Vorteile erzielen. Hierzu gehören unter anderem:At the same time, the polymer dispersions according to the invention can achieve a number of further advantages. These include:
• Die er indungsgemäßen Polymerdispersionen können besonders hohe Anteile an Polyolefinen umfassen, die eine viskositätsindexverbessemde bzw. in Schmierölen eine verdickende Wirkung aufweisen.The polymer dispersions according to the invention can comprise particularly high proportions of polyolefins which have a viscosity index improver or a thickening effect in lubricating oils.
• Die Polymerdispersionen der vorliegenden Erfindung können auf besonders einfache Weise auf eine vorgegebene Viskosität eingestellt werden.• The polymer dispersions of the present invention can be adjusted to a predetermined viscosity in a particularly simple manner.
• Die Herstellung der Polymerdispersionen der vorliegenden Erfindung können besonders leicht und einfach hergestellt werden. Hierbei können übliche, großtechnische Anlagen eingesetzt werden. Die Komponente A)• The polymer dispersions of the present invention can be produced particularly easily and simply. Conventional large-scale plants can be used here. Component A)
Als erfindungswesentliche Komponente umfasst die Polymerdispersion Polyolefine, die vorzugsweise eine viskositätsindexverbessemde bzw. verdickende Wirkung aufweisen. Derartige Polyolefine sind seit längerem bekannt und in den im Stand der Technik genannten Dokumenten beschrieben.As a component essential to the invention, the polymer dispersion comprises polyolefins which preferably have a viscosity-index-improving or thickening effect. Such polyolefins have long been known and are described in the documents mentioned in the prior art.
Zu diesen Polyolefinen gehören insbesondere Polyolefincopolymere (OCP) und hydrierte Styrol-Dien-Copolymere (HSD).These polyolefins include in particular polyolefin copolymers (OCP) and hydrogenated styrene-diene copolymers (HSD).
Die erfindungsgemäß zur verwendenden Polyolefincopolymere (OCP) sind an sich bekannt. Es handelt sich in erster Linie um aus Ethylen-, Propylen-, Isopren-, Butylen- und/oder weiteren -Olefinen mit 5 bis 20 C- Atomen aufgebaute Polymerisate, wie sie bereits als Vl-Verbesserer empfohlen worden sind. Ebenso sind Systeme, welche mit geringen Mengen Sauerstoff- oder stickstoffhaltiger Monomere (z.B. 0,05 bis 5 Gew.-% Maleinsäureanhydrid) bepfropft sind, einsetzbar. Die Copolymere, die Dienkomponenten enthalten, werden im allgemeinen hydriert, um die Oxidationsempfindlichkeit sowie die Vemetzungsneigung der Viskositätsindexverbesserer zu vermindern.The polyolefin copolymers (OCP) to be used according to the invention are known per se. These are primarily polymers composed of ethylene, propylene, isoprene, butylene and / or other olefins having 5 to 20 carbon atoms, as have already been recommended as VI improvers. Systems which are grafted with small amounts of oxygen- or nitrogen-containing monomers (e.g. 0.05 to 5% by weight of maleic anhydride) can also be used. The copolymers containing diene components are generally hydrogenated to reduce the sensitivity to oxidation and the tendency to crosslink the viscosity index improvers.
Das Molekulargewicht Mw liegt im allgemeinen bei 10 000 bis 300000, vorzugsweise zwischen 50 000 und 150 000. Derartige Olefincopolymerisate sind beispielsweise in den deutschen Offenlegungsschriften DE-A 16 44 941 , DE-A 17 69 834, DE-A 19 39 037, DE-A 19 63 039 und DE-A 20 59 981 beschrieben.The molecular weight Mw is generally from 10,000 to 300,000, preferably from 50,000 to 150,000. Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037, DE -A 19 63 039 and DE-A 20 59 981.
Besonders gut brauchbar sind Ethylen-Propylen-Copolymere, ebenfalls sind Terpolymere mit den bekannten Terkomponenten, wie Ethyliden- Norbomen (vgl. Macromolecular Reviews, Vol. 10 (1975)) möglich, es ist jedoch deren Neigung zur Vernetzung beim Alterungsprozeß mit einzukalkulieren. Die Verteilung kann dabei weitgehend statistisch sein, es können aber auch mit Vorteil-Sequenzpolymere mit Ethylenblöcken angewendet werden. Das Verhältnis der Monomeren Ethylen-Propylen ist dabei innerhalb gewisser Grenzen variabel, die bei etwa 75 % für Ethylen und etwa 80 % für Propylen als obere Grenze angesetzt werden können. Infolge seiner verminderten Löslichkeitstendenz in Öl ist bereits Polypropylen weniger geeignet als Ethylen-Propylen-Copolymere. Neben Polymeren mit vorwiegend ataktischem Propyleneinbau sind auch solche mit ausgeprägterem iso- oder syndiotaktischen Propyleneinbau einsetzbar.Ethylene-propylene copolymers are particularly useful; terpolymers with the known ter components, such as ethylidene norbomene (cf. Macromolecular Reviews, Vol. 10 (1975)) are also possible however, to take into account their tendency to network in the aging process. The distribution can be largely statistical, but sequence polymers with ethylene blocks can also be used with advantage. The ratio of the monomers ethylene-propylene is variable within certain limits, which can be set as the upper limit at about 75% for ethylene and about 80% for propylene. As a result of its reduced tendency towards solubility in oil, polypropylene is already less suitable than ethylene-propylene copolymers. In addition to polymers with predominantly atactic propylene incorporation, those with more pronounced iso- or syndiotactic propylene incorporation can also be used.
Derartige Produkte sind kommerziell beispielsweise unter den Handelsnamen Dutral® CO 034, Dutral® CO 038, Dutral® CO 043, Dutral® CO 058, Buna® EPG 2050 oder Buna® EPG 5050 erhältlich.Such products are commercially available for example under the trade names Dutral CO 034 ®, ® Dutral CO 038, Dutral CO 043 ®, ® Dutral CO 058, Buna ® EPG 2050 or Buna ® EPG 5050th
Die hydrierten Styrol-Dien-Copolymere (HSD) sind ebenfalls bekannt, wobei diese Polymere beispielsweise in DE 21 56 122 beschrieben sind. Es handelt sich im allgemeinen um hydrierte Isopren- oder Butadien- Styrol-Copolymere. Das Verhältnis von Dien zu Styrol liegt bevorzugt im Bereich von 2:1 bis 1 :2, besonders bevorzugt bei ca. 55:45. Das Molekulargewicht Mw liegt im allgemeinen bei 10 000 bis 300 000, vorzugsweise zwischen 50 000 und 150000. Der Anteil der Doppelbindungen nach der Hydrierung beträgt gemäß einem besonderen Aspekt der vorliegenden Erfindung höchstens 15%, besonders bevorzugt höchstens 5%, bezogen auf die Zahl der Doppelbindungen vor der Hydrierung. Hydrierte Styrol-Dien-Copolymere können kommerziell unter dem Handelsnamen ®SHELLVIS 50, 150, 200, 250 oder 260 erhalten werden.The hydrogenated styrene-diene copolymers (HSD) are also known, these polymers being described for example in DE 21 56 122. They are generally hydrogenated isoprene or butadiene-styrene copolymers. The ratio of diene to styrene is preferably in the range from 2: 1 to 1: 2, particularly preferably around 55:45. The molecular weight Mw is generally from 10,000 to 300,000, preferably between 50,000 and 150,000. According to a particular aspect of the present invention, the proportion of double bonds after the hydrogenation is at most 15%, particularly preferably at most 5%, based on the number of Double bonds before hydrogenation. Hydrogenated styrene-diene copolymers can be obtained commercially under the trade name ®SHELLVIS 50, 150, 200, 250 or 260.
Im allgemeinen beträgt der Anteil der Komponenten A) mindestens 20 Gew.-%, vorzugsweise mindestens 30 Gew.-% und besonders bevorzugt mindestens 40 Gew.-%, ohne dass hierdurch eine Beschränkung erfolgen soll.In general, the proportion of components A) is at least 20% by weight, preferably at least 30% by weight and particularly preferably at least 40% by weight, without any intention that this should impose a restriction.
Die Komponente B)Component B)
Die Komponente B) wird von mindestens einer Dispergierkompente gebildet, wobei diese Komponente häufig als Blockcopolymere angesehen werden kann. Vorzugsweise zeigt mindestens einer dieser Blöcke eine hohe Verträglichkeit mit den zuvor beschriebenen Polyolefinen der Komponenten A), wobei mindestens ein weiterer der in der Dispergierkomponenten enthaltenen Blöcke mit den zuvor beschriebenen Polyolefinen nur eine geringe Verträglichkeit aufweist. Derartige Dispergierkomponenten sind an sich bekannt, wobei bevorzugte Verbindungen im zuvor genannten Stand der Technik beschrieben sind.Component B) is formed by at least one dispersing component, which component can often be regarded as block copolymers. At least one of these blocks preferably has a high compatibility with the previously described polyolefins of components A), at least one further of the blocks contained in the dispersing components having only a low compatibility with the previously described polyolefins. Such dispersion components are known per se, preferred compounds being described in the aforementioned prior art.
Der mit der Komponenten A) kompatible Rest zeigt im allgemeinen einen unpolaren Charakter, wohingegen der inkompatible Rest polarer Natur ist. Gemäß einem besonderen Aspekt der vorliegenden Erfindung lassen sich bevorzugte Dispergierkomponenten als Blockcopolymere auffassen, welches ein oder mehrere Blöcke A und ein oder mehrere Blöcke X umfassen, wobei der Block A Olefincopolymerisat-Sequenzen, hydrierte Polyisopren-Sequenzen, hydrierte Copolymere aus Butadien/Isopren oder hydrierte Copolymere aus Butadien/Isopren und Styrol darstellt und der Block X Polyacrylat-, Polymethacrylat-, Styrol-, -Methylstyrol oder N- Vinyl-heterocyclische Sequenzen bzw. Sequenzen aus Gemischen von Polyacrylat-, Polymethacrylat-, Styrol-, α-Methylstyrol oder N-Vinyl- Heterocyclen darstellt.The residue compatible with component A) generally shows a non-polar character, whereas the incompatible residue is polar in nature. According to a particular aspect of the present invention, preferred dispersing components can be regarded as block copolymers which comprise one or more blocks A and one or more blocks X, the block A being olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene / isoprene or hydrogenated Copolymers of butadiene / isoprene and styrene represents and Block X represents polyacrylate, polymethacrylate, styrene, methylstyrene or N-vinyl heterocyclic sequences or sequences from mixtures of polyacrylate, polymethacrylate, styrene, α-methylstyrene or N-vinyl heterocycles.
Bevorzugte Dispergierkomponenten lassen sich durch Pfropfpolymerisation herstellen, wobei auf die zuvor beschriebenen Polyolefine, insbesondere auf die OCP und HSD, polare Monomere aufgepfropft werden. Hierzu können die Polyolefine durch mechanischen oder/und thermischen Abbau vorbehandelt werden.Preferred dispersion components can be prepared by graft polymerization, with polar monomers being grafted onto the polyolefins described above, in particular onto the OCP and HSD. For this purpose, the polyolefins can be pretreated by mechanical or / and thermal degradation.
Zu den polaren Monomeren gehören insbesondere (Meth)acrylate und Styrol-Verbindungen.The polar monomers include in particular (meth) acrylates and styrene compounds.
Der Ausdruck (Meth)acrylate umfaßt Methacrylate und Acrylate sowie Mischungen aus beiden.The term (meth) acrylates encompasses methacrylates and acrylates and mixtures of the two.
Gemäß einem besonderen Aspekt der vorliegenden Erfindung wird bei der Pfropfreaktion eine Monomerzusammensetzung eingesetzt aufweisend ein oder mehrere (Meth)acrylate der Formel (I)According to a particular aspect of the present invention, a monomer composition comprising one or more (meth) acrylates of the formula (I) is used in the grafting reaction
worin R Wasserstoff oder Methyl und R1 Wasserstoff, einen linearen oder verzweigten Alkylrest mit 1 bis 40 Kohlenstoffatomen bedeuten. wherein R is hydrogen or methyl and R 1 is hydrogen, a linear or branched alkyl radical having 1 to 40 carbon atoms.
Zu den bevorzugten Monomeren gemäß Formel (I) gehören unter anderem (Meth)acrylate, die sich von gesättigten Alkoholen ableiten, wie Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Propyl(meth)acrylat, iso-Propyl(meth)acrylat, n-Butyl(meth)acrylat, tert-Butyl(meth)acrylat, Pentyl(meth)acrylat, Hexyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, Heptyl(meth)acrylat, 2-tert.-Butylheptyl(meth)acrylat, Octyl(meth)acrylat, 3-iso-Propylheptyl(meth)acrylat, Nonyl(meth)acrylat, Decyl(meth)acrylat, Undecyl(meth)acrylat, 5-Methylundecyl(meth)acrylat, Dodecyl(meth)acrylat, 2-Methyldodecyl(meth)acrylat, Tridecyl(meth)acrylat, 5-Methyltridecyl(meth)acrylat, Tetradecyl(meth)acrylat, Pentadecyl(meth)acrylat, Hexadecyl(meth)acrylat, 2-Methylhexadecyl(meth)acrylat, Heptadecyl(meth)acrylat, 5-iso-Propylheptadecyl(meth)acrylat, 4-tert.-Butyloctadecyl(meth)acrylat, 5-Ethyloctadecyl(meth)acrylat, 3-iso-Propyloctadecyl(meth)acrylat, Octadecyl(meth)acrylat, Nonadecyl(meth)acrylat, Eicosyl(meth)acrylat, Cetyleicosyl(meth)acrylat, Stearyleicosyl(meth)acrylat, Docosyl(meth)acrylat und/oder Eicosyltetratriacontyl(meth)acrylat; (Meth)acrylate, die sich von ungesättigten Alkoholen ableiten, wie z. B. 2- Propinyl(meth)acrylat, Allyl(meth)acrylat, Vinyl(meth)acrylat, Oleyl(meth)acrylat;The preferred monomers according to formula (I) include, among others, (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth ) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth ) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5 -Methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-iso-propylheptadecyl (meth) acrylate, 4 -tert.-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyleicosyl (meth) acrylate, stearyleicosyl (meth) acrylate, docosyl (meth) acrylate and / or eicosyltetratriacontyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as. B. 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, oleyl (meth) acrylate;
Cycloalkyl(meth)acrylate, wie Cyclopentyl(meth)acrylat, 3-Vinylcyclohexyl(meth)acrylat, Cyclohexyl(meth)acrylat, Bornyl(meth)acrylat.Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate.
Des weiteren kann die Monomerzusammensetzung ein oder mehrere (Meth)acrylate der Formel (II) aufweisenFurthermore, the monomer composition can have one or more (meth) acrylates of the formula (II)
worin R Wasserstoff oder Methyl und R2 einen mit einer OH-Gruppe substituierten Alkylrest mit 2 bis 20 Kohlenstoffatomen oder einen alkoxylierten Rest der Formel (III) worin R3 und R4 unabhängig für Wasserstoff oder Methyl, R5 Wasserstoff oder einen Alkylrest mit 1 bis 40 Kohlenstoffatomen und n eine ganze Zahl von 1 bis 90 steht, bedeuten. wherein R is hydrogen or methyl and R 2 is an alkyl group with 2 to 20 carbon atoms substituted by an OH group or an alkoxylated group of the formula (III) wherein R 3 and R 4 are independently hydrogen or methyl, R 5 is hydrogen or an alkyl radical having 1 to 40 carbon atoms and n is an integer from 1 to 90.
(Meth)acrylate gemäß Formel (III) sind dem Fachmann bekannt. Zu diesen zählen unter anderem Hydroxylalkyl(meth)acrylate, wie(Meth) acrylates of the formula (III) are known to the person skilled in the art. These include hydroxylalkyl (meth) acrylates such as
3-Hydroxypropylmethacrylat,3-hydroxypropyl methacrylate,
3,4-Dihydroxybutylmethacrylat,3,4-dihydroxybutyl,
2-Hydroxyethylmethacrylat,2-hydroxyethyl methacrylate,
2-Hydroxypropylmethacrylat, 2,5-Dimethyl-1 ,6-hexandiol(meth)acrylat,2-hydroxypropyl methacrylate, 2,5-dimethyl-1, 6-hexanediol (meth) acrylate,
1 , 10-Decandiol(meth)acrylat,1, 10-decanediol (meth) acrylate,
1 ,2-Propandiol(meth)acrylat;1,2-propanediol (meth) acrylate;
Polyoxyethylen- und Polyoxypropylen-Derivate der (Meth)acrylsäure, wiePolyoxyethylene and polyoxypropylene derivatives of (meth) acrylic acid, such as
Triethylenglycol(meth)acrylat,Triethylene glycol (meth) acrylate,
Tetraethylenglycol(meth)acrylat undTetraethylene glycol (meth) acrylate and
Tetrapropylengylcol(meth)acrylat.Tetrapropylengylcol (meth) acrylate.
Die (Meth)acrylate mit langkettigem Alkoholrest lassen sich beispielsweise durch Umsetzen von den entsprechenden Säuren und/oder kurzkettigen (Meth)acrylaten, insbesondere Methyl(meth)acrylat oder Ethyl(meth)acrylat, mit langkettigen Fettalkoholen erhalten, wobei im allgemeinen eine Mischung von Estern, wie beispielsweise (Meth)acrylaten mit verschieden langkettigen Alkoholresten entsteht. Zu diesen Fettalkoholen gehören unter anderem Oxo AlcoholO 7911 und Oxo AlcoholO 7900, Oxo AlcoholO 1100 von Monsanto; AlphanolÖ 79 von ICI; NafolÖ 1620, AlfolÖ 610 und AlfolÖ 810 von Condea; EpalÖ 610 und Epal Ö 810 von Ethyl Corporation; LinevolÖ 79, LinevolÖ 911 und DobanolÖ 25L von Shell AG; Lial 125 von AugustaÖ Mailand; DehydadO und LorolÖ von Henkel KGaA sowie LinopolÖ 7 - 11 und AcropolÖ 91 Ugine Kuhlmann.The (meth) acrylates with a long-chain alcohol residue can be obtained, for example, by reacting the corresponding acids and / or short-chain (meth) acrylates, in particular methyl (meth) acrylate or ethyl (meth) acrylate, with long-chain fatty alcohols, a mixture of Esters, such as (meth) acrylates with different long-chain alcohol residues. These fatty alcohols include, among others, Oxo AlcoholO 7911 and Oxo AlcoholO 7900, Oxo AlcoholO 1100 from Monsanto; Alphanol® 79 from ICI; NafolÖ 1620, AlfolÖ 610 and AlfolÖ 810 from Condea; Epalo 610 and Epalo 810 from Ethyl Corporation; LinevolÖ 79, LinevolÖ 911 and DobanolÖ 25L from Shell AG; Lial 125 from AugustaÖ Milan; DehydadO and LorolÖ from Henkel KGaA as well as LinopolÖ 7 - 11 and AcropolÖ 91 Ugine Kuhlmann.
und/oder ein oder mehrere (Meth)acrylate der Formel (IV)and / or one or more (meth) acrylates of the formula (IV)
worin R Wasserstoff oder Methyl, X Sauerstoff oder eine Aminogruppe der Formel -NH- oder -NR7-, worin R7 für einen Alkylrest mit 1 bis 40 Kohlenstoffatomen steht, und R6 einen mit mindestens einer -NR8R9- Gruppe substituierten linearen oder verzweigten Alkylrest mit 2 bis 20, vorzugsweise 2 bis 6 Kohlenstoffatomen bedeuten, wobei R8 und R9 unabhängig von einander für Wasserstoff, einen Alkylrest mit 1 bis 20, vorzugsweise 1 bis 6 stehen oder worin R8 und R9 unter Einbeziehung des Stickstoffatoms und gegebenenfalls eines weiteren Stickstoff oder Sauerstoffatoms einen 5- oder 6-gliederigen Ring bilden, der gegebenenfalls mit Ci-Cö-Alkyl substituiert sein kann.wherein R is hydrogen or methyl, X is oxygen or an amino group of the formula -NH- or -NR 7 -, wherein R 7 is an alkyl radical having 1 to 40 carbon atoms, and R 6 is substituted by at least one -NR 8 R 9 - group linear or branched alkyl radical having 2 to 20, preferably 2 to 6 carbon atoms, where R 8 and R 9 independently of one another are hydrogen, an alkyl radical having 1 to 20, preferably 1 to 6 or wherein R 8 and R 9 including the Nitrogen atom and optionally a further nitrogen or oxygen atom form a 5- or 6-membered ring which can optionally be substituted with Ci-C ö alkyl.
Zu den (Meth)acrylaten bzw. (Meth)acrylamiden gemäß Formel (IV) gehören unter anderemThe (meth) acrylates or (meth) acrylamides according to formula (IV) include, among others
Amide der (Meth)acrylsäure, wieAmides of (meth) acrylic acid, such as
N-(3-Dimethylaminopropyl)methacrylamid,N- (3-dimethylaminopropyl) methacrylamide,
N-(Diethylphosphono)methacrylamid,N- (diethylphosphono) methacrylamide,
1-Methacryloylamido-2-methyl-2-propanol,1-Methacryloylamido-2-methyl-2-propanol,
N-(3-Dibutylaminopropyl)methacrylamid,N- (3-dibutylaminopropyl) methacrylamide,
N-t-Butyl-N-(diethylphosphono)methacrylamid,N-t-butyl-N- (diethylphosphono) methacrylamide,
N,N-bis(2-Diethylaminoethyl)methacrylamid,N, N-bis (2-diethylaminoethyl) methacrylamide,
4-Methacryloylamido-4-methyl-2-pentanol,4-Methacryloylamido-4-methyl-2-pentanol,
N-(Methoxymethyl)methacrylamid, N-(2-Hydroxyethyl)methacrylamid, N-Acetylmethacrylamid,N- (methoxymethyl) methacrylamide, N- (2-hydroxyethyl) methacrylamide, N-acetyl methacrylamide,
N-(Dimethylaminoethyl)methacrylamid,N- (dimethylaminoethyl) methacrylamide,
N-Methyl-N-phenylmethacrylamid,N-methyl-N-phenylmethacrylamide,
N,N-Diethylmethacrylamid,N, N-diethyl methacrylamide,
N-Methylmethacrylamid,N-methyl methacrylamide,
N,N-Dimethylmethacrylamid,N, N-dimethyl methacrylamide,
N-Isopropylmethacrylamid;N-isopropylmethacrylamide;
Aminoalkylmethacrylate, wie tris(2-Methacryloxyethyl)amin,Aminoalkyl methacrylates, such as tris (2-methacryloxyethyl) amine,
N-Methylformamidoethylmethacrylat,N-Methylformamidoethylmethacrylat,
2-Ureidoethylmethacrylat; heterocyclische (Meth)acrylate, wie 2-(1-lmidazolyl)ethyl(meth)acrylat,2-Ureidoethylmethacrylat; heterocyclic (meth) acrylates, such as 2- (1-imidazolyl) ethyl (meth) acrylate,
2-(4-Morpholinyl)ethyl(meth)acrylat und 1 -(2-Methacryloyloxyethyl)-2- pyrrolidon.2- (4-morpholinyl) ethyl (meth) acrylate and 1 - (2-methacryloyloxyethyl) -2-pyrrolidone.
Des weiteren kann die Monomerzusammensetzung Styrol-Verbindungen aufweisen. Zu diesen gehören unter anderem Styrol, substituierte Styrole mit einem Alkylsubstituenten in der Seitenkette, wie z. B. α-Methylstyrol und α-Ethylstyrol, substituierte Styrole mit einem Alkylsubstitutenten am Ring, wie Vinyltoluol und p-Methylstyrol, halogenierte Styrole, wie beispielsweise Monochlorstyrole, Dichlorstyrole, Tribromstyrole und Tetrabromstyrole.Furthermore, the monomer composition can have styrene compounds. These include styrene, substituted styrenes with an alkyl substituent in the side chain, such as. B. α-methyl styrene and α-ethyl styrene, substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
Darüber hinaus können die Monomerzusammensetzungen heterocyclische Vinylverbindungen, wie 2-Vinylpyridin, 3-Vinylpyridin, 2- Methyl-5-vinylpyridin, 3-Ethyl-4-vinylpyridin, 2,3-Dimethyl-5-vinylpyridin, Vinylpyrimidin, Vinylpiperidin, 9-Vinylcarbazol, 3-Vinylcarbazol, 4-Vinylcarbazol, 1 -Vinylimidazol, 2-Methyl-1-vinylimidazol, N-Vinylpyrrolidon, 2-Vinylpyrrolidon, N-Vinylpyrrolidin, 3-Vinylpyrrolidin, N-Vinylcaprolactam, N-Vinylbutyrolactam, Vinyloxolan, Vinylfuran, Vinylthiophen, Vinylthiolan, Vinylthiazole und hydrierte Vinylthiazole, Vinyloxazole und hydrierte Vinyloxazole umfassen.In addition, the monomer compositions can be heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole , 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinyl caprolactam, N-vinyl butyrolactam, vinyl oxolane, vinyl furan, vinyl thiophene, vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles.
Neben Styrol-Verbindungen und (Meth)acrylaten sind als Monomere insbesondere Monomere bevorzugt, die dispergierende Wirkungen haben, wie beispielsweise die zuvor genannten heterocyclischen Vinylverbindungen. Diese Monomere werden des weiteren als dispergierende Monomere bezeichnet.In addition to styrene compounds and (meth) acrylates, preferred monomers are in particular monomers which have dispersing effects, such as the heterocyclic vinyl compounds mentioned above. These monomers are also referred to as dispersing monomers.
Die zuvor genannten ethylenisch ungesättigten Monomere können einzeln oder als Mischungen eingesetzt werden. Es ist des weiteren möglich, die Monomerzusammensetzung während der Polymerisation zu variieren, um definierte Strukturen, wie beispielsweise Blockcopolymere, zu erhalten.The aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is furthermore possible to vary the monomer composition during the polymerization in order to obtain defined structures, such as block copolymers.
Das Gewichtsverhältnis der mit den Polyolefinen kompatiblen Teile der Dispergierkomponente, insbesondere der Blöcke A, zu den mit den Polyolefinen inkompatiblen Teile der Dispergierkomponente, insbesondere den Blöcken X, kann in weiten Bereichen liegen. Im allgemeinen liegt dieses Verhältnis im Bereich von 50:1 bis 1 :50, insbesondere 20:1 bis 1 :20 und besonders bevorzugt 10:1 bis 1 :10.The weight ratio of the parts of the dispersing component, particularly blocks A, which are compatible with the polyolefins to the parts of the dispersing component, in particular blocks X, which are incompatible with the polyolefins can be within wide ranges. In general, this ratio is in the range from 50: 1 to 1:50, in particular 20: 1 to 1:20 and particularly preferably 10: 1 to 1:10.
Die Herstellung der zuvor dargestellten Dispergierkomponenten ist in der Fachwelt bekannt. Beispielsweise kann die Herstellung über eine Polymerisation in Lösung erfolgen. Derartige Verfahren sind unter anderem in DE-A 12 35 491 , BE-A 592 880, US-A 4 281 081 , US-A 4 338 418 und US-A-4,290,025 beschrieben.The manufacture of the dispersing components shown above is known in the art. For example, it can be produced by polymerization in solution. Such processes are described, inter alia, in DE-A 12 35 491, BE-A 592 880, US-A 4 281 081, US-A 4 338 418 and US-A-4,290,025.
Dabei kann in einem geeigneten Reaktionsgefäß, zweckmäßig ausgestattet mit Rührer, Thermometer, Rückflußkühler und Dosierleitung, ein Gemisch aus dem OCP und einem oder mehreren der zuvor dargelegten Monomere vorgelegt werden. Nach erfolgtem Lösen unter Inertatmosphäre, wie z. B. Stickstoff, unter Erhitzen, beispielsweise auf 110 °C, wird ein Anteil eines an sich üblichen Radikalinitiators, beispielsweise aus der Gruppe der Perester, angesetzt, zunächst beispielsweise ca. 0,7 Gew.-% bezogen auf die Monomeren.A mixture of the OCP and one or more of the monomers set out above can be placed in a suitable reaction vessel, suitably equipped with a stirrer, thermometer, reflux condenser and metering line. After loosening under an inert atmosphere, such as. B. nitrogen, with heating, for example to 110 ° C, a portion of a conventional radical initiator, for example from the group of peresters, is set, initially for example about 0.7 wt .-% based on the monomers.
Demnach dosiert man über einige Stunden, beispielsweise 3,5 Stunden hinweg ein Gemisch aus den restlichen Monomeren unter Zusatz weiteren Initators, beispielsweise ca. 1 ,3 Gew.-% bezogen auf die Monomeren zu. Man füttert zweckmäßig einige Zeit nach Zulaufende noch etwas Initiator nach, beispielsweise nach zwei Stunden. Die Gesamtpolymerisationsdauer kann als Richtwert beispielsweise mit ca. 8 Stunden angenommen werden. Nach Polymerisationsende verdünnt man zweckmäßig mit einem geeigneten Lösungsmittel, wie z. B. einem Phthalsäureester wie Dibutylphthalat. Man erhält in der Regel eine nahezu klare, viskose Lösung.Accordingly, a mixture of the remaining monomers with the addition of further initiators, for example about 1.3% by weight, based on the monomers, is metered in over a few hours, for example 3.5 hours. It is advisable to add some initiator some time after the end of the feed, for example after two hours. The total polymerization time can be taken as a guideline, for example, about 8 hours. After the end of the polymerization, the mixture is expediently diluted with a suitable solvent, such as, for. B. a phthalate such as dibutyl phthalate. As a rule, an almost clear, viscous solution is obtained.
Des weiteren kann die Herstellung der Polymerdispersionen in einem Kneter, einem Extruder oder in einem statischen Mischer erfolgen. Durch die Behandlung im Gerät erfolgt unter dem Einfluß der Scherkräfte, der Temperatur und der Initiator-Konzentration ein Abbau des Molgewichts des Polyolefins, insbesondere des OCPs bzw. HSDs.Furthermore, the polymer dispersions can be produced in a kneader, an extruder or in a static mixer. The treatment in the device reduces the molecular weight of the polyolefin, in particular the OCP or HSD, under the influence of the shear forces, the temperature and the initiator concentration.
Beispiele für bei der Pfropf-Copolymerisation geeignete Initiatoren sind Cumolhydroperoxyd, Diumylperoxyd, Benzoylperoxyd, Azodiisobuttersäure-dinitril, 2,2-Bis(t-Butylperoxy)butan, Diäthylperoxydicarbonat und tert.-Butylperoxyd. Die Verarbeitungstemperatur beträgt zwischen 80 °C und 350 °C. Die Verweilzeit im Kneter oder Extruder beträgt zwischen 1 Minute und 10 Stunden. Je länger die Dispersion im Kneter oder Extruder behandelt wird, desto geringer wird das Molekulargewicht. Die Temperatur und die Konzentration an radikalbildenden Initiatoren können entsprechend dem gewünschten Molekulargewicht eingestellt werden. Die lösungsmittel-freie Polymer-in-Polymer-Dispersion kann durch Einarbeitung in geeignete Trägermedien in eine gut handhabbare, flüssige Polymer-/Polymer- Emulsion überführt werden.Examples of initiators suitable in the graft copolymerization are cumene hydroperoxide, diumyl peroxide, benzoyl peroxide, azodiisobutyric acid dinitrile, 2,2-bis (t-butyl peroxy) butane, diethyl peroxydicarbonate and tert-butyl peroxide. The processing temperature is between 80 ° C and 350 ° C. The residence time in the kneader or extruder is between 1 minute and 10 hours. The longer the dispersion is treated in the kneader or extruder, the lower the molecular weight. The temperature and the concentration of free-radical initiators can be adjusted according to the desired molecular weight. The solvent-free polymer-in-polymer dispersion can be converted into an easy-to-handle, liquid polymer / polymer emulsion by incorporation into suitable carrier media.
Der Anteil der Komponenten B) beträgt im allgemeinen bis zu 30 Gew.-%, insbesondere liegt dieser Anteil im Bereich von 5 bis 15 Gew.-%, ohne dass hierdurch eine Beschränkung erfolgen soll. Der Einsatz von größeren Mengen an Komponente B) ist häufig unwirtschaftlich. Geringere Mengen führen vielfach zu einer geringeren Stabilität der Polymerdispersion.The proportion of components B) is generally up to 30% by weight, in particular this proportion is in the range from 5 to 15% by weight, without any intention that this should impose a restriction. The use of larger amounts of component B) is often uneconomical. Smaller amounts often lead to a lower stability of the polymer dispersion.
Die Komponente C)Component C)
Die Komponente C) ist für den Erfolg der vorliegenden Erfindung wesentlich. Die als flüssiges Trägermedium verwendbaren Lösungsmitteln sollen inert und im ganzen unbedenklich sein. Trägermedien, die die genannten Bedingungen erfüllen, gehören z. B. zur Gruppe der Ester, Ether und/oder zur Gruppe der höheren Alkohole. In der Regel enthalten die Moleküle der als Trägermedium in Frage kommenden Verbindungstypen mehr als 8 Kohlenstoffatome pro Molekül.Component C) is essential for the success of the present invention. The solvents that can be used as the liquid carrier medium should be inert and, on the whole, harmless. Carrier media that meet the conditions mentioned include, for. B. to the group of esters, ethers and / or to the group of higher alcohols. As a rule, the molecules of the types of compounds that can be used as carrier medium contain more than 8 carbon atoms per molecule.
Es sei erwähnt, dass auch Gemische aus den vorstehend beschriebenen Lösungsmitteln für das Trägermedium in Frage kommen.It should be mentioned that mixtures of the solvents described above can also be used for the carrier medium.
Hervorzuheben sind in der Gruppe der Ester: Phosphorsäureester, Ester von Dicarbonsäuren, Ester von Monocarbonsäuren mit Diolen oder Polyalkylen-glykolen, Ester von Neopentylpolyolen mit Monocarbonsäuren. (Vgl. Ullmanns Encyclopädie der Technischen Chemie, 3. Aufl., Bd. 15, S. 287 -292, Urban & Schwarzenber (1964)). Als Ester von Dicarbonsäuren kommen einmal die Ester der Phthalsäure in Frage, insbesondere die Phthalsäureester mit C-4 bis Cs-Alkoholen, wobei Dibutylphthalat und Dioctylphthalat besonders genannt seien, sodann die Ester aliphatischer Dicarbonsäuren, insbesondere die Ester geradkettiger Dicarbonsäuren mit verzweigtkettigen primären Alkoholen. Besonders hervorgehoben werden die Ester der Sebazin-, der Adipin- und der Azelainsäure, wobei insbesondere die 2-Ethylhexyl-, lsooctyl-3,5,5- Trimethylester, sowie die Ester mit den Cs-, Cg- bzw. Cifj-Oxoalkoholen genannt werden sollen.The following should be emphasized in the group of esters: phosphoric acid esters, esters of dicarboxylic acids, esters of monocarboxylic acids with diols or polyalkylene glycols, esters of neopentyl polyols Monocarboxylic acids. (See Ullmann's Encyclopedia of Technical Chemistry, 3rd ed., Vol. 15, pp. 287-292, Urban & Schwarzenber (1964)). Suitable esters of dicarboxylic acids are the esters of phthalic acid, in particular the phthalic esters with C-4 to Cs alcohols, dibutyl phthalate and dioctyl phthalate being particularly mentioned, and then the esters of aliphatic dicarboxylic acids, especially the esters of straight-chain dicarboxylic acids with branched-chain primary alcohols. Particular emphasis is given to the esters of sebacic, adipic and azelaic acid, in particular the 2-ethylhexyl, isooctyl-3,5,5-trimethyl esters and the esters with the Cs, Cg and Cifj oxo alcohols should be.
Besondere Bedeutung besitzen die Ester geradkettiger primärer Alkohole mit verzweigten Dicarbonsäuren. Als Beispiele seien die alkylsubstituierte Adipinsäure, beispielsweise die 2,2,4-Trimethyladipinsäure genannt.The esters of straight-chain primary alcohols with branched dicarboxylic acids are of particular importance. Examples include the alkyl-substituted adipic acid, for example 2,2,4-trimethyladipic acid.
Als Alkoholkoponente kommen mit Vorteil z. B. die vorstehend genannten Oxo-Alkohole in Frage. Als Ester von Monocarbonsäuren mit Diolen oder Polyalkylenglykolen seien die Di-Ester mit Diethylenglykol, Triethylenglykol, Tetraethylenglykol bis zum Decamethylenglykol, ferner mit Dipropylenglykol als Alkoholkomponenten hervorgehoben. Als Monocarbonsäuren seien die Propionsäure, die (Iso)buttersäure sowie die Pelargonsäure spezifisch erwähnt - genannt sei beispielsweise das Dipropylenglykoldipelargonat, das Diäthylenglykoldipropionat - und Diisobutyrat sowie die entsprechenden Ester des Triethylenglykols, sowie der Tetraethylenglykol-di-2-ethylhexansäureester.As alcohol component come with advantage such. B. the above-mentioned oxo alcohols in question. As esters of monocarboxylic acids with diols or polyalkylene glycols, the di-esters with diethylene glycol, triethylene glycol, tetraethylene glycol to decamethylene glycol, and also with dipropylene glycol as alcohol components should be emphasized. The monocarboxylic acids which are specifically mentioned are propionic acid, (iso) butyric acid and pelargonic acid - for example dipropylene glycol dipelargonate, diethylene glycol dipropionate - and diisobutyrate as well as the corresponding esters of triethylene glycol and the tetraethylene glycol di-2-ethylhexanoic acid ester.
Bevorzugte Trägermedien stellen nichtionische Tenside dar. Hierzu zählen unter anderem Fettsäurepolyglykolester, Fettaminpolyglykolether, Alkylpolyglykoside, Fettamin-N-oxide sowie langkettige Alkylsulfoxide. Des weiteren gehören zur Gruppe der nichtionischen Tenside die zuvor genannten Ester mit Ethoxygruppen.Preferred carrier media are nonionic surfactants. These include, inter alia, fatty acid polyglycol esters, fatty amine polyglycol ethers, alkyl polyglycosides, fatty amine N-oxides and long-chain alkyl sulfoxides. Furthermore, the aforementioned esters with ethoxy groups belong to the group of nonionic surfactants.
Eine weitere Gruppe besonders bevorzugter Trägermedien, die nichtionische Tenside darstellen, stellen mit (Oligo)oxyalkyl-Gruppen veretherte Alkohole dar.Another group of particularly preferred carrier media which are nonionic surfactants are alcohols etherified with (oligo) oxyalkyl groups.
Diese umfassen insbesondere ethoxylierte Alkohole, die besonders bevorzugt 1 bis 20, insbesondere 2 bis 8 Ethoxygruppen aufweisen. Der hydrophobe Rest der ethoxylierten Alkohole umfasst vorzugsweise 1 bis 40, vorzugsweise 4 bis 22 Kohlenstoffatome, wobei sowohl lineare als auch verzweigte Alkoholreste eingesetzt werden können. Ebenso sind Oxoalkoholethoxylate einsetzbar.These include, in particular, ethoxylated alcohols which particularly preferably have 1 to 20, in particular 2 to 8, ethoxy groups. The hydrophobic radical of the ethoxylated alcohols preferably comprises 1 to 40, preferably 4 to 22 carbon atoms, it being possible to use both linear and branched alcohol radicals. Oxo alcohol ethoxylates can also be used.
Beispiele für käufliche Ethoxylate, welche zur Herstellung der erfindungsgemäßen Konzentrate herangezogen werden können, sind Ether der Lutensol® A-Marken, insbesondere Lutensol® A 3 N, Lutensol® A 4 N, Lutensol® A 7 N und Lutensol® A 8 IM, Ether der Lutensol® TO-Marken , insbesondere Lutensol® TO 2, Lutensol® TO 3, Lutensol® TO 5, Lutensol® TO 6, Lutensol® TO 65, Lutensol® TO 69, Lutensol® TO 7, Lutensol® TO 79, Lutensol® 8 und Lutensol® 89, Ether der Lutensol® AO- Marken, insbesondere Lutensol® AO 3, Lutensol® AO 4, Lutensol® AO 5, Lutensol® AO 6, Lutensol® AO 7, Lutensol® AO 79, Lutensol® AO 8 und Lutensol® AO 89, Ether der Lutensol® ON-Marken, insbesondere Lutensol® ON 30, Lutensol® ON 50, Lutensol® ON 60, Lutensol® ON 65, Lutensol® ON 66, Lutensol® ON 70, Lutensol® ON 79 und Lutensol® ON 80, Ether der Lutensol® XL-Marken, insbesondere Lutensol® XL 300, Lutensol® XL 400, Lutensol® XL 500, Lutensol® XL 600, Lutensol® XL 700, Lutensol® XL 800, Lutensol® XL 900 und Lutensol® XL 1000, Ether der Lutensol® AP-Marken, insbesondere Lutensol® AP 6, Lutensol® AP 7, Lutensol® AP 8, Lutensol® AP 9, Lutensol® AP 10, Lutensol® AP 14 und Lutensol® AP 20, Ether der IMBENTIN®-Marken, insbesondere der IMBENTIN®-AG-Marken, der IMBENTIN®-U-Marken, der IMBENTIN®-C- Marken, der IMBENTIN®-T-Marken, der IMBENTIN®-OA-Marken, der IMBENTIN®-POA-Marken, der IMBENTIN®-N-Marken sowie der IMBENTIN®-0-Marken sowie Ether der Marlipal®-Marken, insbesondere Marlipal® 1/7, Marlipal® 1012/6, Marlipal® 1618/1 , Marlipal® 24/20, Marlipal® 24/30, Marlipal® 24/40, Marlipal® 013/20 , Marlipal® 013/30, Marlipal® 013/40, Marlipal® 025/30, Marlipal® 025/70, Marlipal® 045/30, Marlipal® 045/40, Marlipal® 045/50, Marlipal® 045/70 und Marlipal® 045/80.Examples of commercially available ethoxylates which can be used for the preparation of the concentrates according to the invention, ethers are the Lutensol ® A brands, especially Lutensol ® A 3 N, Lutensol ® A 4 N, Lutensol ® A 7 N and Lutensol ® A 8 IM, ethers of the Lutensol ® TO brands, in particular Lutensol ® TO 2, Lutensol ® TO 3, Lutensol ® TO 5, Lutensol ® TO 6, Lutensol ® TO 65, Lutensol ® TO 69, Lutensol ® TO 7, Lutensol ® TO 79, Lutensol ® 8 and Lutensol ® 89, ethers of the Lutensol ® AO brands, in particular Lutensol ® AO 3, Lutensol ® AO 4, Lutensol ® AO 5, Lutensol ® AO 6, Lutensol ® AO 7, Lutensol ® AO 79, Lutensol ® AO 8 and Lutensol ® AO 89, ethers of the Lutensol ® ON brands, in particular Lutensol ® ON 30, Lutensol ® ON 50, Lutensol ® ON 60, Lutensol ® ON 65, Lutensol ® ON 66, Lutensol ® ON 70, Lutensol ® ON 79 and Lutensol ® ON 80, ethers of the Lutensol ® XL brands, in particular Lutensol ® XL 300, Lutensol ® XL 400, Lutensol ® XL 500, Lutensol ® X L 600, Lutensol ® XL 700, Lutensol ® XL 800, Lutensol ® XL 900 and Lutensol ® XL 1000, ethers of the Lutensol ® AP brands, in particular Lutensol ® AP 6, Lutensol ® AP 7, Lutensol ® AP 8, Lutensol ® AP 9, Lutensol ® AP 10, Lutensol ® AP 14 and Lutensol ® AP 20, ether of the IMBENTIN ® brands, in particular the IMBENTIN ® -AG brands, the IMBENTIN ® -U brands, the IMBENTIN ® -C brands, the IMBENTIN ® -T brands, the IMBENTIN ® -OA Brands, the IMBENTIN ® POA brands, the IMBENTIN ® N brands and the IMBENTIN ® 0 brands as well as ethers of the Marlipal ® brands, in particular Marlipal ® 1/7, Marlipal ® 1012/6, Marlipal ® 1618 / 1, Marlipal ® 24/20, Marlipal ® 24/30, Marlipal ® 24/40, Marlipal ® 013/20, Marlipal ® 013/30, Marlipal ® 013/40, Marlipal ® 025/30, Marlipal ® 025/70 , Marlipal ® 045/30, Marlipal ® 045/40, Marlipal ® 045/50, Marlipal ® 045/70 and Marlipal ® 045/80.
Besonders bevorzugt sind insbesondere Gemische, die mit(Oligo)oxyalkyl- Gruppen veretherte Alkohole sowie Ester umfassen. Derartige Gemische zeigen eine unerwartet hohe Stabilität. Dies gilt insbesondere für Dispersionen, die hydrierte Styrol-Dien-Copolymere (HSD) aufweisen. Hierbei kann das Gewichtsverhältnis von Ester zu mit(Oligo)oxyalkyl- Gruppen verethertem Alkohol in weiten Bereichen liegen. Besonders bevorzugt liegt dieses Verhältnis im Bereich von 15:1 bis 1 :15, insbesondere 5:1 bis 1 :5.Mixtures comprising alcohols etherified with (oligo) oxyalkyl groups and esters are particularly preferred. Such mixtures show an unexpectedly high stability. This applies in particular to dispersions which have hydrogenated styrene-diene copolymers (HSD). The weight ratio of ester to alcohol etherified with (oligo) oxyalkyl groups can be in wide ranges. This ratio is particularly preferably in the range from 15: 1 to 1:15, in particular 5: 1 to 1: 5.
Eine weitere Gruppe bevorzugter Trägermedien stellen Mineralöle dar. Überraschend konnte festgestellt werden, dass die Stabilität der Polymerdispersion durch die Gegenwart von Mineralöl erheblich gesteigert werden kann.Mineral oils represent a further group of preferred carrier media. Surprisingly, it was found that the stability of the polymer dispersion can be increased considerably by the presence of mineral oil.
Mineralöle sind an sich bekannt und kommerziell erhältlich. Sie werden im allgemeinen aus Erdöl oder Rohöl durch Destillation und/oder Raffination und gegebenenfalls weitere Reinigungs- und Veredelungsverfahren gewonnen, wobei unter den Begriff Mineralöl insbesondere die höhersiedenden Anteile des Roh- oder Erdöls fallen. Im allgemeinen liegt der Siedepunkt von Mineralöl höher als 200 °C, vorzugsweise höher als 300 °C, bei 5000 Pa. Die Herstellung durch Schwelen von Schieferöl, Verkoken von Steinkohle, Destillation unter Luftabschluß von Braunkohle sowie Hydrieren von Stein- oder Braunkohle ist ebenfalls möglich. Zu einem geringen Anteil werden Mineralöle auch aus Rohstoffen pflanzlichen (z. B. aus Jojoba, Raps) od. tierischen (z. B. Klauenöl) Ursprungs hergestellt. Dementsprechend weisen Mineralöle, je nach Herkunft unterschiedliche Anteile an aromatischen, cyclischen, verzweigten und linearen Kohlenwasserstoffen auf.Mineral oils are known per se and are commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and upgrading processes, the term mineral oil in particular referring to the higher-boiling proportions of the crude or petroleum. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. It is also possible to produce by smoldering shale oil, coking hard coal, distilling with the exclusion of air from brown coal and hydrogenating hard coal or brown coal. To a small extent, mineral oils are also made from raw materials of vegetable (e.g. jojoba, rapeseed) or animal (e.g. claw oil) origin. Accordingly, mineral oils have different proportions of aromatic, cyclic, branched and linear hydrocarbons depending on their origin.
Im allgemeinen unterscheidet man paraffinbasische, naphthenische und aromatische Anteile in Rohölen bzw. Mineralölen, wobei die Begriffe paraffinbasischer Anteil für längerkettig bzw. stark verzweigte iso-Alkane und naphtenischer Anteil für Cycloalkane stehen. Darüber hinaus weisen Mineralöle, je nach Herkunft und Veredelung unterschiedliche Anteile an n-Alkanen, iso-Alkanen mit einem geringen Verzweigungsgrad, sogenannte monomethylverzweigten Paraffine, und Verbindungen mit Heteroatomen, insbesondere O, N und/oder S auf, denen bedingt polare Eigenschaften zugesprochen werden. Die Zuordnung ist jedoch schwierig, da einzelne Alkanmoleküle sowohl langkettig verzweigte Gruppen als auch Cycloalkanreste und aromatische Anteile aufweisen können. Für die Zwecke der vorliegenden Erfindung kann die Zuordnung beispielsweise gemäß DIN 51 378 erfolgen. Polare Anteile können auch gemäß ASTM D 2007 bestimmt werden.In general, a distinction is made between paraffin-based, naphthenic and aromatic components in crude oils or mineral oils, the terms paraffin-based component standing for longer-chain or strongly branched iso-alkanes and naphthenic component for cycloalkanes. In addition, depending on their origin and refinement, mineral oils have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are said to have limited polar properties , The assignment is difficult, however, since individual alkane molecules can have long-chain branched groups as well as cycloalkane residues and aromatic components. For the purposes of the present invention, the assignment can be made, for example, in accordance with DIN 51 378. Polar fractions can also be determined in accordance with ASTM D 2007.
Der Anteil der n-Alkane beträgt in bevorzugten Mineralölen weniger als 3 Gew.-%, der Anteil der O, N und/oder S-haltigen Verbindungen weniger als 6 Gew.-%. Der Anteil der Aromaten und der monomethylverzweigten Paraffine liegt im allgemeinen jeweils im Bereich von 0 bis 40 Gew.-%. Gemäß einem interssanten Aspekt umfaßt Mineralöl hauptsächlich naphtenische und paraffinbasische Alkane, die im allgemeinen mehr als 13, bevorzugt mehr als 18 und ganz besonders bevorzugt mehr als 20 Kohlenstoffatome aufweisen. Der Anteil dieser Verbindungen ist im allgemeinen > 60 Gew.-%, vorzugsweise > 80 Gew.-%, ohne daß hierdurch eine Beschränkung erfolgen soll. Ein bevorzugtes Mineralöl enthält 0,5 bis 30 Gew.-% aromatische Anteile, 15 bis 40 Gew.-% naphthenische Anteile, 35 bis 80 Gew.-% paraffinbasische Anteile, bis zu 3 Gew.-% n-Alkane und 0,05 bis 5 Gew.-% polare Verbindungen, jeweils bezogen auf das Gesamtgewicht des Mineralöls.The proportion of n-alkanes in preferred mineral oils is less than 3% by weight, the proportion of O, N and / or S-containing compounds is less than 6% by weight. The proportion of the aromatics and the monomethyl-branched paraffins is generally in each case in the range from 0 to 40% by weight. In an interesting aspect, mineral oil mainly comprises naphthenic and paraffin-based alkanes, which generally have more than 13, preferably more than 18 and very particularly preferably more than 20 carbon atoms. The proportion of these compounds is in in general> 60% by weight, preferably> 80% by weight, without any intention that this should impose a restriction. A preferred mineral oil contains 0.5 to 30% by weight of aromatic components, 15 to 40% by weight of naphthenic components, 35 to 80% by weight of paraffin-based components, up to 3% by weight of n-alkanes and 0.05 up to 5% by weight of polar compounds, in each case based on the total weight of the mineral oil.
Eine Analyse von besonders bevorzugten Mineralölen, die mittels herkömmlicher Verfahren, wie Harnstofftrennung undAn analysis of particularly preferred mineral oils using conventional methods such as urea separation and
Flüssigkeitschromatographie an Kieselgel, erfolgte, zeigt beispielsweise folgende Bestandteile, wobei sich die Prozentangaben auf dasLiquid chromatography on silica gel, for example, shows the following components, the percentages referring to the
Gesamtgewicht des jeweils eingesetzten Mineralöls beziehen: n-Alkane mit ca. 18 bis 31 C-Atome:Obtain the total weight of the mineral oil used: n-alkanes with approx. 18 to 31 C atoms:
0,7 - 1 ,0 %, gering verzweigte Alkane mit 18 bis 31 C-Atome:0.7 - 1.0%, slightly branched alkanes with 18 to 31 C atoms:
1 ,0 - 8,0 %,1.0 - 8.0%,
Aromaten mit 14 bis 32 C-Atomen:Aromatics with 14 to 32 carbon atoms:
0,4 - 10,7 %,0.4 - 10.7%,
Iso- und Cyclo-Alkane mit 20 bis 32 C-Atomen:Iso- and cyclo-alkanes with 20 to 32 carbon atoms:
60,7- 82,4 %, polare Verbindungen:60.7- 82.4%, polar compounds:
0,1 - 0,8 %,0.1 - 0.8%,
Verlust:Loss:
6,9 - 19,4 %.6.9-19.4%.
Wertvolle Hinweise hinsichtlich der Analyse von Mineralölen sowie eine Aufzählung von Mineralölen, die eine abweichende Zusammensetzung aufweisen, findet sich beispielsweise in Ullmanns Encyclopedia of Industrial Chemistry, 5*" Edition on CD-ROM, 1997, Stichwort "lubricants and related products". Gemäß einem besonderen Aspekt der vorliegenden Erfindung werden als Trägermedium Mischungen eingesetzt, die Mineralöl und nichtionische Tenside, insbesondere mit (Oligo)oxyalkyl-Gruppen veretherte Alkohole umfassen.Valuable information regarding the analysis of mineral oils as well as a list of mineral oils with different compositions can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 * "Edition on CD-ROM, 1997, keyword" lubricants and related products ". According to a particular aspect of the present invention, mixtures are used as carrier medium which comprise mineral oil and nonionic surfactants, in particular alcohols etherified with (oligo) oxyalkyl groups.
Derartige Gemische zeigen eine unerwartet hohe Stabilität. Hierbei kann das Gewichtsverhältnis von Mineralöl zu nichtionischem Tensid, insbesondere zu mit(Oligo)oxyalkyl-Gruppen verethertem Alkohol in weiten Bereichen liegen. Besonders bevorzugt liegt dieses Verhältnis im Bereich von 15:1 bis 1 :15, insbesondere 5:1 bis 1 :5.Such mixtures show an unexpectedly high stability. The weight ratio of mineral oil to nonionic surfactant, in particular to alcohol etherified with (oligo) oxyalkyl groups, can be within wide ranges. This ratio is particularly preferably in the range from 15: 1 to 1:15, in particular 5: 1 to 1: 5.
Der Anteil des Trägermediums an der konzentrierten Polymerdispersion kann in weiten Bereichen liegen, wobei dieser Anteil insbesondere von den eingesetzten Polyolefinen und Dispergierkomponenten abhängig ist. Im allgemeinen beträgt der Anteil des Trägermediums 79 bis 25 Gew.-%, vorzugsweise unter 70, speziell 60 bis 40 Gew.-%, bezogen auf die gesamte Polymerdispersion.The proportion of the carrier medium in the concentrated polymer dispersion can be in a wide range, this proportion being dependent in particular on the polyolefins and dispersion components used. In general, the proportion of the carrier medium is 79 to 25% by weight, preferably less than 70, especially 60 to 40% by weight, based on the total polymer dispersion.
Die Komponente D)Component D)
Die Komponente D) ist für die vorliegende Polymerdispersion obligatorisch, wobei diese Komponente ein oder mehrere Verbindungen mit einer Dielektrizitätskonstanten größer oder gleich 9, insbesondere größer oder gleich 20 und besonders bevorzugt größer oder gleich 30 umfasst.Component D) is mandatory for the present polymer dispersion, this component comprising one or more compounds with a dielectric constant greater than or equal to 9, in particular greater than or equal to 20 and particularly preferably greater than or equal to 30.
Die Dielektrizitätskonstante kann gemäß Handbook of Chemistry and Physics, David R. Lide, 79th Edition, CRS Press angegebenen Methoden bestimmt werden, wobei die Dielektrizitätskonstante bei 20°C gemessen wird. Zu den besonders geeigneten Verbindungen gehören unter anderem Wasser, Glykole, insbesondere Ethylenglykol, 1 ,2-Propylenglykol, 1 ,3-Propylenglykol, Polyethylenglykol; Alkohole, insbesondere Methanol, Ethanol, Butanol, Glycerin; ethoxylierte Alkohole, beispielsweise 2-fach ethoxyliertes Butanol, 10-fach ethoxyliertes Methanol; Amine, insbesondere Ethanolamin, 1 ,2 Ethandiamin und Propanolamin; halogenierte Kohlenwasserstoffe, insbesondere 2-Chlorethanol, 1 ,2 Dichlorethan, 1 ,1 Dichloraceton; Ketone, insbesondere Aceton.The dielectric constant can be determined according to the methods given in the Handbook of Chemistry and Physics, David R. Lide, 79th Edition, CRS Press, the dielectric constant being measured at 20 ° C. The particularly suitable compounds include water, glycols, in particular ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, polyethylene glycol; Alcohols, especially methanol, ethanol, butanol, glycerin; ethoxylated alcohols, for example 2-fold ethoxylated butanol, 10-fold ethoxylated methanol; Amines, especially ethanolamine, 1, 2 ethanediamine and propanolamine; halogenated hydrocarbons, especially 2-chloroethanol, 1, 2 dichloroethane, 1, 1 dichloroacetone; Ketones, especially acetone.
Der Anteil der Komponenten D) in der Polymerdispersion kann in weiten Bereichen liegen. Im allgemeinen umfasst die Polymerdispersion 0,01 - 15 Gew.-%, insbesondere 0,3 bis 5 Gew.-% Verbindungen gemäß Komponente D).The proportion of components D) in the polymer dispersion can be in a wide range. In general, the polymer dispersion comprises 0.01-15% by weight, in particular 0.3 to 5% by weight, of compounds according to component D).
Neben den zuvor genannten Komponenten kann die erf indungsgemäße Polymerdispersion weitere Additive und Zusatzstoffe enthalten.In addition to the components mentioned above, the polymer dispersion according to the invention can contain further additives.
Die Polymerdispersionen können durch bekannte Verfahren hergestellt werden, wobei diese Verfahren in den zuvor genannten Dokumenten des Standes der Technik dargelegt sind. So kann man beispielsweise die vorliegenden Polymerdispersionen herstellen, indem man die Komponente A) in einer Lösung der Komponenten B) unter Anwendung von Scherkräften bei einer Temperatur im Bereich von 80 bis 180°C dispergiert. Die Lösung der Komponenten B) umfasst im allgemeinen die Komponente C). Die Komponente D) kann der Dispersion vor, während oder nach dem Dispergieren der Komponenten A) beigefügt werden. Nachfolgend wird die Erfindung durch Beispiele und Vergleichsbeispiele eingehender erläutert, ohne dass die Erfindung auf diese Beispiele beschränkt werden soll.The polymer dispersions can be prepared by known processes, these processes being set out in the aforementioned documents of the prior art. For example, the present polymer dispersions can be prepared by dispersing component A) in a solution of component B) using shear forces at a temperature in the range from 80 to 180 ° C. Component B) generally comprises component C). Component D) can be added to the dispersion before, during or after the dispersion of component A). The invention is explained in more detail below by means of examples and comparative examples, without the invention being restricted to these examples.
Angewandte MethodenMethods used
Im folgenden ist mit KV100 die kinematische Viskosität einer Flüssigkeit gemessen bei 100°C in einem 150N-ÖI gemeint. Die Bestimmung der Viskosität wird nach DIN 51 562 (Ubbelohde-Viskosimeter) vorgenommen. Die Konzentration des OCP's in Öl beträgt hierbei jeweils 2,8 Gew.%. Die Angaben BV20, BV40 bzw. BV100 bezeichnen die kinematischen Viskositäten der Dispersionen (BV = "bulk viscosity") ebenfalls gemessen nach DIN 51 562 (Ubbelohde-Viskosimeter) bei 20, 40 bzw. 100°C.In the following, KV100 means the kinematic viscosity of a liquid measured at 100 ° C in a 150N oil. The viscosity is determined in accordance with DIN 51 562 (Ubbelohde viscometer). The concentration of the OCP in oil is 2.8% by weight. The details BV20, BV40 and BV100 denote the kinematic viscosities of the dispersions (BV = "bulk viscosity") also measured according to DIN 51 562 (Ubbelohde viscometer) at 20, 40 and 100 ° C.
Im Falle der Zugabe von Wasser zu den Dispersion wurde destilliertes Wasser eingesetzt. Beim verwendeten Ethylenglykol handelte es sich um Etylenglykol zur Analyse (Merck), beim verwendeten Polyethylenglykol um Polyethylenglykol 400 zur Synthese (Merck-Schuchardt).If water was added to the dispersion, distilled water was used. The ethylene glycol used was ethylene glycol for analysis (Merck), the polyethylene glycol used was polyethylene glycol 400 for synthesis (Merck-Schuchardt).
Zur Zugabe der letzen Komponente von hydrophilem Charakter wurden 0,5 bzw. 1 ,0 Gew.-% zur jeweiligen auf 90 bis 110°C aufgewärmten Dispersion in einer 11-Glasf lasche gegeben und die resultierende noch warme Mischung in der Glasflasche auf einer Rollbank (Drehzahl: 160 Upm) über einen Zeitraum von einer halben bis einer Stunde homogenisiert. BV20, BV40 bzw. BV100-Werte wurden jeweils vor und nach der Zugabe der hydrophilen Komponente bestimmt.To add the last component of hydrophilic character, 0.5 or 1.0% by weight was added to the respective dispersion heated to 90 to 110 ° C. in an 11-glass bottle and the resulting still warm mixture in the glass bottle on a roller bench (Speed: 160 rpm) homogenized over a period of half an hour to an hour. BV20, BV40 and BV100 values were determined before and after the addition of the hydrophilic component.
Als Initiatoren zur Herstellung der Dispersionen wurden gängige Vertreter wie beispielsweise die Perinitiatoren Di(tert-butylperoxy)-3,3,5- trimethylcyclohexan und/oder tert-Butylperoctoat benutzt. Zur Überprüfung der Stabilität einer Dispersion können 670 g des Produktes in einem 2 Liter Witt'schen Topf eingewogen werden. Ein Inter- Mig-Rührer mit drei Flügeln (Messrührer mit Drehmoment und - Drehzahlanzeige MR-D1 der Fa. Ika) und ein NiCrNi-Thermoelement (Temperaturregler 810 der Fa. Eurotherm) werden in den Witt'schen Topf eingebaut. Das Ölbad (Silikonöl PN 200) wird aufgeheizt, wobei die Drehzahl so eingestellt wird, dass der Leistungseintrag 1 ,3 Watt beträgt. Der Leistungseintrag kann über die Viskosität berechnet werden.Common initiators such as the perinitiators di (tert-butylperoxy) -3,3,5-trimethylcyclohexane and / or tert-butyl peroctoate were used as initiators for the preparation of the dispersions. To check the stability of a dispersion, 670 g of the product can be weighed into a 2 liter Witt pot. An InterMig stirrer with three blades (measuring stirrer with torque and speed display MR-D1 from Ika) and a NiCrNi thermocouple (temperature controller 810 from Eurotherm) are installed in the Witt pot. The oil bath (silicone oil PN 200) is heated, the speed being set so that the power input is 1.3 watts. The power input can be calculated via the viscosity.
Das Produkt wird bis auf 160°C aufgewärmt und diese Innentemperatur dann 2h lang gehalten. Danach wird die Innentemperatur im Reaktor innerhalb von 15 Minuten um 10°C erhöht und wiederum 2h lang gehalten, wobei dieser Vorgang mehrmals wiederholt wird bis die Innentemperatur 190°C beträgt. Sollte das Produkt vorher einer Phasenseparation unterliegen, was an einem sprunghaften Anstieg der Viskosität und damit an einem schnellen Anstieg des Drehmomentes zu erkennen ist, so ist der Versuch beendet. Zeit und Temperatur bis zu diesem Zeitpunkt werden detektiert.The product is warmed up to 160 ° C and this internal temperature is then maintained for 2 hours. The internal temperature in the reactor is then raised by 10 ° C. within 15 minutes and again held for 2 hours, this process being repeated several times until the internal temperature is 190 ° C. If the product is subject to phase separation beforehand, which can be recognized by a sudden increase in viscosity and thus a rapid increase in torque, the test is ended. Time and temperature up to this point in time are detected.
Beispiel 1example 1
In einem 2 Liter-Vierhalskolben ausgestattet mit Rührer, Thermometer und Rückflusskühler werden 63,8 g eines Styrol-Dien-Copolymerisats (z.B. SHELLVIS® 260) in 271 ,3 g eines Esters (z.B. Vestinol® OA) und 90,4 g eines ethoxylierten Fettalkoholes (z.B. Marlipal® 013/20) bei 100°C innerhalb von 3-4 Stunden gelöst. Nach dem Lösevorgang werden 47,3 g eines C12-C16-Alkyl-methacrylats zugegeben und es wird mittels Zugabe von Trockeneis inertisiert. Die Temperatur wird wieder auf 100°C eingestellt, wonach 1 ,14 g tert-Butylperoctoat zugegeben und gleichzeitig ein Zulauf bestehend aus einer Mischung von 527,2 g des C12-C16 Alkyl- methacrylats und 6,33 g tert-Butylperoctoat gestartet wird. Die Zulaufzeit beträgt 3,5 Stunden. Die Zulaufgeschgwindigkeit ist gleichbleibend. 2 Stunden nach Zulaufende werden nochmals 1 ,15 g g tert-Butylperoctoat zugegeben. In einem 1 Liter Witt'schen Topf mit Inter-Mig-Rührer (Verhältnis Rührer/Behälterdurchmesser = 0,7; einzustellende Rührerdrehzahl: 200 UpM) werden 134,2 g der hergestellten Lösung zusammen mit 196,8 g des Styrol-Dien-Copolymerisats (z.B. SHELLVIS® 260) und 169,0 g des ethoxylierten Fettalkoholes (z.B. Marlipal® 013/20) eingewogen. Innerhalb von 8-10 Stunden entsteht bei 100°C und 200 UpM Rührerdrehzahl eine Dispersion. Die aktuelle Viskosität dieser hochkonzentrierten Shellvis 260-Dispersion beträgt bei 40°C ca. 4084 mm2/s und bei 100°C ca.4933 mm2/s.63.8 g of a styrene / diene copolymer (for example SHELLVIS ® 260) in 271.3 g of an ester (for example Vestinol ® OA) and 90.4 g of an ethoxylated are in a 2 liter four-necked flask equipped with a stirrer, thermometer and reflux condenser Fatty alcohols (e.g. Marlipal ® 013/20) dissolved at 100 ° C within 3-4 hours. After the dissolving process, 47.3 g of a C12-C16-alkyl methacrylate are added and the mixture is rendered inert by adding dry ice. The temperature is set again to 100 ° C., after which 1.14 g of tert-butyl peroctoate are added and at the same time an inlet consisting of a mixture of 527.2 g of the C12-C16 alkyl methacrylate and 6.33 g of tert-butyl peroctoate is started. The run-in time is 3.5 hours. The feed rate is constant. 2 hours after the end of the feed, a further 1.15 g of tert-butyl peroctoate are added. 134.2 g of the solution prepared, together with 196.8 g of the styrene-diene copolymer, are placed in a 1 liter Witt's pot with an Inter-Mig stirrer (stirrer / container diameter ratio = 0.7; stirrer speed to be set: 200 rpm) (e.g. SHELLVIS ® 260) and 169.0 g of the ethoxylated fatty alcohol (e.g. Marlipal ® 013/20) weighed out. A dispersion is formed within 8-10 hours at 100 ° C and 200 rpm stirrer speed. The actual viscosity of this highly concentrated Shellvis is 260 dispersion at 40 ° C approximately 4084 mm 2 / s at 100 ° C ca.4933 mm 2 / s.
Zugabe von 0,5 bzw. 1 ,0 Gew.% der folgenden Substanzen nach eingangs beschriebenem Verfahren führt zu den nachfolgend angegebenen Viskositätswerten:Addition of 0.5 or 1.0% by weight of the following substances using the method described at the beginning leads to the viscosity values given below:
zugesetzte Verbindung Zusatzmenge BV40 BV100added compound additional quantity BV40 BV100
[mm2/s] [mm /s][mm 2 / s] [mm / s]
- N/A 4084 4933- N / A 4084 4933
Wasser dest. 0,5 Gew.-% 3038 1907Distilled water 0.5% by weight 3038 1907
Wasser dest. 1 ,0 GΘW.-% 2533 1041Distilled water 1.0% by weight 2533 1041
Ethylenglykol 1 ,0 Gew.-% 2616 1229Ethylene glycol 1.0% by weight 2616 1229
Polyethylenglykol 400 1 ,0 Gew.-% 2926 1670 Beispiel 2Polyethylene glycol 400 1.0% by weight 2926 1670 Example 2
In einem 2 Liter-Vierhalskolben ausgestattet mit Rührer, Thermometer und Rückflusskühler werden 70,3 g eines Ethylen-Propylen-Copolymerisats der Verdickungswirkung 11 ,0 mm2/s in Bezug auf KV100 (z.B. thermisch oder mechanisch abgebautes Dutral® CO 038) in einer Mischung bestehend aus 251 ,8 g eines 150N-Öles und 47,9 g eines 100N-Öles eingewogen und bei 100°C innerhalb 10-12 Stunden gelöst. Nach dem Lösevorgang werden 41 ,1 g einer Mischung bestehend aus Alkylmethacrylaten mit Alkylsubstituenten der Kettenlänge C10-C18 zugegeben und das Reaktionsgemisch durch Zugabe von Trockeneis inertisiert. Nach Erreichen der 130°C Polymerisationstemperatur werden 0,52 g 1 ,1-Di(tert-butylperoxy)-3,3,5-trimethylcyclohexan zugegeben und gleichzeitig ein Monomerzulauf bestehend aus 588,9 g der analogen Zusammensetzung wie oben und 7,66 g 1 ,1-Di(tert-butylperoxy)-3,3,5- trimethylcyclohexan gestartet und über eine Zulaufzeit von 3,5 Stunden gleichmäßig zugegeben. 2 Stunden nach Zulaufende wird mit 472,1g eines ethoxylierten Fettalkoholes (z.B. Marlipal® 013/20) auf 47,55% Polymergehalt verdünnt. Gleichzeitig wird die Temperatur auf 100°C reduziert, 1 ,26 g tert-Butylperoctoat werden zugegeben und es wird weitere 2 Stunden bei 100°C gerührt. In einem 1 Liter Witt'schen Topf ausgestattet mit Inter-Mig-Rührer (Verhältnis Rührer / Behälterdurchmesser = 0,7; eingestellte Rührerdrehzahl: 150 UpM) werden 286,2 g der hergestellten Lösung, 43,2 g eines Ethylen-Propylen- Copolymerisats (z.B. auf 11 ,5 mm2/s abgebautes Dutral® CO 038) und 170,6 g eines weiteren Ethylen-Propylen-Copolymerisats (z.B. auf eine KV100 von 11 ,5 mm2/s abgebautes Dutral® CO 058) eingewogen. Innerhalb von 8-10 Stunden entsteht bei 100°C und 150 UpM Rührerdrehzahl eine bräunliche Dispersion, welche noch innerhalb weniger Wochen bei Raumtemperatur zum Abtrennen der Ethylen- Propylen-Copolymere neigt. Zum Stabilisieren wird daher die Temperatur von 100°C auf 140°C erhöht und bei 150 UpM 6 Stunden weitergerührt. Anschließend wird durch Verdünnung mit 136,6 g eines ethoxylierten Fettalkoholes (z.B. Marlipal® 013/20) auf 55% Polymergehalt verdünnt und das Gemisch eine halbe Stunde bei 100°C weitergerührt. Anschließend wird der Polymergehalt der Dispersion durch weitere Zugabe von Marlipal® 013/20 auf 52 Gew.-% reduziert. Die BV40 einer so hergestellten Dispersion betrug 3834 mm2/s, die BV100 1623 mm2/s. Die Zugabe von 1 ,0 Gew.-% Wasser nach oben beschriebenem Verfahren führte zum Abfall der BV40 auf 3169 mm2/s und zur Erniedrigung der BV100 auf 801 mm2/s.In a 2 liter four-necked flask equipped with a stirrer, thermometer and reflux condenser, 70.3 g of an ethylene-propylene copolymer with a thickening effect of 11.0 mm 2 / s in relation to KV100 (e.g. thermally or mechanically degraded Dutral ® CO 038) are combined in one Weighing mixture consisting of 251, 8 g of a 150N oil and 47.9 g of a 100N oil and dissolved at 100 ° C within 10-12 hours. After the dissolving process, 41.1 g of a mixture consisting of alkyl methacrylates with alkyl substituents of chain length C10-C18 are added and the reaction mixture is rendered inert by adding dry ice. After reaching the 130 ° C. polymerization temperature, 0.52 g of 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane are added, and at the same time a monomer feed consisting of 588.9 g of the composition analogous to those above and 7.66 g 1, 1-Di (tert-butylperoxy) -3,3,5-trimethylcyclohexane started and evenly added over a feed time of 3.5 hours. 2 hours after the end of the feed, the mixture is diluted to 47.55% polymer content with 472.1 g of an ethoxylated fatty alcohol (eg Marlipal ® 013/20). At the same time, the temperature is reduced to 100 ° C., 1.26 g of tert-butyl peroctoate are added and the mixture is stirred at 100 ° C. for a further 2 hours. In a 1 liter Witt pot equipped with an Inter-Mig stirrer (stirrer / container diameter ratio = 0.7; set stirrer speed: 150 rpm) are 286.2 g of the solution prepared, 43.2 g of an ethylene-propylene copolymer (for example Dutral ® CO 038 degraded to 11.5 mm 2 / s) and 170.6 g of a further ethylene-propylene copolymer (for example Dutral ® CO 058 degraded to 11.5 mm 2 / s). A brownish dispersion is formed within 8-10 hours at 100 ° C and 150 rpm stirrer speed, which within a few weeks at room temperature to separate the ethylene Propylene copolymers tend to. For stabilization, the temperature is therefore increased from 100 ° C. to 140 ° C. and stirring is continued at 150 rpm for 6 hours. The mixture is then diluted to 55% polymer content by dilution with 136.6 g of an ethoxylated fatty alcohol (eg Marlipal ® 013/20) and the mixture is stirred at 100 ° C. for half an hour. The polymer content of the dispersion is then reduced to 52% by weight by further adding Marlipal ® 013/20. The BV40 of a dispersion produced in this way was 3834 mm 2 / s, the BV100 1623 mm 2 / s. The addition of 1.0% by weight of water by the process described above led to a drop in the BV40 to 3169 mm 2 / s and to a lowering of the BV100 to 801 mm 2 / s.
Beispiel 3Example 3
Die Herstellung der OCP-Dispersion erfolgt in Analogie zu Beipiel 2 mit dem Unterschied, dass statt Mineralöl Dioctyladipat (z.B. Vestinol OA) eingesetzt wird und dass der letzte Verdünnungsschritt von 55 auf 52 Gew.-% Polymergehalt nicht durchgeführt wird. Die KV100 der Lösung von 2,8 Gew.-% einer so erhaltenen Dispersion in einem 150N-ÖI wurde mit 10,85 mm /s gemessen. Die BV40 betrug 3844 mm2/s, die BV100 1499 mm2/s. Zugabe von 1 ,0 Gew.-% Wasser zur Dispersion erbrachte keine Änderung der KV100, ging allerdings mit einer Absenkung der BV auf 2725 mm2/s sowie einer Abnahme der BV100 auf 746 mm2/s einher.The OCP dispersion is prepared in analogy to Example 2, with the difference that dioctyl adipate (eg Vestinol OA) is used instead of mineral oil and that the last dilution step from 55 to 52% by weight polymer content is not carried out. The KV100 of the solution of 2.8% by weight of a dispersion thus obtained in a 150N oil was measured at 10.85 mm / s. The BV40 was 3844 mm 2 / s, the BV100 1499 mm 2 / s. The addition of 1.0% by weight of water to the dispersion did not change the KV100, but was accompanied by a reduction in the BV to 2725 mm 2 / s and a decrease in the BV100 to 746 mm 2 / s.
Beispiel 4Example 4
Eine in Analogie zu Beispiel 2 hergestellte Dispersion wies eine BV20 von 3450 mm2/s auf. Die Zugabe von 4,5 Gew.-% von 2-fach ethoxyliertem Butanol führte zu einer Absenkung der BV20 auf 2880 mm2/s. A dispersion produced in analogy to Example 2 had a BV20 of 3450 mm 2 / s. The addition of 4.5% by weight of 2-fold ethoxylated butanol led to a reduction in the BV20 to 2880 mm 2 / s.

Claims

Patentansprüche claims
1. Polymerdispersion mit geringer Viskosität umfassend1. A low viscosity polymer dispersion comprising
A) mindestens ein dispergiertes Polyolefin,A) at least one dispersed polyolefin,
B) mindestens eine Dispergierkomponente,B) at least one dispersing component,
C) mindestens ein Trägermedium undC) at least one carrier medium and
D) mindestens eine Verbindung mit einer Dielektrizitätskonstanten größer oder gleich 9.D) at least one connection with a dielectric constant greater than or equal to 9.
2. Polymerdispersion nach Anspruch 1 , dadurch gekennzeichnet, dass die Komponente B) ein Copolymer darstellt, welches ein oder mehrere Blöcke A und ein oder mehrere Blöcke X umfasst, wobei der Block A Olefincopolymerisat-Sequenzen, hydrierte Polyisopren- Sequenzen, hydrierte Copolymere aus Butadien/Isopren oder hydrierte Copolymere aus Butadien/Isopren und Styrol darstellt und der Block X Polyacrylat-, Polymethacrylat-, Styrol-, α-Methylstyrol oder N-Vinyl-heterocyclische Sequenzen und/oder Sequenzen aus Gemischen von Polyacrylat-, Polymethacrylat-, Styrol-, α- Methylstyrol oder N-Vinyl-Heterocyclen darstellt.2. Polymer dispersion according to claim 1, characterized in that component B) is a copolymer which comprises one or more blocks A and one or more blocks X, the block A olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene / Isoprene or hydrogenated copolymers of butadiene / isoprene and styrene and the block X is polyacrylate, polymethacrylate, styrene, α-methylstyrene or N-vinyl heterocyclic sequences and / or sequences from mixtures of polyacrylate, polymethacrylate, styrene represents α-methylstyrene or N-vinyl heterocycles.
3. Polymerdispersion nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Komponente B) durch Pfropfcopolymerisation einer Monomerzusammensetzung umfassend (Meth)acrylate und/oder Styrol-Verbindungen auf Polyolefinen gemäß Komponente A) erhältlich ist. 3. Polymer dispersion according to claim 1 or 2, characterized in that component B) is obtainable by graft copolymerization of a monomer composition comprising (meth) acrylates and / or styrene compounds on polyolefins according to component A).
4. Polymerdispersion nach Anspruch 3, dadurch gekennzeichnet, dass eine Monomerzusammensetzung eingesetzt wird, aufweisend ein oder mehrere (Meth)acrylate der Formel (I)4. Polymer dispersion according to claim 3, characterized in that a monomer composition is used, comprising one or more (meth) acrylates of the formula (I)
worin R Wasserstoff oder Methyl und R1 Wasserstoff, einen linearen oder verzweigten Alkylrest mit 1 bis 40 Kohlenstoffatomen bedeuten, in which R is hydrogen or methyl and R 1 is hydrogen, a linear or branched alkyl radical having 1 to 40 carbon atoms,
und/oder ein oder mehrere (Meth)acrylate der Formel (II)and / or one or more (meth) acrylates of the formula (II)
worin R Wasserstoff oder Methyl und R2 einen mit einer OH-Gruppe substituierten Alkylrest mit 2 bis 20 Kohlenstoffatomen oder einen alkoxylierten Rest der Formel (III) wherein R is hydrogen or methyl and R 2 is an alkyl group with 2 to 20 carbon atoms substituted by an OH group or an alkoxylated group of the formula (III)
worin R3 und R4 unabhängig für Wasserstoff oder Methyl, R5 Wasserstoff oder einen Alkylrest mit 1 bis 40 Kohlenstoffatomen und n eine ganze Zahl von 1 bis 90 steht, bedeuten, in which R 3 and R 4 are independently hydrogen or methyl, R 5 is hydrogen or an alkyl radical having 1 to 40 carbon atoms and n is an integer from 1 to 90,
und/oder ein oder mehrere (Meth)acrylate der Formel (IV)and / or one or more (meth) acrylates of the formula (IV)
worin R Wasserstoff oder Methyl, X Sauerstoff oder eine Aminogruppe der Formel -NH- oder -NR7-, worin R7 für einen Alkylrest mit 1 bis 40 Kohlenstoffatomen steht, und R6 einen mit mindestens einer -NR8R9-Gruppe substituierten linearen oder verzweigten Alkylrest mit 2 bis 20, vorzugsweise 2 bis 6 Kohlenstoffatomen bedeuten, wobei R8 und R9 unabhängig von einander für Wasserstoff, einen Alkylrest mit 1 bis 20, vorzugsweise 1 bis 6 stehen oder worin R8 und R9 unter Einbeziehung des Stickstoffatoms und gegebenenfalls eines weiteren Stickstoff oder Sauerstoffatoms einen 5- oder 6-gliederigen Ring bilden, der gegebenenfalls mit CrC6-Alkyl substituiert sein kann. wherein R is hydrogen or methyl, X is oxygen or an amino group of the formula -NH- or -NR 7 -, wherein R 7 is an alkyl radical having 1 to 40 carbon atoms, and R 6 is a substituted by at least one -NR 8 R 9 group linear or branched alkyl radical having 2 to 20, preferably 2 to 6 carbon atoms, where R 8 and R 9 independently of one another are hydrogen, an alkyl radical having 1 to 20, preferably 1 to 6 or wherein R 8 and R 9 including the Nitrogen atom and optionally a further nitrogen or oxygen atom form a 5- or 6-membered ring which can optionally be substituted with CrC 6 alkyl.
5. Polymerdispersion nach Anspruch 2, 3 oder 4, dadurch gekennzeichnet, dass bei der Pfropfreaktion eine Monomerzusammensetzung eingesetzt wird, die dispergierende Monomere umfasst.5. Polymer dispersion according to claim 2, 3 or 4, characterized in that a monomer composition is used in the grafting reaction, which comprises dispersing monomers.
6. Polymerdispersion nach einem der Ansprüche 2 bis 5, dadurch gekennzeichnet, dass das Gewichtsverhältnis der Blöcke A zu den Blöcken X im Bereich von 20:1 bis 1:20 liegt.6. Polymer dispersion according to one of claims 2 to 5, characterized in that the weight ratio of blocks A to blocks X is in the range from 20: 1 to 1:20.
7. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente A) ein oder mehrere Olefincopolymere, hydriertes Polyisopren, hydrierte Copolymere aus Butadien/Isopren oder hydrierte Copolymere aus Butadien/Isopren und Styrol umfasst. 7. Polymer dispersion according to one or more of the preceding claims, characterized in that component A) comprises one or more olefin copolymers, hydrogenated polyisoprene, hydrogenated copolymers from butadiene / isoprene or hydrogenated copolymers from butadiene / isoprene and styrene.
8. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente C) ein nicht ionisches Tensid ist.8. Polymer dispersion according to one or more of the preceding claims, characterized in that component C) is a nonionic surfactant.
9. Polymerdispersion nach Anspruch 8, dadurch gekennzeichnet, dass das nicht ionische Tensid einen ethoxylierten Alkohol umfasst.9. Polymer dispersion according to claim 8, characterized in that the non-ionic surfactant comprises an ethoxylated alcohol.
10. Polymerdispersion nach Anspruch 9, dadurch gekennzeichnet, dass der ethoxylierte Alkohol 2 bis 8 Ethoxygruppen umfasst, wobei der hydrophobe Rest des Alkohols 4 bis 22 Kohlenstoffatome umfasst.10. Polymer dispersion according to claim 9, characterized in that the ethoxylated alcohol comprises 2 to 8 ethoxy groups, the hydrophobic residue of the alcohol comprising 4 to 22 carbon atoms.
11. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente C) ein oder mehrere Ester umfasst.11. Polymer dispersion according to one or more of the preceding claims, characterized in that component C) comprises one or more esters.
12. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Polymer-Dispersion mindestens 20 Gew.-% der Komponente A) umfasst.12. Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises at least 20% by weight of component A).
13. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Dielektrizitätskonstante der Verbindung gemäß Komponente D) größer oder gleich 20 ist.13. Polymer dispersion according to one or more of the preceding claims, characterized in that the dielectric constant of the compound according to component D) is greater than or equal to 20.
14. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Komponente D) Wasser, Ethylenglykol, Polyethylenglykol und/oder Alkohol umfasst. 14. Polymer dispersion according to one or more of the preceding claims, characterized in that component D) comprises water, ethylene glycol, polyethylene glycol and / or alcohol.
15. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Polymer-Dispersion bis zu 30 Gew.-% Komponente B) umfasst.15. Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises up to 30% by weight of component B).
16. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Polymerdispersion 0,01 - 15 Gew.-% Verbindungen gemäß Komponente D) umfasst.16. Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises 0.01-15% by weight of compounds according to component D).
17. Polymerdispersion nach einem oder mehreren der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Polymerdispersion Mineralöl umfasst.17. Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises mineral oil.
18. Verfahren zur Herstellung von Polymerdispersionen gemäß den Ansprüchen 1 bis 17, dadurch gekennzeichnet, dass man in einer Lösung der Komponenten B) unter Anwendung von Scherkräften bei einer Temperatur im Bereich von 80 bis 180°C die Komponente A) dispergiert.18. A process for the preparation of polymer dispersions according to claims 1 to 17, characterized in that component A) is dispersed in a solution of components B) using shear forces at a temperature in the range from 80 to 180 ° C.
19. Verwendung einer Polymerdispersion gemäß einem der Ansprüche 1 bis 17 als Zusatzstoff für Schmierölformulierungen. 19. Use of a polymer dispersion according to one of claims 1 to 17 as an additive for lubricating oil formulations.
EP03809259A 2002-10-22 2003-08-27 Polymer dispersions with low viscosity and method for production thereof Withdrawn EP1560904A1 (en)

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