WO2004037955A1 - Polymerdispersionen mit hoher stabilität und verfahren zur herstellung - Google Patents
Polymerdispersionen mit hoher stabilität und verfahren zur herstellung Download PDFInfo
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- WO2004037955A1 WO2004037955A1 PCT/EP2003/009464 EP0309464W WO2004037955A1 WO 2004037955 A1 WO2004037955 A1 WO 2004037955A1 EP 0309464 W EP0309464 W EP 0309464W WO 2004037955 A1 WO2004037955 A1 WO 2004037955A1
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- 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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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/16—Ethers
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/74—Esters of polyhydroxy compounds
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- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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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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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
Definitions
- the present invention relates to polymer dispersions with high stability, processes for the preparation and the 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-vinylpyrrolidone for grafting is also mentioned.
- methacrylates can be polymerized onto a polyolefin by grafting (DT-AS 1 235 491).
- EP-A-0 008327 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. -Vinylpyrrolidon) 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 07291 is to be understood as a process patent, which describes in particular the production of the dispersions.
- DE 32 07 292 essentially corresponds 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 07 291.
- the polymer dispersions described in the prior art already show a good property profile. However, their stability is particularly in need of improvement. It should be borne in mind here that polymer dispersions have to be stored for long periods of time without generally using cooling devices. The storage time includes, in particular, transportation, etc., with temperatures above 40 ° C or even 50 ° C.
- polymer dispersions with a low viscosity and a high polyolefin content.
- OCP or HSD content the higher the viscosity of the dispersion.
- 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.
- 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. 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.
- D) comprising at least one compound comprising (oligo) oxyalkyl groups, polymer dispersions which have a particularly high stability can be provided 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-improving effect 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 dispersions of the present invention can be produced particularly easily and simply. Conventional, large-scale plants can be used here.
- 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. It is primarily made of ethylene, Propylene, isoprene, butylene and / or other olefins with 5 to 20 carbon atoms, polymers as have already been recommended as VI improvers. Systems which are grafted with small amounts of oxygen- or nitrogen-containing monomers (for example 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 between 50,000 and 150,000.
- Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 1644941, DE-A 1769 834, DE-A 19 39 037, DE-A 19 63039 and DE-A 2059981.
- 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, but their tendency to crosslink during the aging process must be taken into account.
- 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.
- 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 shows one high compatibility with the polyolefins of component A) described above, with at least one further of the blocks contained in the dispersing components having only low compatibility with the previously described polyolefins.
- dispersing component can often be regarded as block copolymers.
- At least one of these blocks preferably shows one high compatibility with the polyolefins of component A) described above, with at least one further of the blocks contained in the dispersing components having only low compatibility with the previously described polyolefins.
- Such dispersion components are known per se, preferred compounds being described in the aforementioned prior art.
- preferred dispersion components can be understood as block copolymers which comprise one or more blocks A and one or more blocks X, the block A comprising olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene / isoprene or hydrogenated Copolymers of butadiene / isoprene and styrene and the block X polyacrylate, polymethacrylate, styrene, ⁇ -methylstyrene or N-vinyl heterocyclic sequences or sequences from mixtures of polyacrylate, polymethacrylate, styrene, ⁇ -methylstyrene or Represents N-vinyl heterocycles.
- Preferred dispersion components can be prepared by graft polymerization, 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.
- the term (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
- 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)
- R 3 and R 4 are independently hydrogen or methyl
- R 5 is hydrogen or an alkyl radical having 1 to 40 carbon atoms
- n is an integer from 1 to 90.
- 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; Dehydad ⁇ 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 -
- 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 are linear or branched alkyl radicals 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, are preferably 1 to 6 or in which 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 C 1 -C 6 -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, 2- (4-morpholinyl) ethyl (meth) acrylate and 1 - (2-methacryloyloxyethyl) -2-pyrrolidone.
- 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 heterocyclic vinyl compounds such as 2-vinyl pyridine, 3-vinyl pyridine, 2-methyl-5-vinyl pyridine, 3-ethyl-4-vinyl pyridine, 2,3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, vinyl piperidine, 9-vinyl carbazole , 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylhenane, vinylfuran , Vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles.
- heterocyclic vinyl compounds such as 2-vinyl
- 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 also possible to vary the monomer composition during the polymerization.
- 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.
- 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 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 continue feeding some time after the end of the feed some initiator, 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.
- a suitable solvent such as, for. B. a phthalate such as dibutyl phthalate.
- 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 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.
- 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.
- paraffin-based, naphthenic and aromatic components in crude oils or mineral oils, the terms paraffin-based component standing for longer-chain or strongly branched isoalkanes and naphthenic component for cycloalkanes.
- mineral oils have different proportions of n-alkanes, iso-alkanes 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 generally> 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.
- Aromatics with 14 to 32 carbon atoms :
- the polymer dispersion preferably contains 2 to 40% by weight, in particular 5 to 30% by weight and particularly preferably 10 to 20% by weight of mineral oil.
- Component D) is mandatory for the present polymer dispersion, this component containing one or more compounds comprising at least one (oligo) oxyalkyl group.
- the compounds according to component D) preferably comprise 1 to 40, in particular 1 to 20 and particularly preferably 2 to 8, oxyalkyl groups.
- the oxyalkyl groups generally have the formula (V)
- R 6 and R 7 independently represent hydrogen or an alkyl radical with 1 to 10 carbon.
- the oxyalkyl groups include in particular the ethoxy, the propoxy and the butoxy groups, with the ethoxy groups being preferred.
- esters and ethers which have the groups mentioned above.
- esters phosphoric acid esters, esters of monocarboxylic acids and esters of dicarboxylic acids. (See Ullmann's Encyclopedia of Technical Chemistry, 3rd ed., Vol. 15, pp. 287-292, Urban & Schwarzenber (1964)).
- Propionic acid, (iso) butyric acid and pelargonic acid may be mentioned specifically as monocarboxylic acids.
- Suitable esters of dicarboxylic acids are the esters of phthalic acid and then the esters of aliphatic dicarboxylic acids, in particular the esters of straight-chain dicarboxylic acids. Of particular note are the esters of sebacic, adipic and azelaic 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 are emphasized.
- Propionic acid, (iso) butyric acid and pelargonic acid are specific monocarboxylic acids mentioned - may be mentioned, for example, the dipropylene glycol dipelargonate, the diethylene glycol dipropionate - and diisobutyrate and the corresponding esters of triethylene glycol and the tetraethylene glycol d-i-2-ethyl hexanoic acid reester.
- esters can be used individually or as a mixture.
- the compounds according to component D) further comprise ether compounds which have (oligo) alkoxy groups.
- ether compounds which have (oligo) alkoxy 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.
- the preferred hydrophobic residues of these ethers include the methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl, pentenyl, cyclohexyl, heptyl, 2-methylheptenyl, 3-methylheptyl, Octyl, nonyl, 3-ethylnonyl, decyl, undecyl, 4-propenylundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cetyleicos -, Docosyl and / or Eicosyltetratriacontyl group.
- ethers are the Lutensol ® A brands, especially Lutensol ® A 3 N, Lutensol ® A 4 N, Lutensol ® A 7 N and Lutensol ® A 8 N, ethers 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 ® AO brands, in particular Lutensol ® AO 3, Lutensol ®
- ethers can be used individually or as a mixture.
- the polymer dispersion preferably contains 2 to 55% by weight, in particular 5 to 45% by weight and particularly preferably 10 to 40% by weight, of compounds which comprise (oligo) oxyalkyl groups.
- the weight ratio of mineral oil to compounds with (oligo) oxyalkyl groups can be in a wide range. This ratio is particularly preferably in the range from 2: 1 to 1:25, in particular 1: 1 to 1:15.
- the proportion of components C) and D) in the concentrated polymer dispersion can be in a wide range, this proportion being particularly dependent on the polyolefins and dispersing components used.
- the proportion of components C) and D) together is 79 to 25% by weight, preferably less than 70, especially 60 to 40% by weight, based on the total polymer dispersion.
- the polymer dispersion according to the invention can contain further additives.
- carrier media can be used in the polymer dispersion.
- 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 with 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 C4 to Cs alcohols, dibutyl phthalate and dioctyl phthalate being particularly mentioned, and then the esters of aliphatic dicarboxylic acids, in particular 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, C9 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.
- Preferred carrier media are further 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.
- the polymer dispersion of the present invention can comprise 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. Surprisingly, it was found that the viscosity of the polymer dispersion can be reduced by adding these compounds. This in particular allows the viscosity to be set to a predetermined value.
- 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.
- 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
- the proportion of the compounds described above in the polymer dispersion can be in a wide range.
- the polymer dispersion generally comprises up to 15% by weight, in particular 0.3 to 5% by weight, of compounds with a dielectric constant greater than or equal to 9.
- 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.
- Components B) generally comprise components C) and D). These components can be added to the dispersion before, during or after the dispersion of components A).
- the invention is explained in more detail below by means of examples and comparative examples, without the invention being restricted to these examples.
- 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.
- 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.
- the test is ended. Time and temperature up to this point in time are detected.
- 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 it 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.
- an ethoxylated fatty alcohol for example Marlipal ® O13 / 20
- 136.6 g of diluted to 55% polymer content is diluted with 136.6 g of diluted to 55% polymer content and the mixture was further stirred for half an hour at 100 ° C.
- the KV100 of the product thus produced is 3488 mm 2 / s.
- the KV100 of a 2.8% solution of the product in a 150N oil is 11.43 mm 2 / s.
- the dispersion obtained was subjected to the stability test described above, a phase separation occurring after approx. 420 min at a temperature of 180 ° C. and the viscosity suddenly increasing.
- tert-butyl peroctoate After the temperature of the solution was raised to 110 ° C., 0.57 g of tert-butyl peroctoate are added and at the same time an inlet consisting of 422.1 g of alkyl methacrylates of the same composition as above and 8.44 g of tert-butyl peroctoate was started. The total inflow time is 3.5 hours and runs at a constant dosage rate. 2 hours after the end of the feed, 0.96 g of tert-butyl peroctoate are added. After 3-4 hours, a solution is obtained which is subsequently used as a dispersing component. The mixture is then diluted to a polymer content of 35.1% with 589.9 g of dibutyl phthalate.
- the dispersion obtained was subjected to the stability test described above, a phase separation occurring after approx. 250 min at an reached temperature of 170 ° C. and the viscosity suddenly increasing.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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JP2004545759A JP2006503938A (ja) | 2002-10-22 | 2003-08-27 | 高い安定性を有するポリマー分散液及び製造法 |
BRPI0315554-4A BRPI0315554B1 (pt) | 2002-10-22 | 2003-08-27 | Dispersão polimérica, processo para sua preparação e seu uso como aditivo para formulações de óleo lubrificante |
AU2003258669A AU2003258669A1 (en) | 2002-10-22 | 2003-08-27 | Highly stable polymer dispersions and method for the production thereof |
ES03809260.7T ES2562489T3 (es) | 2002-10-22 | 2003-08-27 | Dispersiones de polímero con estabilidad elevada y procedimiento para su obtención |
US10/526,435 US7452932B2 (en) | 2002-10-22 | 2003-08-27 | Highly stable polymer dispersions and method for the production thereof |
BR0315554-4A BR0315554A (pt) | 2002-10-22 | 2003-08-27 | Dispersões poliméricas com alta estabilidade e processos para sua preparação |
EP03809260.7A EP1558713B1 (de) | 2002-10-22 | 2003-08-27 | Polymerdispersionen mit hoher stabilität und verfahren zur herstellung |
CA2498863A CA2498863C (en) | 2002-10-22 | 2003-08-27 | Stable polymer dispersions comprising oxyalkyl compounds |
MXPA05004105A MXPA05004105A (es) | 2002-10-22 | 2003-08-27 | Dispersiones de polimero que tienen una alta estabilidad y los procesos para su elaboracion. |
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DE10249295A DE10249295A1 (de) | 2002-10-22 | 2002-10-22 | Polymerdispersionen mit hoher Stabilität und Verfahren zur Herstellung |
DE10249295.6 | 2002-10-22 |
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US (1) | US7452932B2 (de) |
EP (1) | EP1558713B1 (de) |
JP (3) | JP2006503938A (de) |
KR (1) | KR101070180B1 (de) |
CN (1) | CN100537731C (de) |
AU (1) | AU2003258669A1 (de) |
BR (2) | BR0315554A (de) |
CA (1) | CA2498863C (de) |
DE (1) | DE10249295A1 (de) |
ES (1) | ES2562489T3 (de) |
MX (1) | MXPA05004105A (de) |
WO (1) | WO2004037955A1 (de) |
Cited By (1)
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DE102007025604A1 (de) | 2007-05-31 | 2008-12-04 | Evonik Rohmax Additives Gmbh | Verbesserte Polymerdispersionen |
Families Citing this family (20)
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AU2003210270A1 (en) * | 2002-03-01 | 2003-09-16 | Rohmax Additives Gmbh | Copolymers as dewaxing additives |
DE10249292A1 (de) * | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | Polymerdispersionen mit geringer Viskosität und Verfahren zur Herstellung |
DE10249295A1 (de) | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | Polymerdispersionen mit hoher Stabilität und Verfahren zur Herstellung |
DE10249294A1 (de) * | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | Stabile Polymerdispersionen und Verfahren zur Herstellung |
DE10314776A1 (de) * | 2003-03-31 | 2004-10-14 | Rohmax Additives Gmbh | Schmierölzusammensetzung mit guten Reibeigenschaften |
DE102004018094A1 (de) * | 2004-04-08 | 2005-11-03 | Rohmax Additives Gmbh | Polymere mit H-Brücken bildenden Funktionalitäten zur Verbesserung des Verschleißschutzes |
DE102004018093A1 (de) * | 2004-04-08 | 2005-10-27 | Rohmax Additives Gmbh | Polymere mit H-Brücken bildenden Funktionalitäten |
DE102004021778A1 (de) * | 2004-04-30 | 2005-12-08 | Rohmax Additives Gmbh | Verwendung von Polyalkyl(meth)acrylaten in Schmierölzusammensetzungen |
DE102004021717A1 (de) * | 2004-04-30 | 2005-11-24 | Rohmax Additives Gmbh | Verfahren zur Herstellung von Schmierfett |
US7429555B2 (en) * | 2004-04-30 | 2008-09-30 | Rohmax Additives Gmbh | Lubricating grease with high water resistance |
DE102004034618A1 (de) * | 2004-07-16 | 2006-02-16 | Rohmax Additives Gmbh | Verwendung von Pfropfcopolymeren |
DE102004037929A1 (de) * | 2004-08-04 | 2006-03-16 | Rohmax Additives Gmbh | Verfahren zur radikalischen Polymerisation ethylenisch-ungesättigter Verbindungen |
DE102005015931A1 (de) * | 2005-04-06 | 2006-10-12 | Rohmax Additives Gmbh | Polyalkyl(meth) acrylat-Copolymere mit hervorragenden Eigenschaften |
DE102006001771A1 (de) * | 2006-01-12 | 2007-07-19 | Röhm Gmbh | Verfahren zur Aufreinigung von (Meth)acrylaten |
DE102006039420A1 (de) | 2006-08-23 | 2008-02-28 | Evonik Rohmax Additves Gmbh | Verfahren zur Herstellung von Methacrylatestern |
DE102006061103B4 (de) * | 2006-12-22 | 2008-11-06 | Clariant International Ltd. | Dispersionen polymerer Öladditive |
JP5676076B2 (ja) * | 2008-12-16 | 2015-02-25 | Jx日鉱日石エネルギー株式会社 | 潤滑油添加剤組成物及びその製造方法、潤滑油組成物及びその製造方法 |
DE102010041242A1 (de) | 2010-09-23 | 2012-03-29 | Evonik Rohmax Additives Gmbh | Verfahren zur Herstellung von Polymerdispersionen |
CN110846108B (zh) * | 2019-11-14 | 2021-11-30 | 安徽金德润滑科技有限公司 | 一种公路车辆齿轮油及其制备方法 |
JPWO2023171614A1 (de) * | 2022-03-07 | 2023-09-14 |
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2003
- 2003-08-27 WO PCT/EP2003/009464 patent/WO2004037955A1/de active Application Filing
- 2003-08-27 AU AU2003258669A patent/AU2003258669A1/en not_active Abandoned
- 2003-08-27 US US10/526,435 patent/US7452932B2/en active Active
- 2003-08-27 MX MXPA05004105A patent/MXPA05004105A/es unknown
- 2003-08-27 EP EP03809260.7A patent/EP1558713B1/de not_active Expired - Lifetime
- 2003-08-27 KR KR1020057006783A patent/KR101070180B1/ko active IP Right Grant
- 2003-08-27 ES ES03809260.7T patent/ES2562489T3/es not_active Expired - Lifetime
- 2003-08-27 CN CNB038241919A patent/CN100537731C/zh not_active Expired - Fee Related
- 2003-08-27 CA CA2498863A patent/CA2498863C/en not_active Expired - Fee Related
- 2003-08-27 BR BR0315554-4A patent/BR0315554A/pt not_active IP Right Cessation
- 2003-08-27 BR BRPI0315554-4A patent/BRPI0315554B1/pt unknown
- 2003-08-27 JP JP2004545759A patent/JP2006503938A/ja active Pending
-
2009
- 2009-08-14 JP JP2009188097A patent/JP5114461B2/ja not_active Expired - Fee Related
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Also Published As
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JP2006503938A (ja) | 2006-02-02 |
JP5114461B2 (ja) | 2013-01-09 |
MXPA05004105A (es) | 2005-06-22 |
JP2012052138A (ja) | 2012-03-15 |
AU2003258669A1 (en) | 2004-05-13 |
CA2498863C (en) | 2012-10-09 |
CA2498863A1 (en) | 2004-05-06 |
US7452932B2 (en) | 2008-11-18 |
US20050261143A1 (en) | 2005-11-24 |
BRPI0315554B1 (pt) | 2019-10-08 |
WO2004037955A8 (de) | 2005-05-12 |
EP1558713B1 (de) | 2015-12-09 |
KR101070180B1 (ko) | 2011-10-05 |
BR0315554A (pt) | 2005-08-23 |
JP2010007078A (ja) | 2010-01-14 |
EP1558713A1 (de) | 2005-08-03 |
CN1688679A (zh) | 2005-10-26 |
KR20050075363A (ko) | 2005-07-20 |
DE10249295A1 (de) | 2004-05-13 |
ES2562489T3 (es) | 2016-03-04 |
AU2003258669A8 (en) | 2004-05-13 |
CN100537731C (zh) | 2009-09-09 |
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