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EP2106433B1 - Dispersions d'additifs polymères d'huiles - Google Patents

Dispersions d'additifs polymères d'huiles Download PDF

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Publication number
EP2106433B1
EP2106433B1 EP07764904A EP07764904A EP2106433B1 EP 2106433 B1 EP2106433 B1 EP 2106433B1 EP 07764904 A EP07764904 A EP 07764904A EP 07764904 A EP07764904 A EP 07764904A EP 2106433 B1 EP2106433 B1 EP 2106433B1
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EP
European Patent Office
Prior art keywords
dispersion
water
weight
alkyl
carbon atoms
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.)
Not-in-force
Application number
EP07764904A
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German (de)
English (en)
Other versions
EP2106433B8 (fr
EP2106433A1 (fr
Inventor
Michael Feustel
Matthias Krull
Christoph Kayser
Mario LÖW
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.)
Clariant Finance BVI Ltd
Original Assignee
Clariant Finance BVI Ltd
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Publication date
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Publication of EP2106433A1 publication Critical patent/EP2106433A1/fr
Application granted granted Critical
Publication of EP2106433B1 publication Critical patent/EP2106433B1/fr
Publication of EP2106433B8 publication Critical patent/EP2106433B8/fr
Not-in-force legal-status Critical Current
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    • 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
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
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    • C10L10/16—Pour-point depressants
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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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/52—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring polycarboxylic
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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    • 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
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
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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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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
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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
    • C10N2030/08—Resistance to extreme temperature
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants

Definitions

  • Crude oils and products made from them are complex mixtures of various substances, some of which can cause problems during production, transport, storage and / or further processing.
  • crude oil as well as derived products such as middle distillates, heavy fuel oil, marine diesel, bunker oil or residual oils contain hydrocarbon waxes which precipitate at low temperatures and form a three-dimensional network of scales and / or fine needles.
  • the flowability of the oils is impaired at low temperatures, for example when transported in pipelines, and in storage tanks, considerable quantities of oil remain trapped between the paraffins, which crystallize in particular on the tank walls.
  • paraffin-containing mineral oils for transport and storage. These are predominantly synthetic polymeric compounds. So-called paraffin inhibitors improve the cold flowability of the oils z. B. by modifying the crystal structure of precipitating upon cooling paraffins. They prevent the formation of a three-dimensional network of paraffin crystals and thus lead to a lowering of the pour point of the paraffin-containing mineral oils.
  • the customary polymeric paraffin inhibitors are usually prepared by solution polymerization in organic, predominantly aromatic solvents. Due to the long-chain paraffin-like structural elements and high molecular weights of these polymers, which are required for good activity, their concentrated solutions have intrinsic sticky points which are often above the ambient temperatures prevailing during their processing. Thus, for use, these additives must be highly diluted or handled at elevated temperatures, both resulting in undesirable overhead.
  • pour point depressants prepared by emulsion copolymerization of alkyl (meth) acrylates with water-soluble and / or polar comonomers. These are prepared, for example, in dipropylene glycol monomethyl ether or in water / Dowanol with alkylbenzylammonium chloride and a fatty alcohol alkoxylate as emulsifiers.
  • EP-A-0 359 061 discloses emulsion polymers of long chain alkyl (meth) acrylates with acidic comonomers. However, the effectiveness of these polymers, presumably because of the molecular weight distribution as a result of the polymerization process, and of the highly polar comonomer units incorporated in order to improve their emulsifying properties, is generally unsatisfactory.
  • paraffin inhibitors which are easier to handle consists in the emulsification of polymers dissolved in organic solvents in a non-solvent for the polymeric active ingredient.
  • EP-A-0 448 166 Dispersions of polymers of ethylenically unsaturated compounds containing aliphatic hydrocarbon radicals having at least 10 carbon atoms, in glycols and optionally water. As dispersants, ether sulfates and lignosulfonates are mentioned. The emulsions are stable at 50 ° C for at least one day.
  • WO-05/023907 discloses emulsions of at least two different paraffin inhibitors selected from ethylene-vinyl acetate copolymers, poly (alkyl acrylates) and alkyl acrylate-grafted ethylene-vinyl acetate copolymers.
  • the emulsions contain water, an organic solvent, Unspecified anionic, cationic and / or nonionic surfactants, and a water-soluble solvent.
  • WO-98/33846 discloses dispersions of paraffin inhibitors based on ester polymers in aliphatic or aromatic hydrocarbons.
  • the dispersions contain a second, preferably oxygen-containing, solvent, such as, for example, glycol, which is a non-solvent for the polymer and optionally water.
  • the dispersants used are anionic surfactants such as carboxylic and sulfonic acid salts and in particular fatty acid salts, nonionic dispersants such as nonylphenol alkoxylates or cationic dispersants such as CTAB.
  • the emulsions may contain from 0.2 to 10% of an N-containing surfactant monomeric additive such as tall oil fatty acid derivatives and imidazolines.
  • U.S. 5,851,429 discloses dispersions in which a room temperature solid pour point depressant is dispersed in a non-solvent.
  • Suitable "non" solvents include alcohols, esters, ethers, lactones, ethoxyethyl acetate, ketones, glycols and alkyl glycols, and mixtures thereof with water.
  • anionic surfactants such as neutralized fatty acids or sulfonic acids as well as cationic, nonionic, zwitterionic detergents are used.
  • WO-98/09056 describes a low-viscosity cold flow improver based on an aqueous dispersion which contains an oil-soluble polymer, an organic solvent and as a dispersant a fatty amine and a nonionic surfactant.
  • additives which are suitable as paraffin inhibitors and especially as pour point depressants for paraffin-containing mineral oils and are pumpable as concentrates at low temperatures of below 0 ° C. and in particular below -10 ° C.
  • These additives should retain their performance and physical properties such as in particular their phase stability over a longer period of weeks to months even at elevated temperatures.
  • they should show at least the same efficacy as their active ingredients used from mineral oil-based formulations under optimal mixing conditions.
  • the mixture of water and component IV) and optionally V) at temperatures between 10 ° C and 100 ° C with a mixture of components I) and II) is added.
  • Cold flow improvers for mineral oils are understood as meaning all those polymers which improve the cold properties and in particular the cold flowability of mineral oils.
  • the cold properties are measured, for example, as Pour Point, Cloud Point, WAT (Wax Appearance Temperature), Paraffin Deposition Rate and / or Cold Filter Plugging Point (CFPP).
  • Suitable copolymers of ethylene and ethylenically unsaturated esters, ethers or alkenes i) are, in particular, those which in addition to ethylene contain from 4 to 18 mol%, in particular from 7 to 15 mol% of at least one vinyl ester, acrylic ester, methacrylic acid ester, alkyl vinyl ether and / or alkene ,
  • the alkyl radicals can be linear or branched. In a preferred embodiment, these are linear alkyl radicals having 1 to 18 C atoms. In a further preferred embodiment, R 1 is a branched alkyl radical having 3 to 30 C atoms and preferably having 5 to 16 C atoms.
  • Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group.
  • vinyl esters of tertiary carboxylic acids also referred to as versatic acid vinyl esters, which have neoalkyl radicals having 5 to 11 carbon atoms, in particular 8, 9 or 10 carbon atoms.
  • Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.
  • the vinyl ester is vinyl acetate.
  • said alkyl groups may be substituted with one or more hydroxyl groups.
  • these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 1 in which R 1 is C 4 to C 30 -alkyl, preferably C 4 to C 16 -alkyl, especially C 6 - to C 12 -alkyl , As further vinyl esters, the vinyl esters of this chain length range described above are preferred.
  • the alkyl radicals can be linear or be branched. In a preferred embodiment, they are linear. In a further preferred embodiment, they have a branch in the 2-position to the ester grouping.
  • Suitable acrylic esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, Tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers, wherein the formulation (meth) acrylate comprises the corresponding esters of acrylic acid and methacrylic acid.
  • the alkyl radicals can be linear or branched. Examples which may be mentioned are methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether.
  • the alkenes are preferably monounsaturated hydrocarbons having 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms.
  • Suitable alkenes include propene, butene, isobutene, pentene, hexene, 4-methylpentene, heptene, octene, decene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene.
  • the alkyl radicals R 1 , R 3 and R 4 may contain minor amounts of functional groups such as, for example, amino, amido, nitro, cyano, hydroxyl, keto, carbonyl, carboxy, ester, sulfo groups and / or halogen atoms wear, as long as they do not significantly affect the hydrocarbon character of said radicals. In a preferred embodiment, however, the alkyl radicals R 1 , R 3 and R 4 do not carry any basic-reacting and in particular no nitrogen-containing functional groups.
  • Particularly preferred terpolymers contain, apart from ethylene, preferably 3.5 to 17 mol%, in particular 5 to 15 mol% of vinyl acetate and 0.1 to 10 mol%, in particular 0.2 to 5 mol% of at least one long-chain vinyl ester, (meth) acrylic esters and / or alkene, wherein the total comonomer content is between 4 and 18 mol%, preferably between 7 and 15 mol%.
  • Particularly preferred termonomers are vinyl 2-ethylhexanoate, vinyl neononanoate and vinyl neodecanoate.
  • copolymers contain, in addition to ethylene and from 3.5 to 17.5 mol% of vinyl esters, from 0.1 to 10 mol% of olefins such as propene, butene, isobutene, hexene, 4-methylpentene, octene, diisobutylene, norbornene and / or styrene.
  • olefins such as propene, butene, isobutene, hexene, 4-methylpentene, octene, diisobutylene, norbornene and / or styrene.
  • the molecular weight of the ethylene copolymers i) is preferably between 100 and 100,000 and especially between 250 and 20,000 monomer units.
  • the MFI 190 values of the ethylene copolymers i) measured according to DIN 53735 at 190 ° C. and a contact force of 2.16 kg are preferably between 0.1 and 1200 g / 10 min and especially between 1 and 900 g / min.
  • the means of 1 H-NMR spectroscopy, certain degrees of branching are preferably between 1 and 9 CH 3/100 CH 2 groups, especially between 2 and 6 CH 3/100 CH 2 groups, which do not stem from the comonomers.
  • the polymers underlying the mixtures differ in at least one characteristic.
  • they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.
  • the copolymers i) are prepared by known processes (cf. Ullmanns Encyclopadie der Technischen Chemie, 5th edition, Vol. A 21, pages 305 to 413 ).
  • the polymerization in solution, in suspension, in the gas phase and the high-pressure mass polymerization are suitable. Preference is given to using high-pressure mass polymerization which takes place at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C., preferably 100 to 300 ° C, is performed.
  • the reaction of the comonomers is initiated by free radical initiators (free radical initiators).
  • This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxydicarbonate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di (t -butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in amounts of from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, based on the comonomer mixture.
  • the desired melt flow index MFI of the copolymers i) is adjusted for a given composition of the comonomer mixture by varying the reaction parameters pressure and temperature and optionally by adding moderators.
  • moderators hydrogen, saturated or unsaturated hydrocarbons such as propane and propene, aldehydes such as propionaldehyde, n-butyraldehyde and isobutyraldehyde, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone or alcohols such as butanol, have been proven.
  • the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight, based on the comonomer mixture.
  • the high pressure bulk polymerization is carried out in known high pressure reactors, e.g. As autoclaves or tubular reactors carried out batchwise or continuously, have proven particularly useful tubular reactors. Solvents such as aliphatic hydrocarbons or hydrocarbon mixtures, toluene or xylene, may be included in the reaction mixture, although the solvent-free procedure has proven particularly useful.
  • the comonomer streams can be composed differently ( EP-B-0 271 738 ).
  • Suitable homopolymers or copolymers of esters of ethylenically unsaturated carboxylic acids (ii) which carry C 10 -C 30 -alkyl radicals are, in particular, those which contain recurring structural units of the formula 4, where R 5 and R 6 independently of one another are hydrogen, phenyl or a group of the formula COOR 8 , R 7 is hydrogen, methyl or a group of the formula -CH 2 COOR 8 and R 8 is a C 10 - to C 30 - Alkyl or alkylene radical, preferably a C 12 to C 26 alkyl or alkylene radical, with the proviso that these recurring structural units contain at least one and at most two carboxylic acid ester units in a structural element.
  • R 5 and R 6 is hydrogen or a group of the formula COOR 8 and R 7 is hydrogen or methyl.
  • These structural units are derived from esters of monocarboxylic acids such as acrylic acid, methacrylic acid, cinnamic acid, or of diesters or half esters of dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid.
  • esters of acrylic acid particularly preferred are the esters of acrylic acid.
  • Alcohols suitable for the esterification of the ethylenically unsaturated mono- and dicarboxylic acids are those having 10-30 C atoms, in particular those having 12 to 26 C atoms, for example those having 18 to 24 C atoms. They can be natural or synthetic.
  • the alkyl radicals are preferably linear or at least largely linear.
  • Suitable fatty alcohols include 1-decanol, 1-dodecanol, 1-tridecanol, isotridecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, eicosanol, docosanol, tetracosanol, hexacosanol and naturally occurring mixtures such as coconut fatty alcohol, tallow fatty alcohol, hydrogenated tallow fatty alcohol and behenyl alcohol ,
  • the copolymers of component (ii) may comprise, in addition to the C 10 -C 30 -alkyl esters of unsaturated carboxylic acids, further comonomers such as vinyl esters of formula 1, shorter-chain (meth) acrylic esters of formula 2, alkylvinyl ethers of formula 3 and / or alkenes.
  • Preferred vinyl esters correspond to the meaning given for formula 1.
  • Particularly preferred is vinyl acetate.
  • Preferred alkenes are ⁇ -olefins, that is, linear olefins having a terminal double bond, preferably having chain lengths of from 3 to 50, and especially from 6 to 36, especially from 10 to 30, such as from 18 to 24 carbon atoms.
  • Suitable ⁇ -olefins are propene, 1-butene, isobutene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-butene Heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicose, 1-docoses, 1-tetracoses.
  • chain cuts such as C 13-18 ⁇ -olefins, C 12-16 ⁇ -olefins, C 14-16 ⁇ -olefins, C 14-18 ⁇ -olefins, C 16-18 ⁇ -olefins, C 16-20 ⁇ -olefins, C 22-28 ⁇ -olefins, C 30+ ⁇ -olefins.
  • heteroatom-carrying ethylenically unsaturated compounds such as allyl polyglycols, Acrylklarebenzylester, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, dimethylaminoethyl acrylate, perfluoroalkyl, and the corresponding esters and amides of methacrylic acid, vinylpyridine, vinylpyrrolidone, acrylic acid, methacrylic acid, p-acetoxystyrene, and methoxyacetic acid as comonomers in Component ii) suitable.
  • Their proportion of the polymer is preferably below 20 mol%, in particular between 1 and 15 mol%, for example between 2 and 10 mol%.
  • Preferred homopolymers or copolymers ii) contain at least 10 mol%, in particular 20 to 95 mol%, especially 30 to 80 mol%, such as, for example, 40 to 60 mol% of esters of ethylenically unsaturated carboxylic acids carrying C 10 -C 30 -alkyl radicals structural units.
  • the cold flow improvers ii) consist of structural units derived from C 10 -C 30 -alkyl radicals bearing esters of ethylenically unsaturated carboxylic acids.
  • Preferred homopolymers or copolymers of C 10 -C 30 -alkyl radicals bearing esters of ethylenically unsaturated carboxylic acids ii) are, for example, poly (alkyl acrylates), poly (alkyl methacrylates), copolymers of alkyl (meth) acrylates with vinylpyridine, copolymers of alkyl (meth) acrylates with Allylpolyglykolen, esterified copolymers of alkyl (meth) acrylates with maleic anhydride, copolymers of esterified ethylenically unsaturated dicarboxylic acids such as maleic or Fumarklaredialkylestern with ⁇ -olefins, copolymers of esterified ethylenically unsaturated dicarboxylic acids such as maleic or Fumarklaredialkylestern with unsaturated vinyl esters such as Vinyl acetate as well as copolymers of esterified ethy
  • the molecular weights or molar mass distributions of the copolymers according to the invention are characterized by a K value (measured according to Fikentscher in 5% strength solution in toluene) of 10 to 100, preferably 15 to 80.
  • the average molecular weights Mw may range from 5,000 to 1,000,000, preferably from 10,000 to 300,000, especially from 25,000 to 100,000, and may be determined, for example, by gel permeation chromatography GPC against poly (styrene) standards.
  • the preparation of the copolymers ii) is usually carried out by (co) polymerization of esters of ethylenically unsaturated carboxylic acids, in particular alkyl acrylates and / or alkyl methacrylates, optionally with further comonomers by conventional free-radical polymerization.
  • a suitable preparation process for preparing the cold flow improvers ii) is to dissolve the monomers in an organic solvent and to polymerize in the presence of a radical initiator at temperatures in the range of 30 to 150 ° C.
  • Suitable solvents are preferably aromatic hydrocarbons, such as. As toluene, xylene, trimethylbenzene, dimethylnaphthalene or mixtures of these aromatic hydrocarbons. Commercially available mixtures of aromatic hydrocarbons such as eg solvent naphtha or Shellsol AB® are also used. Aliphatic hydrocarbons are also suitable as solvents. Also, alkoxylated aliphatic alcohols or their esters such as butyl glycol are used as solvents, but preferably as a mixture with aromatic hydrocarbons. In special cases, a solvent-free polymerization for the preparation of the cold flow improvers ii) is possible.
  • free radical initiators commonly used initiators such as azo-bis-isobutyronitrile, esters of peroxycarboxylic acids such as e.g. t-butyl perpivalate and t-butyl-per-2-ethylhexanoate or dibenzoyl peroxide.
  • cold flow improvers ii) Another possibility for the preparation of the cold flow improvers ii) consists in the polymer-analogous esterification or transesterification of already polymerized ethylenically unsaturated carboxylic acids, their esters with short-chain alcohols or their reactive equivalents such as acid anhydrides with fatty alcohols having 10 to 30 carbon atoms.
  • the transesterification of poly (meth) acrylic acid with fatty alcohols or the esterification of polymers of maleic anhydride and ⁇ -olefins with fatty alcohols leads to cold flow improvers ii) suitable according to the invention.
  • the ethylene copolymer a) is one of the copolymers described as cold flow improvers i).
  • Ethylene copolymers which are preferred as the copolymer a) for the grafting are, in particular, those which contain, in addition to ethylene, 7.5 to 15 mol% of vinyl acetate.
  • preferred ethylene copolymers a) have MFI 190 values between 1 and 900 g / min and especially between 2 and 500 g / min.
  • the (co) polymers b) grafted onto the ethylene copolymers a) preferably comprise from 40 to 100% by weight and in particular from 50 to 90% by weight of one or more structural units derived from alkyl acrylates and / or methacrylates. Preferably carry at least 10 mol%, in particular from 20 to 100 mol%, especially from 30 to 90 mol%, such as, for example, from 40 to 70 mol% of the grafted-on structural units, alkyl radicals having at least 12 carbon atoms.
  • Particularly preferred monomers are (meth) acrylic acid alkyl esters with C 16 -C 36 -alkyl radicals, in particular with C 18 -C 30 -alkyl radicals, for example with C 20 -C 24 -alkyl radicals.
  • the grafted polymers contain b) 0 to 60 wt .-%, preferably 10 to 50 wt .-% of one or more further structural units derived from other ethylenically unsaturated compounds.
  • Suitable further ethylenically unsaturated compounds are, for example, vinyl esters of carboxylic acids having 1 to 20 C atoms, ⁇ -olefins having 6 to 40 carbon atoms, vinylaromatics, dicarboxylic acids and their anhydrides and esters with C 10 -C 30 fatty alcohols, acrylic acid, methacrylic acid and in particular heteroatom-carrying ethylenically unsaturated compounds such as, for example, benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, p-acetoxystyrene, methoxyacetic acid vinyl ester, dimethylaminoethyl acrylate, perfluoroal
  • the graft polymers ii) usually contain ethylene copolymer a) and homo- or copolymer of an ester of an ⁇ , ⁇ -unsaturated carboxylic acid with a C 6 - to C 30 -alcohol b) in a weight ratio of 1:10 to 10: 1, preferably from 1: 8 to 5: 1, such as from 1: 5 to 1: 1.
  • graft polymers iii) are prepared by known methods.
  • the graft polymers iii) are obtainable by mixing ethylene copolymer a) and comonomer or comonomer mixture b), if appropriate in the presence of an organic solvent, and adding a radical initiator.
  • polymers of ⁇ -olefins having 3 to 30 carbon atoms are suitable. These can be derived directly from monoethylenically unsaturated monomers or can be prepared indirectly by hydrogenation of polymers derived from polyunsaturated monomers such as isoprene or butadiene.
  • Preferred copolymers contain structural units derived from ⁇ -olefins having 3 to 24 carbon atoms and having molecular weights of up to 120,000 g / mol.
  • Preferred ⁇ -olefins are propene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
  • these polymers may also contain minor amounts of structural units derived from ethylene.
  • These copolymers can also be small amounts, e.g. up to 10 mol% of other comonomers such as e.g. contain non-terminal olefins or non-conjugated olefins. Particularly preferred are ethylene-propylene copolymers.
  • copolymers of various olefins having 5 to 30 carbon atoms such as poly (hexene-co-decene). It may be both random copolymers as well as block copolymers.
  • the olefin homo- and copolymers can be prepared by known methods, e.g. by Ziegler or metallocene catalysts.
  • condensation products of alkylphenols and aldehydes and / or ketones v) are those polymers which comprise structural units which contain at least one phenolic, i. from directly to the aromatic system bound OH group, and at least one directly attached to an aromatic system alkyl, alkenyl, alkyl ether or alkyl ester group have.
  • the condensation products of alkylphenols and aldehydes or ketones (v) are alkylphenol-aldehyde resins.
  • Alkylphenol-aldehyde resins are known in principle and, for example in the Rompp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351 et seq , described.
  • Particularly suitable according to the invention are those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in the ortho and / or para position to the OH group.
  • alkylphenols which carry at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols whose alkyl radical is in the para position.
  • the alkyl radicals may be the same or different in the case of the alkylphenol-aldehyde resins which can be used in the process according to the invention. They may be saturated or unsaturated, preferably they are saturated.
  • the alkyl radicals preferably have 1 to 200, preferably 4 to 50, in particular 6 to 36, carbon atoms.
  • the alkyl radicals can be linear or branched, preferably they are linear.
  • Particularly preferred alkyl radicals having more than 6 C atoms preferably have at most one branch per 4 C atoms, more preferably at most one branch per 6 C atoms, and especially they are linear.
  • preferred alkyl radicals are n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n - and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals and of commercially available raw materials such as ⁇ - Olefin chain cuts or fatty acids in the chain length range of, for example, C 13-18 , C 12-16
  • Particularly suitable alkylphenol-aldehyde resins are derived from linear alkyl radicals having 8 and 9 C atoms.
  • Other particularly suitable alkylphenol-aldehyde resins are derived from linear alkyl radicals in the chain length range from C 12 to C 36 .
  • Suitable aldehydes for the preparation of the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxalic acid and their reactive equivalents such as paraformaldehyde and trioxane.
  • Particularly preferred is formaldehyde in the form of paraformaldehyde and especially formalin.
  • the molecular weight of the alkylphenol-aldehyde resins can vary within wide limits. However, a prerequisite for their suitability according to the invention is that the alkylphenol-aldehyde resins are oil-soluble at least in application-relevant concentrations of from 0.001 to 1% by weight. Preferably, this is by gel permeation chromatography (GPC) against polystyrene standards in THF measured molecular weight between 400 and 50,000, in particular between 800 and 20,000 g / mol such as between 1,000 and 20,000.
  • GPC gel permeation chromatography
  • the cold flow improvers v) are alkylphenol-formaldehyde resins, the oligomers or polymers having a repetitive structural unit of the formula 6 wherein R 13 is C 1 -C 200 alkyl or C 2 -C 200 alkenyl and n is a number from 2 to 250.
  • R 13 is preferably C 4 -C 50 -alkyl or -alkenyl and in particular C 6 -C 36 -alkyl or -alkenyl.
  • n is a number from 3 to 100 and especially a number from 5 to 50, for example a number from 10 to 35.
  • the inventively suitable alkylphenol-aldehyde resins are accessible by known methods, for example by condensation of the corresponding alkylphenols with formaldehyde, ie with 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of formaldehyde per mole of alkylphenol.
  • the condensation can be free of solvent, but preferably it is carried out in the presence of an inert or only partially water-miscible inert organic solvent such as mineral oils, alcohols, ethers and the like.
  • biogenic raw materials such as fatty acid methyl esters based solvents are suitable as the reaction medium.
  • the condensation preferably takes place in the organic, water-immiscible solvent II).
  • solvents which can form azeotropes with water.
  • solvents in particular aromatic compounds such as toluene, xylene, diethylbenzene and higher boiling commercial solvent mixtures, such as Shellsol ® AB, and solvent naphtha may be used.
  • the condensation is preferably carried out between 70 and 200 ° C such as between 90 and 160 ° C. It is usually catalysed by 0.05 to 5 wt .-% bases or preferably acids.
  • the various cold flow improvers (i) to (v) may be used alone or as a mixture of various cold flow improvers of one or more groups.
  • the individual components are usually used in a proportion of 5 to 95 wt .-%, such as 20 to 90 wt .-% based on the total amount of cold flow improver used (I).
  • water immiscible solvents (II) are aliphatic, aromatic and alkyl aromatic hydrocarbons and mixtures thereof especially proven.
  • the cold flow improvers (I) which can be used according to the invention are at least 20% strength by weight soluble at temperatures above 50 ° C.
  • Preferred solvents do not contain any polar groups in the molecule and have boiling points which allow the lowest possible expenditure on equipment at the required working temperature of 60 ° C and more, ie boiling points of at least 60 ° C and preferably from 80 to 200 ° C under normal conditions exhibit.
  • Suitable solvents are: decane, toluene, xylene, diethylbenzene, naphthalene, tetralin, decalin, and commercial solvent mixtures, such as Shellsol ® -, Exxsol ®, Isopar ® -, Solvesso ® grades, solvent naphtha and / or kerosene.
  • the water-immiscible solvents comprise at least 10 wt .-%, preferably 20 to 100 wt .-%, such as 30 to 90 wt .-% of aromatic ingredients. These solvents can also be used for the preparation of the cold flow improvers used according to the invention.
  • Suitable alkanolammonium salts of polycyclic carboxylic acids (IV) are in particular those compounds which can be prepared by neutralization of at least one polycyclic carboxylic acid with at least one alkanolamine.
  • Suitable polycyclic carboxylic acids are derived from polycyclic hydrocarbons containing at least two five- and / or six-membered rings which are linked together via two preferably vicinal carbon atoms. These rings contain at most one heteroatom such as oxygen or nitrogen, but preferably all of the ring atoms are carbon atoms.
  • the rings can be saturated or unsaturated. They may be unsubstituted or substituted and bear at least one carboxyl group or a substituent carrying at least one carboxyl group or an equivalent of a carboxyl group capable of salt formation with amines.
  • the polycyclic carboxylic acids preferably contain at least three ring systems, which are each linked via two vicinal carbon atoms of two ring systems.
  • Particularly preferred polycyclic hydrocarbon compounds have from 12 to about 30 carbon atoms, and more preferably from 16 to 24 carbon atoms, such as from 18 to 22 carbon atoms. Further preferably, at least one ring system contains a double bond.
  • the radicals R 19 , R 20 , R 21 and R 22 are preferably alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.
  • Z is preferably a carboxyl group bonded directly to a ring system. Furthermore, Z is preferably a carboxyl group bonded via an alkylene group, for example via a methylene group, to a ring system.
  • the polycyclic carboxylic acids of the formula (8) and / or (9) used are acids based on natural resins. These natural acids are obtainable, for example, by extraction of resinous trees, in particular resinous coniferous trees, and can be isolated by distillation from these extracts.
  • resinous acids For example, abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, levopimaric acid and palustric acid and derivatives thereof are preferred.
  • Preferred mixtures of resin-based acids have acid numbers between 150 and 200 mg KOH / g and in particular between 160 and 185 mg KOH / g.
  • Naphthenic acids are also suitable as polycyclic carboxylic acids. Naphthenic acids are understood as meaning mixtures of fumed and alkylated cyclopentane and cyclohexanecarboxylic acids extracted from mineral oils. The average molecular weights of preferred naphthenic acids are generally between 180 and 350 g / mol and in particular between 190 and 300 g / mol. The acid number is preferably in the range of 140-270 mg KOH / g and in particular between 180 and 240 mg KOH / g.
  • B particularly preferably represents an alkylene radical having 2 to 5 C atoms and in particular a group of the formula -CH 2 -CH 2 - and / or -CH (CH 3 ) -CH 2 -.
  • P is preferably a number between 2 and 20 and in particular a number between 3 and 10.
  • p is 1 or 2.
  • Alkoxy chains with p ⁇ 3 and in particular with p ⁇ 5 may be a Block polymer chain having alternating blocks of different alkoxy units, preferably ethoxy and propoxy units. Particularly preferred is - (BO) p - a homopolymer.
  • the hydrocarbon radicals R 24 and R 25 are interrupted by heteroatoms such as nitrogen alkyl and alkenyl radicals.
  • alkanolamines in which R 23 and R 24 independently of one another are a group of the formula - (BO) p -H and R 25 is H, in which the meanings for B and p in R 23 and R 24 are identical or different could be. In particular, the meanings for R 23 and R 24 are the same.
  • R 23 , R 24 and R 25 independently of one another represent a group of the formula - (BO) p -H, in which the meanings for B and p in R 23 , R 24 and R 25 are identical or different can be. In particular, the meanings for R 23 , R 24 and R 25 are the same.
  • alkanolamines are aminoethanol, 3-amino-1-propanol, isopropanolamine, N-butyldiethanolamine, N, N-diethylaminoethanol, N, N-dimethylisopropanolamine, 2- (2-aminoethoxy) ethanol, 2-amino-2-methyl- 1-propanol, 3-amino-2,2-dimethyl-1-propanol, 2-amino-2-hydroxymethyl-1,3-propanediol, diethanolamine, dipropanolamine, diisopropanolamine, di (diethylene glycol) amine, N-butyldiethanolamine, triethanolamine, Tripropanolamine, tri (isopropanol) amine, tris (2-hydroxypropylamine), aminoethylethanolamine and poly (ether) amines such as poly (ethylene glycol) amine and poly (propylene glycol) amine having in each case 4 to 50 alkylene oxide units
  • R 23 and R 24 or R 23 and R 25 together represent a cyclic hydrocarbon radical interrupted by at least one oxygen atom.
  • the remaining radical R 24 or R 25 is preferably hydrogen, a lower alkyl radical having 1 to 4 C atoms or a group of the formula (11) in which B is an alkylene radical having 2 or 3 C atoms and p is 1 or 2 and R 26 is hydrogen or a group of the formula -B-NH 2 .
  • morpholine and its N-alkoxyalkyl derivatives such as 2- (2-morpholin-4-yl-ethoxy) -ethanol and 2- (2-morpholin-4-yl-ethoxy) -ethylamine have been used successfully to prepare the dispersions of the invention.
  • the alkanolamine salts of the polycyclic carboxylic acids can be prepared by mixing the polycyclic carboxylic acids with the corresponding amines.
  • Alkanolamine and polycyclic carboxylic acid can, based on the content of acid groups on the one hand and amino groups on the other hand in a molar ratio of 10: 1 to 1:10, preferably from 5: 1 to 1: 5, especially from 1: 2 to 2: 1 as in im Ratio of 1.2: 1 to 1: 1.2 are used.
  • alkanolamine and polycyclic carboxylic acid based on the content of acid groups on the one hand and amino groups on the other hand are used equimolar.
  • melting salts as a solution or dispersion in one of the solvents (II) and / or (V) and / or in admixture with at least one further low viscosity co-emulsifier.
  • polycyclic carboxylic acid salts can be used as such or in combination with other emulsifiers (coemulsifiers) (VI).
  • emulsifiers coemulsifiers
  • they are used in combination with anionic, cationic, zwitterionic and / or nonionic emulsifiers.
  • Anionic coemulsifiers contain a lipophilic moiety and a polar headgroup bearing an anionic group such as a carboxylate, sulfonate or phenolate group.
  • Typical anionic co-emulsifiers include, for example, fatty acid salts of fatty acids having a preferably linear, saturated or unsaturated hydrocarbon radical having 8 to 24 carbon atoms.
  • Preferred salts are the alkali, alkaline earth and ammonium salts such as sodium palmitate, potassium oleate, ammonium stearate, diethanolammonium talloate and triethanolammonium cocoate.
  • anionic co-emulsifiers are polymeric anionic surfactants, for example based on neutralized copolymers of alkyl (meth) acrylates and (meth) acrylic acid and neutralized partial esters of styrene-maleic acid copolymers.
  • alkyl, aryl and alkylaryl sulfonates, sulfates of alkoxylated fatty alcohols and alkylphenols and sulfosuccinates and in particular their alkali, alkaline earth and ammonium salts are suitable as co-emulsifiers.
  • Cationic coemulsifiers contain a lipophilic moiety and a polar headgroup bearing a cationic group.
  • Typical cationic co-emulsifiers are salts of long-chain primary, secondary or tertiary amines of natural or synthetic origin.
  • quaternary ammonium salts such as tallow fat derived tetraalkylammonium salts and imidazolinium salts are useful as cationic coemulsifiers.
  • Zwitterionic coemulsifiers are understood to mean amphiphiles, whose polar head group is both an anionic and a cationic center carries, which are linked together via covalent bonds.
  • Typical zwitterionic co-emulsifiers include, for example, N-alkyl N-oxides, N-alkyl betaines and N-alkyl sulfobetaines.
  • nonionic coemulsifiers are, for example, 10 to 80 times, preferably 20 to 50 times, ethoxylated C 8 to C 20 alkanols, C 8 to C 12 alkylphenols, C 8 to C 20 fatty acids or C 8 to C 20- fatty acid amides.
  • Further suitable examples of nonionic coemulsifiers are poly (alkylene oxides) in the form of block copolymers of various alkylene oxides, such as ethylene oxide and propylene oxide, as well as partial esters of polyols or alkanolamines with fatty acids.
  • the coemulsifiers are preferably used in a weight ratio of 1:20 to 20: 1 and in particular 1:10 to 10: 1, for example 1: 5 to 5: 1, based on the mass of the polycyclic carboxylic acid salt.
  • Particularly preferred co-emulsifiers are salts of fatty acids having 12 to 20 carbon atoms and in particular of unsaturated fatty acids having 12 to 20 carbon atoms, such as, for example, oleic acid, linoleic acid and / or linolenic acid with alkali, ammonium and in particular alkanolammonium ions of the formula (10) ,
  • mixtures of salts of cyclic carboxylic acids and tall oil fatty acids containing at least 5% by weight of salts of cyclic carboxylic acids, in particular between 10 and 90% by weight, especially between 20 and 85% by weight, for example between 25 and 60 wt .-% used.
  • These are preferably mixtures of salts of so-called resin acids and tall oil fatty acid.
  • Suitable water-miscible solvents are preferably those solvents which have a high polarity and, in particular, those which have a dielectric constant of at least 3 and in particular at least 10.
  • solvents contain 10 to 80 wt .-% of heteroatoms such as oxygen and / or nitrogen. Particularly preferred are oxygen-containing solvents.
  • Preferred water-miscible organic solvents are alcohols having 2 to 14 C atoms, glycols having 2 to 10 C atoms and poly (glycols) having 2 to 50 monomer units.
  • the glycols and polyglycols may also be terminally etherified with lower alcohols or esterified with lower fatty acids. However, it is preferred that only one side of the glycol is closed.
  • suitable water-miscible organic solvents are ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, propylene glycol, dipropylene glycol, polypropylene glycols, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerol and the monomethyl ethers, monopropyl ethers, monobutyl ethers and monohexyl ethers of these glycols.
  • solvents examples include alcohols (eg, methanol, ethanol, propanol), acetates (eg, ethyl acetate, 2-ethoxyethyl acetate), ketones (eg, acetone, butanone, pentanone, hexanone), lactones such as butyrolactone, and alcohols such as butanol, diacetone alcohol, 2,6-dimethyl-4-heptanol, hexanol, isopropanol, 2-ethylhexanol and 1-pentanol.
  • Particularly preferred water-miscible organic solvents (V) are ethylene glycol and glycerol.
  • the water-miscible solvents mentioned can be present in the ratio of 1: 3 to 3: 1, based on the amount of water, in the dispersions according to the invention.
  • the cold flow improvers (I) which can be used according to the invention are substantially insoluble, at least at room temperature and often also at temperatures up to 40 ° C. and sometimes up to 50 ° C., ie they dissolve these solvents the polymers (I) at room temperature preferably less than 5 wt .-%, in particular less than 2 wt .-% such as less than 1 wt .-%.
  • the dispersions according to the invention particularly preferably contain from 10 to 50 and in particular from 25 to 45% by weight of the cold flow improver (I).
  • the cold flow improver of the dispersions of the invention is an ethylene copolymer (i)
  • its concentration is in particular between 10 and 40 wt .-%, such as between 15 and 30 wt .-%.
  • the proportion of the water-immiscible solvent is in particular between 10 and 40 wt .-%, such as between 15 and 30 wt .-%.
  • the water content of the dispersions according to the invention is in particular between 10 and 40% by weight, for example between 15 and 30% by weight.
  • the proportion of the polycyclic carboxylic acid salt (IV) is in particular between 0.05 and 3 wt .-%, such as between 0.1 and 2 wt .-%.
  • the proportion of the water-miscible solvent (V) is between 2 and 40% by weight and in particular between 5 and 30% by weight, for example between 10 and 25% by weight.
  • the constituents of the additive according to the invention may optionally be combined with heating and homogenized with heating and stirring.
  • the order of addition is not critical.
  • the cold flow improver (I) is dissolved in the water-immiscible solvent (II), optionally with heating. Preference is given to working at temperatures between 20 and 180 ° C and in particular at temperatures between the melting point of the polymer or the pour point of the polymer in the solvent used and the boiling point of the solvent.
  • the amount of solvent is preferably selected so that the solutions contain at least 20, preferably 35 to 60 wt .-% dissolved cold flow improvers.
  • polycyclic carboxylic acid salt (IV) and optionally coemulsifiers (VI) and, if desired, the water-miscible solvent (III) are added to this viscous solution, preferably with stirring and at an elevated temperature of for example 70 to 90 ° C.
  • the order of addition is generally not critical.
  • Emulsifier (IV) and optionally co-emulsifier (VI) can also be added as a solution or dispersion in the water-miscible solvent (V).
  • the polycyclic carboxylic acid salt is prepared in situ in the polymer solution or in the water-miscible solvent (V) by adding polycyclic carboxylic acid and alkanolamine to the polymer solution and to the water-miscible solvent (V), respectively.
  • water (III) is added.
  • the water is heated before the addition to a temperature of 50 to 90 ° C and in particular to a temperature between 60 and 80 ° C.
  • the water can also be added at higher temperatures, such as temperatures up to 150 ° C, but then working in a closed system under pressure is required.
  • at least as much water is added until the reversible phase, which is due to a decrease in viscosity, results in an oil-in-water suspension.
  • the polycyclic carboxylic acid salt (IV) is initially introduced into water and optionally water-miscible solvent (V) and mixed with the viscous solution of the cold flow improver (I) in the water-immiscible solvent (II).
  • water-soluble polymers are used.
  • ABA poly (alkylene glycols) and poly (alkylene glycol) diesters of long-chain fatty acids natural, modified and synthetic water-soluble polymers are particularly suitable.
  • Preferred ABA block poly (alkylene glycols) preferably contain A blocks of poly (propylene glycol) having average molecular weights of 100 to 10,000 D, especially 150 to 1,500 D and B blocks of poly (ethylene glycol) having average molecular weights of 200 to 20,000 D, in particular from 300 to 3000 D.
  • Preferred polyalkylene glycol diesters preferably consist of poly (ethylene glycol) units having an average molecular weight of from 100 to 10,000 D, in particular from 200 to 750 D.
  • the long-chain fatty acids of the ester preferably carry alkyl radicals having from 14 to 30 ° C Atoms, in particular with 17 to 22 C atoms.
  • preferred natural or modified natural polymers are, for example, guar, locust bean gum and their modified derivatives, starch, modified starch such as dextran, xanthan and xeroglucan, cellulose ethers such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and carboxymethyl hydroxyethyl cellulose and hydrophobically modified, associative Thickening cellulose derivatives and their combinations.
  • particularly preferred synthetic water-soluble polymers are in particular crosslinked and uncrosslinked homo- and Copolymers of (meth) acrylic acid and its salts, acrylamidopropanesulfonic acid and its salts, acrylamide, N-vinylamides such as N-vinyl-formamide, N-vinyl-pyrrolidone or N-vinyl-caprolactam.
  • their crosslinked and uncrosslinked hydrophobically modified polymers are also of interest as rheology modifiers for formulations according to the invention.
  • Viscoelastic surfactant combinations of nonionic, cationic and zwitterionic surfactants are also suitable as rheology-modifying additives.
  • the rheology modifying substances are added together with the water. However, they may also be added to the dispersion, preferably before shearing.
  • the dispersions according to the invention preferably contain from 0.01 to 5% by weight and in particular from 0.05 to 1% by weight, based on the amount of water, of one or more rheology-modifying substances.
  • water and the water-miscible solvent (V) are used as a mixture.
  • this mixture is heated before addition to a temperature between 50 and 100 ° C and in particular to a temperature between 60 and 80 ° C.
  • the optionally heated dispersion is exposed to high shear rates of at least 10 3 s -1 and preferably of at least 10 5 s -1 such as of at least 10 6 s -1 , as for example by means of sprocket dispersants (eg Ultra-Turrax ® ), or high-pressure homogenizers with classic or preferred Angled channel architecture (Microfluidizer ® ) can be generated. Also by Cavitron or ultrasound suitable shear rates can be achieved.
  • the average particle size of the dispersions is below 50 ⁇ m and in particular between 0.1 and 20 ⁇ m, for example between 1 and 10 ⁇ m.
  • inventive alkanolamine salts of polycyclic carboxylic acids containing emulsifiers as dispersions are low viscous liquids despite a high active ingredient content of up to 50 wt .-%.
  • Their viscosities at 20 ° C are below 2,000 mPa ⁇ s and often below 1,000 mPa ⁇ s such as below 750 mPa ⁇ s.
  • Their eigenstock point is usually below 10 ° C, often below 0 ° C and in special cases below -10 ° C such as below -24 ° C. They can thus be used even under unfavorable climatic conditions such as in Arctic regions as well as in off-shore applications without further precautions against the sticking of the additives.
  • a down-the-hole application is also possible without prior dilution of the additives and without heating the delivery lines.
  • they also show excellent long-term stability even at elevated temperatures of more than 30 ° C., for example above 45 ° C., that is to say above the melting temperature of the dispersed polymer.
  • the dispersions of the invention show no or only negligible amounts of coagulum or settled solvent. Any occurring inhomogeneities can also be homogenized by simply stirring again.
  • the dispersions according to the invention are particularly suitable for improving the cold properties of crude oils and products produced therefrom, such as, for example, heating oils, bunker oils, residual oils and mineral oils containing residual oils.
  • the additized crude oils and the paraffin-containing products derived therefrom usually contain about 10 to 10,000 ppm and preferably 20 to 5,000 ppm, for example 50 to 2,000 ppm of the dispersions according to the invention.
  • With the inventive dispersion added in amounts of 10 to 10,000 ppm - based on mineral oil - achieved Pour point depressions of frequently more than 10 ° C, often more than 25 ° C and sometimes up to 40 ° C, both crude oils and refined oils, such as lubricating oil or heavy fuel oil.
  • the dispersions of the present invention exhibit superior potency to the solutions of pour point depressants used in organic solvents.
  • the resin acids used to prepare the emulsifiers of the present invention were mixtures of polycyclic carboxylic acids obtained from distillate fractions of natural oils extracted from conifer resins. Main constituents were abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, pimaric acid and levopimaric acid.
  • the emulsifiers according to the invention After dissolving in organic solvent or in unsaturated fatty acids, an equimolar amount of the alkanolamine mentioned in the respective experiment was added to the polycyclic carboxylic acids and the mixture was stirred for 30 minutes. In the case of using fatty acids as solvents, these too were converted into the alkanolamine salt.
  • unsaturated fatty acid tall oil fatty acid having a fatty acid content of over 98% was used.
  • the viscosities of the dispersions were determined using a plate and cone viscometer with a diameter of 35 mm and a cone angle of 4 ° at 25 ° C. and a shear rate of 100 s -1 .
  • the particle sizes and distributions were determined by means of a Mastersizer 2000 instrument from Malvern Instruments. Pour points were measured according to ISO 3016.
  • the dispersion thus obtained had an average particle size of 1.6 ⁇ m and a viscosity of 625 mPa ⁇ s (25 ° C). After five-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • the dispersion thus obtained had a viscosity of 140 mPa.s After six weeks' storage of an aliquot of this sample at room temperature or at 50 ° C., the samples were homogeneous and the viscosities unchanged.
  • the dispersion thus obtained had an average particle size of 1.7 microns and a viscosity of 270 mPa ⁇ s. After five-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • the dispersion thus obtained had an average particle size of 1.9 microns and a viscosity of 312 mPa ⁇ s. After six-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and their viscosities unchanged.
  • the dispersion thus obtained had an average particle size of 1.7 microns and a viscosity of 283 mPa ⁇ s. After six-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • the dispersion thus obtained had a viscosity of 280 mPa ⁇ s. After storage of an aliquot of this sample at room temperature or at 50 ° C. for six weeks, the samples were homogeneous and the viscosities unchanged.
  • the dispersion thus obtained had an average particle size of 4 ⁇ m. After storage of aliquots of this sample both at room temperature and at 50 ° C overnight, the samples showed significant inhomogeneities in the form of creaming of the polymer or gel formation (pasty) and simultaneous deposition of specific heavier, clear solvent.
  • a solution of 18 g of a 4: 1 behenyl acrylate grafted ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by weight and a MFI 190 of 7 g / 10 minutes in 18 g of xylene was heated to 75 ° C. Within 30 minutes, this was added, while stirring, in portions to a tempered to 60 ° C solution of 2 g of an emulsifier, by reacting a solution of 26 wt .-% resin acids in tall oil fatty acid with 2- (2-morpholin-4-yl-ethoxy ) ethanol in a weight ratio of 3: 1 was added in 13 g of monoethylene glycol.
  • the dispersion thus obtained had an average particle size of 1.5 microns and a viscosity of 1180 mPa ⁇ s. After six-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • Example 8 only a dispersion was prepared in which triethanolamine was used as alkanolamine instead of the 2- (2-morpholin-4-yl-ethoxy) ethanol. The result is a microdispersion with a viscosity of 137 mPa ⁇ s. After six-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • a solution of 18 g of a 4: 1 behenyl acrylate grafted ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by weight and a MFI 190 of 7 g / 10 minutes in 18 g of xylene was heated to 60 ° C. With stirring, a mixture of 0.5 g resin triethanolammonium salt and 1.5 g triethanolammonium talloate was added and homogenized for 30 minutes. To this solution was added at 80 to 85 ° C with further stirring slowly 26 g of water containing 2.5 g / l xanthan gum and 1 g / l biocide added. This formed a white, low-viscosity suspension. After cooling to 40 ° C, the suspension was sheared for 2 minutes with an Ultra-Turrax ® T25B with tool S25N-25F at 20,000 rpm.
  • the dispersion thus obtained had a viscosity of 78 mPa.s measured at 25 ° C. After six-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • Example 8 a dispersion was prepared using 2 g of a mixture of equal parts by weight of diethanolammonium naphthenate (acid number of the naphthenic acid used 260 mg KOH / g, Mw: 216 g / mol) and diethanolammonium tallow as emulsifier.
  • the resulting Microdispersion had a viscosity of 139 mPa.s measured at 25 ° C. After six-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • Example 8 a dispersion was prepared by using 2.3 g of a mixture of equal parts by weight of rosin acid diethanolammonium salt and xylene as an emulsifier.
  • the resulting microdispersion had a viscosity of 143 mPa.s measured at 25 ° C. After six-week storage of aliquots of this sample at room temperature or at 50 ° C, the samples were homogeneous and the viscosities unchanged.
  • the dispersion thus obtained had a viscosity of 163 mPa ⁇ s. After storage of an aliquot of this sample at room temperature or at 50 ° C. for six weeks, the samples were homogeneous and the viscosities unchanged.
  • the experiments show that the superior stability of the dispersions according to the invention is decisively conditioned by the presence of alkanolamine salts of polycyclic carboxylic acids. Furthermore, they show that the activity of the active ingredients formulated in the form of the dispersion according to the invention is at least equal to, and sometimes even superior to, the solutions of the corresponding active ingredients in organic solvents.

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Abstract

L'invention concerne des dispersions contenant : I) au moins un polymère soluble dans l'huile, agissant comme promoteur d'écoulement à froid pour des huiles minérales : II) au moins un solvant organique non miscible avec l'eau; III) de l'eau; IV) au moins un sel d'alcanolamine d'un acide carboxylique polycyclique comme dispersant; et V) éventuellement au moins un solvant organique miscible avec l'eau.

Claims (29)

  1. Dispersions, contenant
    I) 5-60 % en poids d'au moins un polymère liposoluble actif en tant qu'agent améliorant l'écoulement à froid pour huiles minérales,
    II) 5-45 % en poids d'au moins un solvant organique, non miscible à l'eau,
    III) 5-60 % en poids d'eau,
    IV) 0,001 à 5 % en poids d'au moins un sel d'alcanolamine d'un acide carboxylique polycyclique et
    V) 0-40 % en poids d'au moins un solvant organique miscible à l'eau.
  2. Dispersion selon la revendication 1, dans laquelle l'agent améliorant l'écoulement à froid I est un copolymère d'éthylène et d'au moins un éther ou ester à insaturation éthylénique ou un alcène.
  3. Dispersion selon la revendication 1, dans laquelle l'agent améliorant l'écoulement à froid est un homopolymère ou copolymère d'au moins un ester portant des radicaux alkyle en C10-C30 d'au moins un acide carboxylique à insaturation éthylénique.
  4. Dispersion selon la revendication 2, dans laquelle l'ester à insaturation éthylénique est un ester vinylique.
  5. Dispersion selon la revendication 3, dans laquelle l'acide carboxylique à insaturation éthylénique est l'acide acrylique et/ou l'acide méthacrylique.
  6. Dispersion selon la revendication 1, dans laquelle l'agent améliorant l'écoulement à froid est un copolymère d'éthylène greffé avec des éthers et/ou esters à insaturation éthylénique.
  7. Dispersion selon la revendication 6, dans laquelle l'ester à insaturation éthylénique est un ester portant des radicaux alkyle en C10-C30 de l'acide acrylique et/ou de l'acide méthacrylique.
  8. Dispersion selon la revendication 1, dans laquelle l'agent améliorant l'écoulement à froid est un homopolymère ou copolymère d'α-oléfines ayant de 3 à 30 atomes de carbone.
  9. Dispersion selon la revendication 1, dans laquelle l'agent améliorant l'écoulement à froid est un produit de condensation d'au moins un alkylphénol et d'au moins un aldéhyde ou une cétone.
  10. Dispersion selon la revendication 9, dans laquelle le produit de condensation correspond à la formule 6
    Figure imgb0013
     dans laquelle R13 représente un groupe alkyle en C1-C200 ou alcényle en C2-C200 et n représente un nombre valant de 2 à 250.
  11. Dispersion selon une ou plusieurs des revendications 1 à 10, dans laquelle le dispersant IV peut être préparé par neutralisation d'au moins un acide carboxylique polycyclique par au moins une alcanolamine.
  12. Dispersion selon une ou plusieurs des revendications 1 à 11, dans laquelle l'acide carboxylique polycyclique dérive d'au moins un hydrocarbure polycyclique qui contient au moins deux cycles à cinq et/ou six chaînons, qui sont liés l'un à l'autre par deux atomes de carbone de préférence vicinaux.
  13. Dispersion selon une ou plusieurs des revendications 1 à 12, dans laquelle l'acide carboxylique polycyclique correspond à la formule 8
    Figure imgb0014
     dans laquelle
    X représente des atomes de carbone ou trois atomes de carbone, d'azote et/ou d'oxygène, étant entendu que chacune des unités structurales consistant en quatre X liés entre eux consiste en soit 4 atomes de carbone, soit 3 atomes de carbone et un atome d'oxygène ou un atome d'azote
    R19, R20, R21 et R22 sont identiques ou différents et représentent un atome d'hydrogène ou des groupes hydrocarbonés qui sont liés chacun à au moins un atome de l'un des deux cycles, ces groupes hydrocarbonés étant choisis parmi des groupes alkyle ayant de un à cinq atomes de carbone,
    des groupes aryle,
    des cycles hydrocarbonés ayant cinq ou six atomes, qui contiennent éventuellement un hétéroatome, tel qu'un atome d'azote ou d'oxygène, le cycle hydrocarboné étant saturé ou insaturé, non substitué ou substitué par un radical aliphatique éventuellement oléfinique ayant de un à quatre atomes de carbone, chaque fois deux des radicaux R19, R20, R21 et R22 formant un tel cycle hydrocarboné et
    Z représente un groupe carboxy ou un radical alkyle portant au moins un groupe carboxy.
  14. Dispersion selon une ou plusieurs des revendications 1 à 12, dans laquelle l'acide carboxylique polycyclique correspond à la formule (9) :
    Figure imgb0015
     dans laquelle
    au maximum un X de chaque cycle représente un hétéroatome, tel qu'un atome d'azote ou d'oxygène, et les autres atomes X représentent des atomes de carbone,
    R19, R20, R21 et R22 ont la signification indiquée plus haut et
    Z est lié à au moins un atome d'au moins l'un des deux cycles et représente un groupe carboxy ou un radical alkyle portant au moins un groupe carboxy.
  15. Dispersion selon une ou plusieurs des revendications 1 à 14, dans laquelle l'acide carboxylique polycyclique est un acide à base de résines naturelles.
  16. Dispersion selon une ou plusieurs des revendications 1 à 15, dans laquelle l'acide carboxylique polycyclique est un acide naphténique.
  17. Dispersion selon une ou plusieurs des revendications 1 à 16, dans laquelle l'alcanolamine est une amine primaire, secondaire ou tertiaire, qui porte au moins un radical alkyle substitué par un groupe hydroxy.
  18. Dispersion selon une ou plusieurs des revendications 1 à 17, dans laquelle l'alcanolamine correspond à la formule 10 suivante :

            NR23R24R25     (10)

    dans laquelle
    R23 représente un radical hydrocarboné ayant de 1 à 10 atomes de carbone, portant au moins un groupe hydroxy et
    R24, R25 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un radical hydrocarboné éventuellement substitué ayant de 1 à 50 atomes de carbone, en particulier un groupe alkyle en C1-C20, alcényle en C3-C20, aryle en C6-C20 ou R23 ou
    R23 et R24 ou R23 et R25 représentent ensemble un radical hydrocarboné cyclique interrompu par au moins un atome d'oxygène.
  19. Dispersion selon la revendication 18, dans laquelle l'alcanolamine représente un composé hétérocyclique de formule (10), dans laquelle R23 et R24 ou R23 et R25 représentent ensemble un radical hydrocarboné cyclique interrompu par au moins un atome d'oxygène et le radical R24 ou R25 restant représente un radical alkyle inférieur ayant de 1 à 4 atomes de carbone ou un groupe de formule (11), dans lequel B représente un radical alkylène ayant 2 ou 3 atomes de carbone et p représente 1 ou 2 et R26 représente un atome d'hydrogène ou un groupe de formule -B-NH2.
  20. Dispersion selon une ou plusieurs des revendications 1 à 19, dans laquelle le sel d'acide carboxylique polycyclique IV est utilisé conjointement avec un co-émulsifiant.
  21. Dispersion selon une ou plusieurs des revendications 1 à 20, dans laquelle le solvant (V) miscible à l'eau présente une constante diélectrique d'au moins 3.
  22. Dispersion selon une ou plusieurs des revendications 1 à 21, dans laquelle le solvant (V) miscible à l'eau est choisi parmi des alcools, des glycols, des polyglycols, des acétates, des cétones et des lactones.
  23. Dispersion selon une ou plusieurs des revendications 1 à 22, dans laquelle on ajoute une substance modifiant la rhéologie, engendrant une limite d'écoulement.
  24. Procédé pour la préparation de dispersions, contenant
    I) 5-60 % en poids d'au moins un polymère liposoluble actif en tant qu'agent améliorant l'écoulement à froid pour huiles minérales,
    II) 5-45 % en poids d'au moins un solvant organique, non miscible à l'eau,
    III) 5-60 % en poids d'eau,
    IV) 0,001 à 5 % en poids d'au moins un sel d'alcanolamine d'un acide carboxylique polycyclique et
    V) 0-40 % en poids d'au moins un solvant organique miscible à l'eau,
    par mélange sous agitation des composants I, II, III, IV et éventuellement V.
  25. Procédé pour la préparation d'une dispersion selon la revendication 24, par addition d'un mélange des composants I et II à un mélange d'eau et du composant IV) ainsi qu'éventuellement du composant V), à des températures comprises entre 10 °C et 100 °C, de sorte qu'il se forme une dispersion huile-dans-eau.
  26. Procédé pour la préparation de dispersions selon la revendication 24, par homogénéisation des composants I), II) et éventuellement V) avec le composant IV) et ensuite addition d'eau à des températures comprises entre 10 °C et 100 °C, de sorte qu'il se forme une dispersion huile-dans-eau.
  27. Procédé pour la préparation d'une dispersion selon une ou plusieurs des revendications 24 à 26, par cisaillement du mélange des composants.
  28. Utilisation de dispersions selon une ou plusieurs des revendications 1 à 23, pour l'amélioration des propriétés d'écoulement à froid d'huiles minérales paraffiniques et de produits élaborés à partir de celles-ci.
  29. Procédé pour l'amélioration des propriétés d'écoulement à froid d'huiles minérales paraffiniques et de produits élaborés à partir de celles-ci, par addition aux huiles minérales paraffiniques et produits élaborés à partir de celles-ci de dispersions qui contiennent
    I) 5-60 % en poids d'au moins un polymère liposoluble actif en tant qu'agent améliorant l'écoulement à froid pour huiles minérales,
    II) 5-45 % en poids d'au moins un solvant organique, non miscible à l'eau,
    III) 5-60 % en poids d'eau,
    IV) 0,001 à 5 % en poids d'au moins un sel d'alcanolamine d'un acide carboxylique polycyclique et
    V) 0-40 % en poids d'au moins un solvant organique miscible à l'eau.
EP07764904A 2006-12-22 2007-06-28 Dispersions d'additifs polymères d'huiles Not-in-force EP2106433B8 (fr)

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