DE102004014080A1 - Nucleating agent based on hyperbranched polymer, used in paraffinic oil or biofuel to reduce cold filter plugging point, has long-chain linear alkyl-terminated ester, carbonate, (thio)ether, amide, urethane, urea or aminopropionyl groups - Google Patents

Abstract

Nucleating agent based on hyperbranched polymer (I) is claimed, where (I) has a 10-500 divalent ester, carbonate, ether, thioether, amide, urethane, urea or aminopropionyl groups, each terminated by a linear saturated 8-40 carbon alkyl group and optionally a smaller number of such groups terminated by organic groups that increase solubility and/or dispersibility. Nucleating agent based on hyperbranched polymers of formula (I) is claimed: [Structure (I) as given below] n, m : 0 or 1 or n+m is less than k; k : about 10-500; L1, L2, L3 : divalent ester, carbonate, ether, thioether, amide, urethane, urea or -C(O)-CH2-CH2-NR' groups; R, R' : the same or different linear saturated 8-40 C alkyl groups; M1 : the same or different 10-1000 C organic groups promoting solubility; M2 : the same or different 10-100 C organic groups causing dispersion, which can contain N atom(s) in uncharged or zwitterion form . An independent claim is also included for preparation of this nucleating agent.

Description

The The invention relates to the preparation of novel nucleating agents (Crystal nucleating agent) based on hyperbranched polymers, and their use in paraffinic crude oils, fuels, fuels, oils or Lubricants.

The The invention further relates to the use of these nucleating agents on fat Fuels and fuels, such as fatty acid methyl esters.

at the storage of paraffin-containing fuels, fuels or oils At lower temperatures, the excretion of solid paraffins is observed. The temperature at which the first precipitating crystals visible as turbidity to be called cloud point ("Cloud point"). Solidified on further cooling the liquid through the paraffin crystallization on and on, until the so-called Pour point ("Pour Point ") reached is.

The Cause for This solidification lies in the crystallization behavior of the precipitating Paraffins. As it solidifies, it forms a three-dimensional network from needles or leaflets, the great Quantities of liquid includes. In practice leads this leads to pump failure and filter clogging during fluid delivery.

Fat-based force and fuels, such as mixtures of fatty acid methyl esters show when cooling a similar one adverse behavior, as is the case of paraffinic fuels is known. Thus, for example, when cooling from Biodiesel based on rapeseed oil a crystal network of palmitic acid methyl ester and stearic acid methyl ester crystallites, causing filter clogging in the supply system to the combustion units to lead can.

In order to improve the described unfavorable cold behavior, a number of methods have become known:
Dewaxing of fuels, fuels or oils can be accomplished by selective adsorption on molecular sieves, by deposition as urea inclusion compounds, by solvent extraction or by fractional crystallization separation. In the case of grease-based fuels, the separation of fatty acid methyl esters which are difficult to dissolve in the cold is possible by means of fractional crystallization, which is referred to as "winterization".

to Improvement of the adverse cold behavior be the paraffinic fuels, fuels, oils and the fat-stemmed Fuels and fuels in practice so-called pour point improvers (PPD, Pour point depressant) and anti-settling agents (WASA, Wax Anti Settling Additives added).

pour point depressants modify crystal growth by being the fastest growing surfaces the paraffin crystals are deposited. The outer shape of the growing Crystals changes from needle or leaflet shape spherical. As a result, the cold flow properties of the additized improve Products, because no crystal network can form.

antisettling are common surfactant dispersants based on paraffin or fatty acid methyl ester crystals accumulate and their agglomeration by electrostatic or steric rejection prevent. The disadvantageous sedimentation which precipitates on cooling Paraffin crystals is thereby prevented.

in the Contrary to these usually Added additives is the targeted use of nucleating agents to improve the cold properties not yet common, because reliable effective, cost-effective additions have not become known.

It is already known that dendritic polymers having a hydrophobic outer shell can serve as nucleating agents in the preparation of small cell foams. This is what the patent teaches US 5,393,795 in that the nucleating agents claimed there can promote the formation of uniformly small gas bubbles in the production of foams.

In the patent US 5,418,301 describes the production of hyperbranched polyesters, which are terminally esterified with fatty acids and are suitable as constituents of coating resins or lubricants. The patent, however, makes no reference to the use of such polyesters as nucleating agents.

Furthermore, as a teaching of the patent US 5,906,970 It is known that dendrimers based on polyamidoamines are suitable in principle as flow improvers for fossil and fat-based fuels. The disadvantage is that the dendrimers described in the patent are accessible only by very complex, multi-step synthesis and therefore not previously used in the art.

Task and solution the task

It It was therefore an object to provide nucleating agents which in paraffinic crude oils, fuels, Fuels, oils or lubricants already in low concentrations the cold flow behavior can improve and in a simple way for the respective matrix can be optimized. Another task was to provide nucleating agents which are produced in grease and fuels already in low concentrations the cold flow behavior can improve and in a simple way for different composite grease-based fuels can be optimized.

nach Patentanspruch 1, wobei
n oder m unabhängig voneinander 0, 1 oder n+m<k,
und k 10 bis 500 sein können,
R gleiche oder verschiedene unverzweigte, gesättigte Alkylreste mit 8 bis 40 C-Atomen bedeutet,
M1 ein gleicher oder verschiedener organischer, löslichkeitsvermittelnder Rest mit 10 bis 1000 C-Atomen ist,
M2 ein gleicher oder verschiedener organischer, dispergierend wirkender Rest mit 10 bis 100 C-Atomen ist, der wenigstens ein N-Atom enthält und der ungeladen oder zwitterionisch sein kann
L1, L2 und L3 jeweils eine gleiche oder verschiede divalente Ester-, Carbonat-, Ether-, Thioether-, Amid-, Urethan-, Harnstoff- oder eine -C(O)-CH₂-CH₂-NR'-Gruppe ist,
und R' ein unverzweigter, gesättigter Alkylrest mit 8 bis 40 C-Atomen ist.This object is achieved by hyperbranched polymers as nucleating agents of the formula (I)

according to claim 1, wherein
n or m are independently 0, 1 or n + m <k,
and k can be from 10 to 500,
R is the same or different unbranched, saturated alkyl radicals having 8 to 40 carbon atoms,
M1 is an identical or different organic, solubilizing radical having 10 to 1000 carbon atoms,
M2 is an identical or different organic, dispersing radical having 10 to 100 carbon atoms, which contains at least one N atom and which may be uncharged or zwitterionic
L1, L2 and L3 are each the same or different divalent ester, carbonate, ether, thioether, amide, urethane, urea or a -C (O) -CH ₂ -CH ₂ -NR 'group .
and R 'is an unbranched, saturated alkyl radical having 8 to 40 carbon atoms.

These Nucleating agents can alone or in combination with known pour point improvers and / or Anti-settling agents in paraffinic crude oils, fuels, fuels, oils, lubricants or in fat Fuels in a concentration range of 0.005 to 5 weight percent preferably from 0.01 to 2 percent by weight, more preferably from 0.05 - 1 Percent by weight, to be added.

mode of action

The The following model presentations are intended to explain the concept of the invention, without to restrict him.

Crooked molecular Surfaces, which carry paraffinic end groups may contain other unbranched paraffins store and store. This spontaneously forms crystalline areas, which can lead to further crystal growth. In difference for homogeneous nucleation, by the contribution of surface energy is inhibited, here any attachment of a paraffin molecule is energetic advantageous.

A model of this induced homogeneous nucleation shows 1 ,

there stands for -L- a divalent group containing the hyperbranched polymer core a terminal Linked alkyl group.

The nucleating agent according to the invention can according to this Model presentation regarded as homogeneously dissolved nano-crystal germs become.

at decreasing temperature decreases the relative supersaturation of paraffins in paraffin-containing Fuels, fuels, oils or lubricants too. An addition of the nucleating agents according to the invention already works at low supersaturation the advantageous formation of many small crystallites, their growth form optionally by the addition of known polymeric crystal modifiers can be further influenced.

Surprised was found that the nucleating agent according to the invention also in fat Fuels, in particular in fatty acid methyl esters are effective. Obviously you can also fatty acid methyl ester chains analogous to paraffin chains on the outside of the nucleating agent induce crystallization.

The Optimization of the nucleating effect in paraffin-containing crude oils, fuels, Fuels, oils, Lubricants or in grease Fuels and fuels, for example, by the radius of curvature of the hyperbranched polymer core, by targeted variation of the Number of outward standing alkyl groups, the chain length of these alkyl groups and the chain length distribution respectively.

Furthermore, the solubility and the agglomeration behavior of the nucleating agents can be influenced by optionally bonding solubility-promoting radicals via a divalent group L ₁ and / or dispersing radicals via a divalent group L ₂ to the hyperbranched polymer core. 2 shows an example of solubilizing radicals. 3 shows an example of dispersing radicals.

manufacturing the nucleating agent

hyperbranched Polymers are obtained by providing branching-capable polyfunctional Monomers under controlled conditions one-stage to polydispersen Reacting polymers. The outer shape Such polymers may vary depending on the monomers used and the conditions of preparation almost spherical or ellipsoidal, cylindrical, hemispherical or one irregularly curved shape accept.

hyperbranched Polymers and their method of preparation are described, for example, in Hult et al. in "Advances in Polymer Science ", Pages 1 to 34, volume. 143 (1999), ed. J. Roovers, Springer Verlag New York, or in A. Sunder et al., Advanced Materials, page 235 to 239, Volume 12 (2000) in detail described.

in the In contrast, dendritic polymers are derived from a polyvalent starter molecule stepwise construction made by means of polyfunctional monomers. In general, the respective intermediates are after each synthesis stage purified to give, as an end product, an approximately monodisperse polymer to obtain.

dendritic Polymers and their method of preparation are for example in Tomalia et al. "Starburst Dendrimers: Molecular-Level Control of Size, Shape, Surface Chemistry, Topology and Flexibility from Atoms to Macroscopic Matter ", Angew. Chem. Int Ed. Engl., Vol. 29, pages 138 to 175 (1990).

The nucleating agent according to the invention have as a basis preferably hyperbranched polymers, since these in greater Variations are easy and inexpensive to produce.

The for the Preparation of the nucleating agents according to the invention suitable hyperbranched polymers bear from 10 to 500, preferably 20 to 300, more preferably 30 to 200 same or different terminal Hydroxyl, carboxyl or amino groups, preferably hydroxyl and Carboxyl groups.

Prefers become commercially available hyperbranched polymers as a basis for preparing the nucleating agents of the invention used. examples for such polymers are hyperbranched polyglycerols with terminal OH groups and hyperbranched amino-terminated polyethyleneimines of the company Hyperpolymers GmbH, Freiburg (Germany) under the name PG-2, PG-5, PG-8, PEI-5, PEI-25 and hyperbranched polyesters with terminal OH groups Perstorp, Perstorp (Sweden), under the name Boltorn H-20, Boltorn H-30, Boltorn H-40 are sold.

Furthermore, all hyperbranched polymers are suitable, which in the patent US 5,418,301 have been described.

wobei R' ein Wasserstoff-Rest oder ein unverzweigter gesättigter Alkyl-Rest mit 8 bis 40 C-Atomen darstellt.To prepare the nucleating agents according to the invention, the hyperbranched polymers mentioned are linked to suitable long-chain, terminally functionalized, unbranched alkyl compounds. The resulting linkage preferably consists of one of the following divalent groups.

wherein R 'represents a hydrogen radical or an unbranched saturated alkyl radical having 8 to 40 carbon atoms.

When divalent linking groups Ester, amide, or urethane groups are preferred.

• a) Hyperverzweigtes Polymer mit endständigen Hydroxyl-Gruppen + Fettsäuren oder aktivierte Fettsäurederivate, wie beispielsweise Fettsäurechloride,
• b) hyperverzweigtes Polymer mit endständigen Carboxyl-Gruppen oder endständigen Säurechlorid-Gruppen + Fettalkohole.

For example, to prepare a nucleating agent with ester-linked alkyl groups, one of the following combinations of starting materials can be reacted with each other:

• a) hyperbranched polymer having terminal hydroxyl groups + fatty acids or activated fatty acid derivatives such as fatty acid chlorides,
• b) hyperbranched polymer having terminal carboxyl groups or acid chloride terminal groups + fatty alcohols.

to Preparation of the nucleating agents according to the invention suitable long-chain compounds are unbranched, saturated fatty acids, fatty alcohols or fatty isocyanates each having 10 to 40 carbon atoms, preferably with each 14 to 24 carbon atoms. Also suitable are derived from it activated fatty acid or activated fatty alcohol derivatives.

Farther are unbranched, saturated primary and secondary Fatty amines of the structure HNRR 'suitable, where R and R 'are the same or different hydrogen or saturated unbranched aliphatic Radicals having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms, are.

Examples for preferred fatty acids or fatty acid derivatives are lauric, myristic, palmitic, stearic, arachidic, behenic, Cerotinic and melissic acid, and mixtures thereof and the acid chlorides derived therefrom, anhydrides, Methyl esters, as well as mixtures thereof.

Examples for preferred Fatty alcohols or fatty alcohol derivatives are lauryl, myristyl, palmityl, Stearyl, arachidyl, behenyl and cerotyl alcohol and mixtures and the derived chloroformates.

Also suitable for the reaction are technical mixtures of essentially unbranched C8-C24 alcohols, as they are called oxo alcohols from oxo processes.

Examples for preferred primary Amines are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecylamine, Aminopropylstearylamine, aminopropyllaurylamine, aminopropyloleylamine, and mixtures thereof.

Examples for preferred secondary Amines are dipalmitinamine, dioleylamine, dicoco fatty amine, dibehenylamine, especially Ditalgfettamin, and mixtures thereof.

Production process / reaction / reaction conditions

The Esterification of hyperbranched hydroxyl-functionalized polymers with fatty acids or conversely, hyperbranched carboxylic functionalized Polymers with fatty alcohols can be catalyzed or uncatalyzed, preferably acid catalyzed by heating with dehydration at reaction temperatures between 60 to 200 ° C, preferably between 80 to 180 ° C in if necessary, the melt or in a suitable solvent under application an azeotrope former.

suitable Esterification catalysts are, for example, toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, phosphoric acid, boron trifluoride, Tin tetrachloride, tetrabutyl orthotitanate, Sn powder or tin organic Compounds, such as so-called Fascat catalysts.

If the reaction in a solvent or solvent mixture carried out After the end of the reaction, the solvent can be added by evaporation increased Temperature are removed and the remaining melt through Dripping on a chilled Be granulated steel strip.

Instead of of the free fatty acids can also activated fatty acid derivatives, such as fatty acid chlorides or fatty acid anhydrides be used for esterification.

Full Information on catalysis and reaction in esterification and Transesterifications are detailed in the monograph by J. Otera, Esterification, Wiley-VCH (2003).

The Preparation of nucleating agents with amide-linked alkyl groups can by reaction of an amino-terminated hyperbranched polymer with fatty acids or activated fatty acid derivatives or conversely by reaction of a carboxyl-terminated hy-branched Polymers with primary or secondary fatty amines respectively. When using an amino-terminated hyperbranched Polymers are activated fatty acid derivatives as reaction components the fatty acid methyl ethers prefers.

Such Amidations are made by heating with elimination of water at reaction temperatures between 80 and 200 ° C, preferably between 80 and 160 ° C in the melt or in a suitable solvent, if necessary using an azeotrope former.

in the Trap of hydroxyl- or amino-terminated hyperbranched polymers can Akyl chains are introduced by a two-step reaction: In the first step is acrylic acid with the corresponding acrylic acid ester or the corresponding acrylamide with water leakage on known Made way. In a second stage, primary or secondary Fatty amines or long-chain alkyl thiols by means of a Michael addition with or without the use of a solvent in a temperature range between 80 to 140 ° C, preferably between 100 to 120 ° C, on the double bond added.

application Technology Modification of the nucleating agent

Next the for The nucleating effect of essential alkyl groups may be for another application optimization additional modifying groups in the outer shell the hyperbranched polymers are incorporated. The incorporation of the solubilizing or dispersing radicals takes place analogously to the type and Way, as already above at introduction the alkyl radicals described.

solubilizing leftovers

Thus, solubility-promoting radicals M1 of the formula (I) can be used to further optimize the overall effect of the nucleating agents according to the invention. If, for example, the nucleating agent in a paraffin-containing matrix has too low a solubility at room temperature, solubility-promoting radicals, such as branched polyalkylene, branched and unbranched polyoxalkylene radicals can be linked to the polymer core via a divalent group L ₁ .

• – Guerbetalkohole hergestellt aus Talgfettalkoholen,
• – Guerbetsäuren, hergestellt mittels Oxidation aus Guerbetalkoholen,
• – Einseitig blockierte Plytetrahydrofurane mit einem Molgewicht < 10000g/Mol,
• – Verzweigte und/oder ungesättigte Fettsäuren, wie beispielsweise 2-Ethylhexansäure, Isostearinsäure, Ölsäure, Elaidinsäure, Linolsäure,
• – Hydroxyl- oder Amino-terminierte Polyisobutene mit einem Molgewicht < 1000 g/Mol.

Examples of suitable solubilizing compounds are

• Guerbet alcohols made from tallow fatty alcohols,
• Guerbetsäuren, manufactured by oxidation from Guerbetalkoholen,
• Unilaterally blocked plytetrahydrofurans having a molecular weight <10000 g / mol,
• Branched and / or unsaturated fatty acids, such as, for example, 2-ethylhexanoic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid,
• Hydroxyl- or amino-terminated polyisobutenes having a molecular weight <1000 g / mol.

dispersing acting residues

Farther can according to formula (I) the hyperbranched polymer core with dispersing action Remains linked become. Such dispersing side chains M2, over the divalent groups L2 are bound to the hyperbranched core, can the agglomeration of the nucleating agent according to the invention and prevent the resulting very small crystallites and thereby settling the forming very small crystallites prevent.

The principle procedure in the production of such modified Nucleating agent can be to explain with an example: Hydroxyl-terminated hyperbranched polymers are used in a first Step by esterification with saturated, unbranched fatty acids converted to nucleating agents. This is the stoichiometry adjusted so that still free hydroxyl groups are present. Subsequently, this product is with an acid anhydride esterified. The resulting free carboxyl function is then through stoichiometric Addition of an amine compound converted into a salt.

Examples for acid anhydrides, the for this reaction is preferably used are maleic anhydride, phthalic anhydride and succinic anhydride.

preferred Amines are secondary and tertiary Fatty amines, but also cyclic compounds such as morpholine.

combination with known flow improvers and paraffin dispersants

The nucleating agent according to the invention can alone or in combination with known pour point depressants be applied.

• – Ethylen-Vinylacetat-Hexen-Terpolymere gemäß DE-A-34 43 475
• – Ethylen-Vinylacetat-Diisobutylen-Terpolymere gemäß EP-A-0 203 554
• – Mischpolymerisate des Ethylens mit Alkylcarbonsäurevinylesters gemäß EP-A-0 491 225
• – Fumarat-Vinylacetat-Kammpolymere gemäß EP-A-0 153 176
• – Kammpolymere aus einem C6-C24-α-Olefin und einem N-C6- bis C22-Alkylmaleinsäureimid gemäß EP-A-0 320 766

Suitable pour point depressants are copolymers or terpolymers or comb polymers based on ethylene and vinyl esters, polyacrylates or polymethacrylates. Examples of such products are:

• - Ethylene-vinyl acetate-hexene terpolymers according to DE-A-34 43 475
• Ethylene-vinyl acetate-diisobutylene terpolymers according to EP-A-0 203 554
• - Copolymers of ethylene with alkylcarboxylic acid vinyl ester according to EP-A-0 491 225
• Fumarate-vinyl acetate comb polymers according to EP-A-0 153 176
• - Comb polymers of a C6-C24-α-olefin and an N-C6 to C22-alkylmaleimide according to EP-A-0 320 766

• – Umsetzungsprodukte von Alkenylspirobislactonen mit Aminen gemäß EP-A-0 413 279,
• – Öllösliche Umsetzungsprodukte von Phthalsäureanhydrid mit Aminen gemäß EP-A-0 061 894,
• – Umsetzungsprodukte von Aminoalkylencarbonsäuren mit Aminen gemäß EP-A-0 597 278,
• – Umsetzungsprodukte von alternierenden Copolymeren auf der Basis von α,β-ungesättigten Verbindungen und Maleinsäureanhydrid mit primären Aminen und a liphatischen Alkoholen gemäß EP-A-0 154 177,
• – Copolymere auf der Basis von aliphatischen Olefinen und Maleinsäureanhydrid, wobei das Copolymere Ester- als auch Amidgruppen aufweist gemäß EP-A-0 283 293,
• – Umsetzungsprodukte von Copolymeren auf der Basis von Maleinsäureanhydrid und α, β-ungesättigten Verbindungen wie Styrol mit Dialkylaminen gemäß EP-A-0 436 151,
• – Copolymere auf der Basis von α,β-ungesättigten Olefinen mit mindestens 3 C-Atomen und α,β-ungesättigten Dicarbonsäureanhydriden, wobei die Dicarbonsäureanhydrideinheiten durch polymeranaloge Umsetzung mit Polyetheraminen oder Alkanolaminen in Imid-, Amid- und Ammonium-Einheiten überführt wurden EP-A-0 688 796.

Furthermore, the nucleating agents according to the invention can be used in combination with polar nitrogen-containing monomeric or polymeric paraffin dispersants (anti-settling agents). Examples of such nitrogen-containing paraffin dispersants are:

• Reaction products of alkenyl spiro-bis-lactones with amines according to EP-A-0 413 279,
• Oil-soluble reaction products of phthalic anhydride with amines according to EP-A-0 061 894,
• Reaction products of aminoalkylenecarboxylic acids with amines according to EP-A-0 597 278,
• Reaction products of alternating copolymers based on α, β-unsaturated compounds and maleic anhydride with primary amines and aliphatic alcohols according to EP-A-0 154 177,
• Copolymers based on aliphatic olefins and maleic anhydride, the copolymer having ester and amide groups according to EP-A-0 283 293,
• Reaction products of copolymers based on maleic anhydride and α, β-unsaturated compounds such as styrene with dialkylamines according to EP-A-0 436 151,
• Copolymers based on α, β-unsaturated olefins having at least 3 C atoms and α, β-unsaturated dicarboxylic acid anhydrides, the dicarboxylic anhydride units being converted into imide, amide and ammonium units by polymer-analogous reaction with polyetheramines or alkanolamines. A-0 688 796.

combination with other additives

The nucleating agent according to the invention can alone or in combination with other additives such as Antioxidants, anti-corrosion agents, anti-wear or lubricity additives, Dyes or markers, antistatic agents, cetane improvers, demulsifiers, Anti-foam agents or metal deactivators are used.

application the compounds of the invention

The nucleating agent according to the invention find use as additive in paraffinic crude oils, fuels, Fuels, oils or lubricants and in grease fuels, fuels or oils.

Examples for middle distillates are refinery products with a boiling range of about 150 - 500 ° C, which as heating oils, Diesel fuel kerosene, jet fuel are available.

Farther are the nucleating agents according to the invention especially for Hydrocarbon mixtures from technical or semi-technical Fischer-Tropsch processes suitable. Such fuels are u. a. known as "Synfuel" or "Sunfuel". Furthermore you can the nucleating agents according to the invention be used in paraffinic fuels and fuels based on pyrolysis oils. The extraction of such pyrolysis oils is, for example, in H. Kopetz, T. Weber, W. Palz, P. Chartier, G.L. Ferrero (ed.), Biomass for Energy and Industry, Proceedings of the International Conference Würzburg, Germany 8-11 June 1998 described.

Examples for grease-based power and fuels are fatty acid methyl esters, made from rapeseed oil, soybean oil, palm oil, beef tallow, Sunflower oil, Used cooking oil from restaurants and mixtures thereof. As well are the nucleating agents according to the invention good in mixtures of middle distillate products with fat Fuels, especially in mixtures of fatty acid methyl esters with Diesel fuel in mixing ratios from 1:99 up to 99: 1.

The advantageous effect of the nucleating agent according to the invention is based on the fact that in the aforementioned products already at a very low supersaturation the precipitated paraffin constituents or the corresponding fatty acid esters a simultaneous and throughout the product matrix detecting crystal growth starts. The fluidity The product remains on cooling over a huge Temperature range obtained.

Farther can the nucleating agents according to the invention as additives (Seed crystals) in the recovery of paraffin waxes from petroleum products, for dewaxing lubricating oils or for adjusting the flow properties used by greases.

detailed Information on the production of paraffin waxes and dewaxing found in M. Freund, Paraffin Products, Elsevier Scientific Publishing Company (1982)

The nucleating agent according to the invention be paraffinic fuels, fuels, oils or Lubricants and grease Fuels in a concentration range of between 0.005 and 5% by weight, preferably 0.01-2 Percent by weight, more preferably 0.05-1% by weight.

to easier dosage can liquid or pasty Concentrates made with up to 70 weight percent nucleating agent become. As a solvent for the Preparation of these concentrates is advantageous to be added Matrix used. Other suitable solvents are chlorinated hydrocarbons, such as dichloromethane or chloroform, liquid isoparaffins, Aromatics such as toluene, xylene, methylnaphthalene mixtures, high-boiling aromatic mixtures such as solvent naphtha.

The Temperature during the incorporation of the nucleating agent according to the invention into a matrix is chosen so that one homogeneous solution is formed with the matrix. The control, whether the nucleating agent homogeneously dissolved is, by investigative methods, in colloid chemistry common are such as microscopy, light scattering or ultracentrifugation respectively.

suitable Incorporation temperatures are 20 to 120 ° C, preferably 30 to 100 ° C, especially preferably 40 to 80 ° C.

test methods for examination of effectiveness

The following test methods were used to assess the effectiveness of the nucleating agents according to the invention:
Test A: Determination of filterability: CFPP value (Cold Filter Plugging Point) determined according to DIN EN 116
Test B: The additized products were stored in 1000 ml graduated cylinders for 20 hours in a refrigerated cabinet at -13 ° C. Subsequently, the volume and appearance of the paraffin phase as well as the liquid phase were determined visually.

Examples:

The The following examples 1 to 8 are shown in the attached drawing figures 4 to 11 each shown graphically.

Example 1 (Additive A)

Apparatus: 250 mL three-necked flask equipped with internal thermometer, reflux condenser with Dean-Stark water separator, mechanical stirrer, Argon introduction to inerting and heating bath.

In the apparatus are weighed as reaction components:
22.0 g Boltorn H40, hydroxyl-terminated hyperbranched polymer
21.3 g of stearic acid
19.2 g of palmitic acid
50 ml of xylene
0.2 g of p-toluenesulfonic acid

The The reaction mixture was stirred heated to boiling. This was a weak argon stream through the reaction solution passed and collected the formed reaction water. It was heated until a sample showed an acid number <5 mg KOH / g.

Subsequently was the solvent distilled off (internal temperature 155 ° C) and the remaining melt for 30 min at 130 ° C in water jet vacuum from the residual solvent and fleeting Components released.

Subsequently was the melt dripped onto a cold sheet and thereby pastilized. The colorless waxy product is in diesel fuel at room temperature and biodiesel readily soluble.

Example 2 (additive B)

The experiment from Example 1 was repeated with the following initial weights:
22.0 g Boltorn H40
42.6 g of stearic acid
5.6 oleic acid
0.2 ml of methanesulfonic acid as the esterification catalyst
50 ml of xylene

The colorless waxy product is in diesel fuel at room temperature and biodiesel readily soluble.

Example 3 (additive C)

In of an apparatus as described in Example 1, 22.0 g Boltorn H40, 42.6 g of stearic acid and 0.2 ml of methanesulfonic acid in 70 ml of toluene with stirring and refluxing for 4 h heated and the reaction water removed. Subsequently was a mixture of 3.6 g of acrylic acid and 0.1 g of methylhydroquinone and the reaction solution under stir for further Heated for 4 h. In the next Step was the solvent and the unreacted acrylic acid distilled off in a water-jet vacuum. The internal temperature should not exceed 120 ° C. To the melt was added 5.2 g of distearylamine and added for 2 h Stirred at 120 ° C. Subsequently was the melt poured onto a cold sheet and the solidified mass granulated.

Example 4 (Additive D)

In of an apparatus as described in Example 1, 22.0 g Boltorn H40, 38.4 g palmitic acid and 0.1 g of p-toluenesulfonic acid in 50 ml of xylene with stirring and refluxing heated until a sample showed an acid number <5 mg KOH / g. Subsequently was the solvent and fleeting By-products distilled off in a water-jet vacuum at 120 ° C. To this melt was a mixture of 50 ml of diesel fuel, 3 g of stearyl isocyanate and 0.1 g of diazabicyclononane were added and stirred for 3 h. The resulting product mixture was diluted with 1 liter of diesel fuel and provided a ready to use additive solution represents.

Example 5 (Additive E)

In of an apparatus as described in Example 1, 18.0 g Boltorn H40, 3 g Boltorn H30, 44.0 g stearic acid and 0.1 g p-toluenesulfonic acid in 50 ml of xylene with stirring and refluxing heated until a sample showed an acid number <5 mg KOH / g. Subsequently was the solvent and fleeting By-products distilled off in a water-jet vacuum at 130 ° C. To this melt was a mixture of 50 ml of waste fat methyl ester and 1.5 g of phthalic anhydride given and at 120 ° C for 2 h touched. To this reaction solution was subsequently a mixture of 3.3 g of N, N-dimethyl-stearylamine and 1 liter of diesel fuel added and stirred for 10 minutes. The resulting product mixture was a ready-to-use additive solution.

Example 6 (additive F)

In an apparatus as described in Example 1, 22.0 g of Boltorn H40, 42.6 g of stearic acid, 0.2 ml of methanesulfonic acid as the esterification catalyst and 60 ml of xylene were heated with stirring and refluxing until a sample has an acid number> 5 mg KOH / g showed. Subsequently, the solvent and volatile By-products distilled off in a water-jet vacuum at 130 ° C. To this melt was added 5.0 g of polyisobutenyl succinic anhydride (PIBSA, Mn 1000) dissolved in 1 liter of biodiesel and stirred for 10 minutes. The product mixture obtained was a ready-to-use additive solution.

The nucleating agents according to the invention were tested in various middle distillates (diesel fuel DK1, diesel fuel DK2) and fatty fuels (fatty acid methyl ester FAME1, prepared from rapeseed oil, fatty acid methyl ester FAME2, produced from used cooking oil), which exhibited the following properties:

These fuels were tested with the manufactured products A-F from Examples 1-6 and showed according to Test A and Test B the following results:

Out The examples show that the prepared nucleating agent in very low concentration lower the CFPP value to a well-dispersed, very fine Lead crystal mass.

Claims (20)

Nucleating agent based on hyperbranched polymers, characterized by the formula I.

where n or m independently of one another is 0 or 1 or n + m <k, k is about 10 to 500, R is identical or different unbranched saturated alkyl radicals having 8 to 40 C atoms, M1 denotes in each case a same or different organic solubility-promoting radical 10 to 1000 carbon atoms, M2 means a same or different organic dispersing radical having 10 to 100 carbon atoms, which contains at least one N-atom and which may be uncharged or zwitterionic, L1, L2 and L3 each have a same or various divalent ester, carbonate, ether, tioether, amide, urethane, urea or a -C (O) -CH ₂ -CH ₂ -NR 'group, in which latter R' is an unbranched saturated Alkyl radical having 8 to 40 carbon atoms, means. A nucleating agent according to claim 1, wherein k is the value 20 to 300 has. A nucleating agent according to claim 2, wherein k is the value 30 to 200 has. Nucleating agent according to one of claims 1 to 3, wherein R is an alkyl radical having 10 to 36 carbon atoms. A nucleating agent according to claim 4, wherein R is an alkyl radical with 12 to 32 carbon atoms. Nucleating agent according to one of claims 1 to 5, wherein L1, L2 and L3 are each an ester or an amide group is. Nucleating agent according to one of claims 1 to 5, wherein R 'a Alkyl radical having 10 to 36 carbon atoms. Nucleating agent according to claim 7, wherein R 'is an alkyl radical 12 to 32 carbon atoms. Use of a nucleating agent according to one of claims 1 to 8 for improving the cold flow behavior in paraffinic crude oils, Fuels, fuels, oils, Lubricants or in grease Fuels in a concentration range of 0.005 to 5 weight percent. Use according to claim 9 in a concentration range from 0.01 to 2% by weight. Use according to claim 10 in a concentration range from 0.05 to 1 percent by weight. Use according to any one of claims 9 to 12 in combination with a pour point improver and / or an anti-settling agent. Process for the preparation of a nucleating agent according to one of the claims 1 to 8 using hyperbranched polymers with 10 to 500 identical or different terminal hydroxyl, carboxyl or amino groups by linkage with long-chain, terminal functionalized unbranched alkyl compounds. The method of claim 13, wherein as hyperbranched Polymer hyperbranched polyglycerines with terminal OH groups or hyperbranched Polyethyleneimines with terminal Amino groups or hyperbranched polyesters with terminal OH groups be used. The method of claim 1 or 2, wherein hyperbranched Polymers with 20 to 300 terminal groups be used. The method of claim 15, wherein hyperbranched Polymers with 30 to 200 terminal Groups are used. Method according to one of claims 13 to 16, wherein as long-chain Compounds unbranched saturated fatty acids, Fatty alcohols or fatty isocyanates or derivatives derived therefrom Fatty acid- or activated fatty alcohol derivatives each having 10 to 40 carbon atoms. The method of claim 17, wherein the long chain Compounds each have 14 to 24 carbon atoms. A process according to any one of claims 13 to 16, wherein the long chain compounds are unbranched ge saturated primary or secondary fatty amines of the structure HNRR 'are where R and R' are the same or different each hydrogen or saturated unbranched aliphatic radicals having 10 to 30 carbon atoms. The method of claim 19, wherein the aliphatic Radicals each have 14 to 24 carbon atoms.