EP2530138A1 - Lubricant with reduced remnant viscosity - Google Patents

Abstract

Lubricant comprises a polymer-ionic liquid mixture, or a polymeric ionic liquid. Independent claims are also included for: (1) the polymer-ionic liquid mixture or the polymeric ionic liquid exhibiting a conductivity of 2000-10000 mu s/cm, a pH of 5-10, a pour point of greater than -15[deg] C, and a viscosity of 10-150 mm 2>/s at 40[deg] C; and (2) preparing the polymer-ionic liquid mixture, comprising separating salts.

Description

The invention relates to lubricants which contain a mixture of an ionic liquid and a polymer or a polymeric ionic liquid (so-called PIL "polymeric ionic liquid").

In all devices where mechanical parts move relative to each other, friction and wear occurs. The task of lubricants is to reduce friction in such cases and to minimize signs of wear.

In the field of lubricants, liquid lubricants are the most widely used and subject to special requirements. Their properties must be adapted to the intended use and the respective operating conditions. For example, they should have a viscosity-temperature and viscosity-pressure behavior suitable for the particular application, possess a low pour point and be as non-volatile as possible, have a high temperature, shear, and oxidation stability and should be hydrolyzable. and be radiation-proof in special cases. In addition, a liquid lubricant should be environmentally friendly.

In the field of liquid lubricants, the cooling lubricants or cooling lubricants (abbreviation: KSS, see DIN standard DIN 51385) represent a separate class. In production technology, they are used for separating and forming on machine tools the heat dissipation and reduction of friction between Tool and workpiece through lubrication. In addition, they are used in some machining processes to remove the chips by rinsing from the work environment.

Viscous, aqueous fluids can only be used for technical lubrication purposes if other requirements are also met, such as corrosion protection against iron, aluminum and non-ferrous metals and their alloys, tribological effectiveness in contact between the tool and workpiece, stability against microbial colonization, high rinsing - and mesh effect to remove abrasion and chips from the cutting zone and fulfill all obligations under European Chemicals Law.

The crucial property of a lubricant for both hydrodynamic and hydrostatic lubrication is its dynamic viscosity η. It is dependent on pressure and temperature. Liquids have a substance-specific viscosity, which can be changed by application of special additives; These include predominantly polymers. As is known, these polymers, also referred to as so-called viscosity index (VI) improvers, are very effective in non-water-miscible liquids, e.g. Mineral oils and ester oils.

When water is used as the polar liquid, water-soluble polymers, e.g. Cellulose derivatives, sugars, sugar derivatives, polyvinylpyrrolidone compounds successfully used.

So revealed the WO 2009/106359 a low to high viscosity waterborne lubricant composition that is mineral oil free and contains polymeric lubricants. In this case, the carboxymethylcellulose derivatives prove to be very suitable.

However, the use of polymers in lubricants also brings disadvantages. So far, known polymeric lubricant systems yield after evaporation of the water content of viscous, partially solid residues that lead in practice to disruption and technical overhead (in particular by cleaning). So residues affect the lubricity and can lead to increased wear. Their removal can be very time consuming and costly.

The invention is therefore based on the object of providing a polymer-based lubricant which is at least improved with respect to the abovementioned disadvantages. This object is achieved according to the invention by the provision of a lubricant containing a mixture of a polymer and an ionic liquid (polymer-IL mixture) or a polymeric ionic liquid (PIL).

It has been found that the use of a polymeric ionic liquid or a polymer-IL mixture in a lubricant prevents the formation of a viscous or solid residue. Thus, the lubricity is maintained even under heavy use and the wear of the material is minimized. A costly and time-consuming removal of the residue is no longer necessary.

Of particular importance here is that a lubricant by the addition of a polymeric ionic liquid or a polymer-IL mixture meets the tribological requirements by having a suitable viscosity-temperature and viscosity-pressure behavior, a low pour point (pour point) has and further having high temperature and oxidation stability.

In addition, such a lubricant is compatible with the materials of construction used.

The ionic liquids used for the lubricants represent a new way to adapt the lubricants to the specific requirements. The physical and chemical properties of ionic liquids can be selectively varied over a wide range by suitable selection of the cations and anions used.

A particular advantage of the invention lies in the formation of a film-like residue, which causes oxidation protection and thus corrosion protection.

Since this residue film is also water-soluble, it can be removed quickly and easily, thus allowing easy reuse of the residue-free workpiece.

Furthermore, the lubricants according to the invention have high shear stability and stability in water and can be prepared independently of the temperature. The addition according to the invention of anticorrosion, lubrication-wear protection additives and wetting agents and solubilizers assures the viscous water solution of all the properties that are necessary for use in metalworking.

Preferably, the lubricant according to the invention is a water-based lubricant, ie it contains water as the starting base. The finished lubricant Accordingly, it is present as a single-phase aqueous solution or as an emulsion / dispersion or colloid with water as the outer phase.

The lubricant according to the invention is preferably a water-based cooling lubricant.

The lubricant composition according to the invention preferably has a proportion of the polymer IL mixture or of the polymeric ionic liquid in the range of up to 10.0% by weight of the aqueous phase, more preferably in the range of up to 5% by weight and especially of 0.3 to 2 , 0% by weight based on the finished lubricant or on the possibly present aqueous phase.

In one embodiment of the invention, the lubricant is characterized in that the polymer-IL mixture or the polymeric ionic liquid contains a cation which is selected from the group consisting of ammonium cations, guanidinium cation, imidazolium cations, morpholinium cations. Cations, phosphonium cations, piperidinium cations, pyridinium cations, pyrrolidinium cations and sulfonium cations.

For a polymeric ionic liquid comprising a cationic polymer, the cations listed may also be functional groups of the polymer, which polymer may also carry different cationic groups.

For a polymeric ionic liquid comprising an anionic polymer, the listed cations, or mixtures thereof, may function as cationic counterions.

Specific examples of the preferred cations include:

Ammonium cation:

Ethyl dimethyl (2-methoxyethyl) ammonium, ethyl dimethyl propyl ammonium, ethyl dimethyl propyl ammonium, (2-hydroxyethyl) trimethyl ammonium, methyl trioctyl ammonium, tetrabutyl ammonium and tetramethyl ammonium.

Imidazolium cation:

1. a) Disubstituted imidazolium cation: 1-cyanomethyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-benzyl-3 -methylimidazolium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium, 1-propyl-3-methylimidazolium, 3-propyl-1-methylimidazolium.
2. b) Trisubstituted imidazolium cation: 1-butyl-2,3-dimethylimidazolium, 2,3-dimethyl-1-propylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1- (2- hydroxyethyl) -3-methylimidazolium.

Morpholinium cation:

N-methoxyethyl-N-methylmorpholine, 4- (2-methoxyethyl) -4-methyl morpholinium.

Phosphonium cation:

Trihexyl (tetradecyl) phosphonium

Piperidinium cation:

1- (2-methoxyethyl) -1-methylpiperidinium

Pyridinium cation:

N-butyl-3-methylpyridinium, N-butyl-4-methylpyridinium, N-butylpyridinium, 1-ethyl-3-hydroxymethylpyridinium, 1-ethyl-3-methylpyridinium, N-hexyl-4- (dimethylamino) pyridinium, N-hexylpyridinium and N - (3-hydroxypropyl) pyridinium

Pyrrolidinium cation:

1-butyl-1-methylpyrrolidinium, 1,1-dimethylpyrrolidinium and 1- (2-methoxyethyl) -1-methylpyrrolidinium

Sulfonium cation:

triethylsulfonium

In one embodiment of the invention, the lubricant is characterized in that the polymer-IL mixture or the polymeric ionic liquid contains an anion which is selected from the group consisting of carboxylates, nitrate, borates, cyanates, amides, imides, phosphates, Sulfates, sulfonates, tricyanomethane and nonaflate.

For a polymeric ionic liquid comprising an anionic polymer, the listed anions may also be functional groups of the polymer, which polymer may also carry various anionic groups.

For a polymeric ionic liquid comprising a cationic polymer, the listed anions, or mixtures thereof, may function as anionic counterions.

For the preferred anions, mention may be made in detail, for example:

Borate anion:

Cyanoborates, in particular tetracyano borate, fluoroborates, in particular tetrafluoroborate, and oxalato borates, in particular bis [oxalato (2 -)] borate and bis [oxalato (2 -) - O, O ⁺ ] borate

Halide anion:

Bromides, iodides and fluorides, in particular cetylamine hydrofluoride, triflate or tetrafluoroborate

Imide anion:

Bis (trifluoromethylsulfonyl) imide

Phosphate anion:

Alkyl phosphates, in particular dimethyl phosphate and / or diethyl phosphate, fluoroalkyl, in particular tris (pentafluoroethyl) trifluorophosphate, and fluorophosphates, in particular hexafluorophosphate

Sulfate anion:

Hydrogen sulfate, methyl sulfate, octyl sulfate, ethyl sulfate, n-butyl sulfate, n-hexyl sulfate, 2- (2-methoxyethoxy) ethyl sulfate

Sulfonate anion:

Trifluoromethanesulfonate, methanesulfonate and tosylate (p-toluenesulfonate).

The amount of possible ILs that are suitable for ensuring the water-solubility of the film-like residue and high tribological performance data is very large.

Preferably, ILs with a relatively low viscosity in the range of 50 cSt, measured in the range of 40 to 50 ° C should be used.

A preferred embodiment of the invention additionally contains an IL which contains a di- or trisubstituted imidazolium cation, more preferably a disubstituted imidazolium cation, particularly preferably an ethylmethylimidazolium cation.

Specific embodiments of the ILs to be used are: 1-ethyl-3-methylimidazolium tetrafluoroborate, 1- (2-hydroxyethyl) -3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1,3-dimethylimidazolium methylsulfate, 1-ethylpyridinium tetrafluoroborate, 1-isobutenyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, and 1-methyl-3-propylimidazolium hexafluorophosphate.

In a further embodiment, the polymer of the polymer-IL mixture or the polymeric ionic liquid is a natural, synthetic or chemically modified polymer, preferably polysaccharide, more preferably a cellulose derivative and especially carboxymethyl cellulose or a derivative thereof.

• völlige Wasserlöslichkeit des Gemisches
• keine Zersetzung bei Temperaturen > 100°C
• Bildung eines niedrig viskosen Rückstandes mit V₄₀< 200 mm²/s
• Verbesserte Schmierungseigenschaften

In a preferred embodiment of the invention, a mixture of carboxymethylcellulose salts with IL is used. The resulting completely water-soluble, polymeric liquids lead as an additive to lubricants having surprising properties according to the invention:

• complete water solubility of the mixture
• no decomposition at temperatures> 100 ° C
• Formation of a low viscous residue with V ₄₀ <200 mm ² / s
• Improved lubrication properties

Preferably, the lubricant according to the invention is characterized in that it contains exactly one ionic liquid, preferably an ionic liquid containing an imidazolium cation and exactly one polymer, preferably carboxymethylcellulose or a derivative thereof, or that it contains as PIL an imidazolium salt of carboxymethylcellulose.

• bis zu 5 Gew.% Netzmittel und/oder Emulgatoren und/oder Lösungsvermittler,
• bis zu 1 Gew.% Entschäumer,
• bis zu 1 Gew.% Schwermetallinhibitoren,
• bis zu 15 Gew.% Korrosionschutzverbindungen,
• je bis zu 10 Gew.% wasserlösliche Hochdruckadditive, Schmierfähigkeits- und Verschleißschutzverbesserer, sowie
• bis zu 0,5 Gew.% Biozide.

In one embodiment of the invention, the lubricant composition additionally contains at least one of the following constituents in the stated proportions:

• up to 5% by weight wetting agents and / or emulsifiers and / or solubilizers,
• up to 1% by weight defoamer,
• up to 1% by weight of heavy metal inhibitors,
• up to 15% by weight of corrosion protection compounds,
• up to 10% by weight of water-soluble high-pressure additives, lubricity and wear protection improvers, as well as
• up to 0.5% by weight of biocides.

Specific examples of substance groups for the listed additives include:

Wetting agents, emulsifiers and solubilizers:

monohydric or polyhydric alcohols and alcohol ethoxylates with at least 5 moles of EO (ethylene oxide) and ethanol ethers

defoamers:

Modified siloxanes or silicic acid derivatives

Heavy metal inhibitors:

Substances based on water-soluble triazole and thiadiazole derivatives

Corrosion protection additives:

Reaction products of fatty acids with at least C8 chain length with alkanolamines such as monoethanolamine, triethanolamine, diglycolamine, isobutanolamine or hydroxides such as potassium hydroxide, sodium hydroxide

Lubricity improver:

Water soluble ester compounds and polymeric ethylene oxide (EO) or ethylene oxide / polypropylene oxide (EO / PO) based glycol compounds

High-pressure additives:

These are water-soluble phosphoric acid partial esters, neutralized sulfurized fatty acids and esters, and neutralized thiol derivatives.

Wear additives:

Water-soluble phosphoric acid derivatives, in particular neutralized phosphoric acid partial ester derivatives

Biological stability enhancers / biocides:

Formaldehyde-releasing compounds, especially hexahydrotriazine compounds, methyl bisoxazolidine compounds; Heterocycles, especially Benzisothiazolidinverbindungen, Natriumpyrithion and Isothiazolonverbindungen

Particularly preferred is a lubricant composition according to the invention whose kinematic viscosity covers a range of about 2 to 50 mm ² / s at 40 ° C and their lubricity in Brugger wear protection tests specific surface pressures ≥ 30 N / mm ² and in Reichert wear protection tests values of 2000 N. / cm ² .

• Leitfähigkeit im Bereich von 1.000 bis 20.000 µS/cm
• pH-Wert im Bereich von 7,0 bis 10,0
• Pourpoint im Bereich von -5 bis -30 °C
• Viskosität im Bereich von 2 bis 100mm²/s

In a further embodiment of the invention, the lubricant according to the invention has one or more of the following typical data:

• Conductivity in the range of 1,000 to 20,000 μS / cm
• pH in the range of 7.0 to 10.0
• Pour point in the range of -5 to -30 ° C
• Viscosity in the range of 2 to 100mm ² / s

• Leitfähigkeit im Bereich von 2.000 - 10.000 µS/cm
• pH-Wert im Bereich von 5,0 - 10,0
• Pourpoint im Bereich von < -15 °C
• Viskosität im Bereich von 10 - 150 mm²/s bei 40 °C

The lubricant according to the invention is preferably characterized in that the anhydrous residue has a maximum film viscosity of V ₄₀ <200 mm ² / s and the poly-IL mixture used to prepare the lubricant composition or the polymeric ionic liquid has one or more of the following typical data:

• Conductivity in the range of 2,000 - 10,000 μS / cm
• pH in the range of 5.0-10.0
• Pour point in the range of <-15 ° C
• Viscosity in the range of 10 - 150 mm ² / s at 40 ° C

In an additional aspect of the invention, this relates to a polymer-IL mixture or a polymeric ionic liquid which is characterized in that the cation is a quaternary ammonium ion and the anion is a polysaccharide, preferably a cellulose derivative, more preferably carboxymethylcellulose.

A further aspect of the invention relates to the use of a polymer-IL mixture or a polymeric ionic liquid as lubricants, anti-corrosion and / or thickening agents in lubricants.

In one embodiment of the invention, the lubricant according to the invention can be used as a water-based cooling lubricant for metal cutting, mechanical forming or high-performance grinding of carbide tools and gears as well as hydraulic, gear and / or drilling fluid.

production method Polymeric ionic liquid - PIL

The PIL can be prepared by polymerizing a reactive monomer salt. Suitable monomers are olefinic compounds such as allyl compounds and in particular acrylic and vinyl compounds. The polymerization can be carried out by the skilled worker reactions. This can be carried out, for example, as radical, as cationic, as anionic or as coordination polymerization. The polymerization may result in the reaction of only one type of monomer to a homopolymer, but it can also be polymerized several types of monomers, which then give a copolymer. Depending on the distribution of the various monomer types in the polymer, this leads to random, alternating, block or graft copolymers.

If the reactive monomer salt does not carry the counterion suitable for the ionic liquid, it may be exchanged or converted by one of the following methods before or after the polymerization. This will be described below with reference to the cationic monomer 1-vinylimidazolium [VIM] ⁺ with a halide anion X ^- :

On the one hand, the halide [VIM] ⁺ X ^- can be reacted with a Lewis acid MX _y . This forms a precursor for an ionic liquid of the type [VIM] ⁺ [MX _{y + 1} ] ^- .

In this case, often there are several anions in equilibrium, which the used ratio of the two components [VIM] ⁺ X ^- dependent and MX _y, as illustrated in the following equation:

Alternatively, a replacement of the halide anion X is ^- the desired anion possible. This can be done by adding a metal salt M ⁺ [A ^- ] which acts as a Lewis acid (with precipitation of M ⁺ X ^- ), via an ion exchanger or by displacing the halide ion by the Brønsted acid H ⁺ [A ^- ] (with release from H ⁺ X ^- ) so that the result is the salt [VIM] ⁺ [A ^- ].

In a particular embodiment of the invention, the salts which may be formed in the preparation of the polymer IL mixture or the polymeric ionic liquid are removed by filtration. For this purpose, a filter with a pore diameter between 1 to 20 microns, more preferably 5 microns, are separated.

These reactions, described with reference to a monomer, apply analogously to a cationic polymer. Furthermore, this also applies to an anionic monomer / polymer, wherein instead of the Lewis acid, a Lewis base and instead of the Brønsted acid Brønstedt base are used.

In one embodiment of the invention, the PIL can be prepared by quaternization of 1-vinylimidazole and subsequent polymerization (see the following figure). The desired anions can be introduced before or after the polymerization by anion exchange.

Poly-IL-mixture

In the simplest case, the preparation of the poly-IL mixture is carried out by mixing a preferably aqueous solution of the polymer with one or more ionic liquids. Alternatively, the preferably solid polymer may also be dissolved directly in the ionic liquid.

The polymer can be used as a neutral polymer or as a polymer salt. In a preferred aspect of the invention, a salt of carboxymethylcellulose, and more preferably the sodium salt of CMC, is used.

In the case that the salt of a polymer is used (such as a polymeric anion POL- with a cation M +), by mixing with the ionic liquid (for example consisting of cation BMIM ⁺ with anion X ^- ), the counterion of the polymer M + be replaced by the corresponding counter ion of the ionic liquid BMIM + according to the following equation:

M ⁺ POL ^- + BMIM ⁺ X ^- → BMIM ⁺ POL + M ⁺ X ^-

In a preferred aspect of the invention, the salt M ⁺ X- formed by this reaction is separated from the reaction mixture. This is done in a preferred manner by precipitation.

In a further aspect of the invention, the counterion of the polymer can also be modified by reaction with a Lewis acid or a Lewis base analogously to the reactions set forth for the PILs. Also an appropriate implementation with a Brønstedt base or Bronsted acid or ion exchange via an ion exchanger is possible.

DEFINITIONS

A lubricant in the context of the invention is a liquid mixture which causes a friction reduction of the base liquid (in particular water), which leads to an improvement of the tribological load capacity. According to DIN 51502, this presupposes the following properties: An increase of the surface pressure by at least 10 N / mm2, an increase of the specific surface pressure by at least 1.000 N / cm2 and / or an increase of the load by at least 1.000 N good load. These properties can be determined by methods known to the person skilled in the art, for example with Brugger wear test stand, Reichert friction wear balance and shell four-ball apparatus (VKA).

An ionic liquid ("English" ionic liquid "IL") in the context of the invention is a salt whose melting point is below 100 ° C.

In the present invention, the term "polymeric ionic liquid" (PIL) refers to an ionic liquid in which there is at least one polymeric ion. A polymer in this case a chemical compound of chain or branched molecules (macromolecules), which in turn consists of the same or similar units (the so-called monomers). The polymeric ion may be present as a polymeric cation or as a polymeric anion. By a polymeric cation and anion are also understood zwitterions, i. Ions having both positive and negative charges, wherein, taking into account all charges, the polymeric cation carries a net positive charge and the polymeric anion carries a net negative charge. The PIL may also contain polymeric cations and polymeric anions, and in extreme cases may consist entirely of polymeric cations and polymeric anions.

A polymer in the context of the invention is a chemical compound of chain or branched molecules (macromolecules), which in turn consists of identical or similar units (the so-called monomers).

According to the invention, a polymer-IL mixture is defined as a mixture obtained by reacting at least one polymer with at least one ionic liquid.

According to the present invention, an anhydrous residue of a lubricant is defined as the residue which results after application of the test method described in Example 4. This method is the standard method for the analysis of lubricant residues published by the VKIS and involves the concentration of a lubricant sample for 24 hours at 70 ° C ± 2 ° C (see Example 4, point 8.1).

For the purposes of the present invention, a solid residue is defined as a "non-flowable" residue as obtained according to the test method described in Example 4. This method is the standard method for the analysis of lubricant residues published by the VKIS and includes the determination of the flow behavior on a vertically arranged watch glass (see example 4, point 8.2.1).

The film viscosity V40 reflects the viscosity of the anhydrous residue defined above. It describes the viscosity at T = 40 ° C and is determined according to DIN51562.

Examples Example 1: Lubricant containing 10% polymer-IL mixture

In 85% water, up to 1.2% alkalizing agent (alkanolamine or alkali metal hydroxide) is mixed with 0.7% anticorrosive acids and stirred until clear reaction (about 1 hour). Wetting agents, solubilizers, heavy metal inhibitors are then added and the reaction mixture is admixed by adding 10% of a polymer IL mixture (mixture of 1-ethyl-3-methylimidazolium carboxymethylcellulose (EMIM-CMC) and 1-ethyl-3-methylimidazolium diethyl phosphate (EMIM-CMC)). DEP) 1:10) to the desired viscosity. The result is a clear, viscous solution with an average viscosity of 4.0 mm ² / s at 20 ° C and a pH of 9.0-9.3.

Example 2: Lubricant containing 15% polymer-IL mixture

In 80% water, up to 1.2% alkalizing agent (alkanolamine or alkali metal hydroxide) is mixed with 0.7% anticorrosion acid and stirred until clear reaction (about 1 hour). After that, wetting agents, solubilizers, heavy metal inhibitors are added and the reaction mixture is adjusted to the desired viscosity by adding 15% of a polymer IL mixture (according to Example 1). The result is a clear, viscous solution with an average viscosity of 10.0 mm ² / s at 40 ° C and a pH of 9.0-9.3.

Example 3: Lubricant containing 35% polymer-IL mixture

In 60% water, up to 2.4% alkalizing agent (alkanolamine or alkali hydroxide) is mixed with 1.4% anticorrosive acid and stirred until clear reaction (about 1 hour). Thereafter, esters, high performance and wear protection additives and wetting agents, solubilizers and heavy metal inhibitors are added and the reaction mixture by the addition of 35% polymer-IL mixture (according to Example 1) adjusted to the desired viscosity. The result is a clear, viscous solution with an average viscosity of 46.0 mm ² / s at 40 ° C and a pH of 9.0-9.3.

Example 4: Analysis method for the assessment of coolant lubricant residues and testing of the redissolvability 1 Scope

Water-miscible and water-miscible cooling lubricants with a mineral oil content of max. 50% and mineral oil-free organic solutions.

Annotation:

For cooling lubricants with a mineral oil volume> 50%, which generally do not tend to stick, this test method is only conditionally applicable.

2. Purpose of the provision

The test method should provide information on whether the residues of water-mixed cooling lubricants in the application state tend to resinification or sticking to measuring tools, machine tools and workpieces. Furthermore, it should be checked whether a redissolution of the residues is given.

3rd term

Residue after this test is understood to be the mixture of substances remaining after evaporation of the aqueous phase from the water-mixed cooling lubricant. This substance mixture can have different consistency. Resolutability is understood to mean the soluble fraction of the residue after exposure to demineralized water, in short. Called water.

4. Brief description of the procedure

The water-mixed coolant is removed from the aqueous phase at a test temperature of 70 ° C ± 2 ° C. The residue is visually evaluated and weighed. Subsequently, the redissolution in the. Water at 25 ° C ± 1 ° C determined.

5. Equipment and chemicals

• Full pipette 20 A DIN 20690
• 2 watch glasses, outside diameter 100 mm, DIN 12341, curved
• 2 beakers 1000 cm ³ , low form, DIN 12332
• Separating funnels, as required with holding device 250 cm ³ , DIN 12451
• Tempering device, which is a setting of the test temperature to 70 ° C ± 2 ° C
• permitted (eg warming cabinet).
• Tempering device, which has a setting of the test temperature to 25 ° C ± 1 ° C
• allowed.
• Agitator, speed adjustable to 600 min.-1 and 750 min.-1, to which a stirring blade
• Stainless steel with a length of 120 mm, width of 19 mm and thickness of
• 1.5 mm belongs.
• Lid with watch glass holder (see Figure XX).
• Desiccator, z. B. according to DIN 12491
• Analytical balance, reading accuracy 1 mg, weighing range up to 150 g max.
• Funnel 80 DIN 12445
• Pleated filter made of filter paper 595 1/2 ø 185 mm
• Standard water according to DIN 51367 paragraph 6.1
• Solvent mixture, eg. B. 50 cm ^{3 of} toluene + 5 cm ^{3 of} water to 495 cm ^{3 of} anhydrous
• Isopropyl alcohol according to DIN 51558 / 7.3
• Demineralized water max 15 Js / cm-1

6. Sampling

The sampling takes place in accordance with DIN 51750 Part 1 and Part 2

7. Pretreatment of the sample 7.1 Inspection in delivery condition

According to DIN 51367 item 8.1, a 5% mixture of the coolant to be tested with standard water is produced. Note: By agreement, the operating water used in each case can also be used as batch water.

7.2 Testing in use

To separate the foreign oil, the sample is allowed to stand for 4 hours in a separating funnel. The aqueous phase is filtered through a pleated filter.

8. Implementation 8.1 Residue formation

20 cm ^{3 of} the water-mixed cooling lubricant are pipetted onto two residue-free, dried watch glasses weighed to the nearest 1 mg. The samples are concentrated in a drying oven at 70 ° C ± 2 ° C for 24 hours. Thereafter, the watch glasses are cooled for 1 hour in a desiccator to room temperature and weighed.

8.1.1 Result A

Weighing in g - empty weight Watch glass in g = dry residue in g (A)

8.2 Determination of the flow behavior and the consistency of the residue 8.2.1 Flow behavior

• Liegt die Zeit < 30 sec ist der Rückstand fließfähig.
• Liegt die Zeit > 30 sec ist der Rückstand nicht fließfähig

To determine the flow behavior of one of the two dried and weighed watch glasses between the thumb and index finger 30 sec. held that the watch glass edge forms a vertical. The time until the appearance of the first drop on the edge of the watch glass is measured:

• If the time is <30 sec, the residue is free-flowing.
• If the time is> 30 seconds, the residue is not fluid

8.2.2 Consistency

If the residue contains visible changes, this should be indicated, eg. B. crystalline precipitates. If the residue pulls threads, it is classified as sticky.

8.3 Determination of the re-solubility of the residue

The re-solubility is with the in illustration 1 reproduced test apparatus. In a 1000 cm ³ beaker low form of the stirrer with stirring blade is set 10 mm from the beaker bottom. Beaker with the. Fill water up to 35 mm from the top of the beaker. With constant stirring, the water is heated to 25 ° C ± 1 ° C with a suitable tempering. After reaching this temperature watch glass in the in Figure 2 pinch the illustrated holding device with curvature (concave) to the stirrer. Place cover with holding device on the beaker, set the speed of the stirrer to 600 min.-1 and set for 15 min. stir. Then put the watch glass 3 times in a beaker with the. Dip water. Drain for 15 seconds. If residues have formed on the reverse side of the watch glass, they must be removed with the cellulose cloth or cotton wool pad soaked in solvent mixture. Subsequently, the watch glass is dried for 2 hours at 70 ° C ± 2 ° C in a warming cabinet. Then cool to room temperature in a desiccator for 1 hour and weigh.

8.3.1 Result B

Weighing in g - empty weight Watch glass in g 0 residue in g (B)

9. Evaluation

$$\frac{C\times 100}{\mathrm{A}}=\%\mathrm{R}\ddot{\mathrm{u}}\mathrm{ckl}\ddot{\mathrm{o}}\mathrm{slichkeit}$$

Hierin bedeuten:

• A = g Gesamttrockenrückstand aus 8.1.1
• B = g Rückstand auf Uhrglas aus 8.3.1

The redissolvability is rounded off in mass fraction in% to 0.01%, calculated according to the following numerical value equation. $$\mathrm{A}\mathrm{-}\mathrm{B}\mathrm{=}\mathrm{C}$$

$$\frac{C\times 100}{\mathrm{A}}=\%\mathrm{R}\ddot{\mathrm{u}}\mathrm{ckl}\ddot{\mathrm{O}}\mathrm{solubility}$$

Herein mean:

• A = g total dry residue from 8.1.1
• B = g residue on watch glass 8.3.1

With regard to the rounding to the last place to be specified, DIN 1333 must be taken into account.

10. Indication of the test results

The assessment of the cooling lubricant residue and the redissibility in% by weight shall be indicated with reference to this supplementary sheet.

11. repeatability

Mass fraction in% = 10

Claims (20)

Lubricant, characterized in that it contains a polymer-IL mixture or a polymeric ionic liquid. Lubricant according to claim 1, characterized in that it is a water-based lubricant, and preferably a water-based cooling lubricant. Lubricant according to claim 2, characterized in that the proportion of the polymer-IL mixture or the polymeric ionic liquid in the range up to 35 wt.% Of the aqueous phase, preferably in the range of 0.3 to 2.0 wt.% Of the aqueous Phase is. Lubricant according to one of claims 1 to 3, characterized in that the polymer-IL mixture or the polymeric ionic liquid contains a cation which is selected from the group consisting of ammonium cations, guanidinium cation, imidazolium cations, morpholinium Cations, phosphonium cations, piperidinium cations, pyridinium cations, pyrrolidinium cations and sulfonium cations. Lubricant according to one of claims 1 to 4, characterized in that the polymer-IL mixture or the polymeric ionic liquid containing an anion is selected from the group consisting of carboxylates, nitrate, borates, cyanates, amides, imides, phosphates, sulfates , Sulfonates, tricyanomethane and nonaflate. Lubricant according to one of the preceding claims, characterized in that the polymer is a natural, synthetic or chemically modified polymer and is preferably carboxymethyl cellulose or a derivative thereof. Lubricant according to one of the preceding claims, characterized in that the polymer has cations selected from the group consisting of ammonium cations, guanidinium cation, imidazolium cations, morpholinium cations, phosphonium cations, piperidinium cations, pyridinium Cations, pyrrolidinium cations and sulfonium cations. or mixtures of these cations. Lubricant according to one of the preceding claims, characterized in that the polymer has anions selected from the group consisting of carboxylates, nitrate, borates, cyanates, amides, imides, phosphates, sulphates, Sulfonates, tricyanomethane and nonaflate, or mixtures of these anions. Lubricant according to one of the preceding claims, characterized in that the polymer-IL mixture or the ionic polymeric liquid contains an imidazolium cation, preferably an ethylmethylimidazolium cation. Lubricant according to one of the preceding claims, characterized in that it contains imidazolium cations and exactly one polymer, preferably carboxymethyl cellulose, or a derivative thereof, or that it contains as polymeric ionic liquid an imidazolium salt of carboxymethyl cellulose. Lubricant according to claim 5, characterized in that as further constituents up to 5 wt.% Wetting agents and / or emulsifiers, up to 1 wt.% Defoamer, up to 1 wt.% Heavy metal inhibitors, up to 15 wt.% Corrosion protection compounds, depending to to 10% by weight of water-soluble high-pressure additives, lubricity and wear protection improvers, up to 1% by weight of heavy metal inhibitors and up to 0.5% by weight of biocides. Lubricant according to one of the preceding claims, characterized in that its kinematic viscosity covers a range of about 2 to 50 mm ² / s at 40 ° C and its lubricity in Brugger wear protection tests specific surface pressures ≥ 30 N / mm ² and in Reichert wear protection tests Values of 2000 N / cm ² . Lubricant according to one of the preceding claims, characterized in that it has the following typical data: • Conductivity in the range of 0.5 - 20 mS / cm • pH in the range of 7-10 • pour point in the range of at least -10 ° C • Viscosity in the range of 2- 150 mm ² S at 40 ° C Lubricant according to one of the preceding claims, characterized in that the anhydrous residue has a maximum film viscosity of V ₄₀ <200 mm ² / s. A polymer-IL mixture or a polymeric ionic liquid, characterized in that they have the following typical data: • conductivity in the range of 2,000 - 10,000 μS / cm; PH in the range of 5.0-10.0; • pour point in the range of <-15 ° C, and • Viscosity in the range of 10-150 mm ² / s at 40 ° C A polymer-IL mixture or a polymeric ionic liquid, characterized in that the cation is a quaternary ammonium ion and the anion is a polysaccharide, preferably a cellulose derivative, more preferably carboxymethylcellulose. Use of a polymer-IL mixture or a polymeric ionic liquid as lubricants, anti-corrosion and / or thickeners in lubricants. Use of a lubricant according to one of the preceding claims as a water-based cooling lubricant for metal cutting, mechanical forming or high-performance grinding of carbide tools and gears as well as hydraulic, gear and / or drilling fluid. Process for the preparation of the polymer-IL-mixture according to one of the preceding claims, characterized in that possibly occurring salts are separated off. A method according to claim 19, characterized in that the possibly resulting salts are separated by a filter with a pore diameter in the range of 1 to 10 microns, preferably 5 microns.

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