DE102005026405A1 - Polymers Dithiophosphorsäurehydroxyfettsäureester, process for their preparation and their use as a lubricant additive - Google Patents

Abstract

The invention relates to novel polymeric Dithiophosphorsäurehydroxyfettsäureester. They are prepared by a process in which an epoxidized fatty acid ester with a substituted dithiophosphoric acid is reacted so that not all epoxy groups of the fatty acid ester are attacked. This is followed by intermolecular crosslinking to form hydroxyl groups. An alternative method is to crosslink the epoxidized fatty acid ester to a polymeric intermediate having unreacted epoxide groups and then react the free epoxide groups with the substituted dithiophosphoric acid to form hydroxyl groups. The polymeric Dithiophosphorsäurehydroxyfettsäureester invention are generally suitable as a lubricant additive, in particular for improving the wear protection effect and the aging stability of lubricants.

Description

The The present invention relates to novel polymers based on dithiophosphoric acid hydroxy fatty acid esters, Process for their preparation and their use as a lubricant additive.

metal dialkyl dithiophosphates have long been known and until today much used lubricant additives. They are mainly due to their multifunctional properties to improve the wear protection effect and aging stability of mineral oils, for the production of motor oils, Metalworking fluids, industrial oils and greases used. As particularly effective here the zinc salts of dialkyldithiophosphoric acids (zinc dialkyldithiophosphates) proved. However, these zinc compounds do not meet all requirements due to their metal or zinc content fair. The metals cause disturbing by ash formation Deposits on the lubricated friction elements.

One Another disadvantage of these Zinkdialkyldithiophosphate is their instability across from Acids and Water to form decomposition products, which is the shelf life of the base oil adversely affect odor, sludge formation and oil clouding.

metal-free dithiophosphoric acid are also known in the art.

In the DE 42 42 502 A1 describes metal-free lubricant additives based on addition products of glycidyl ethers and dialkyldithiophosphoric acids of different alkyl, aryl or mixed alkyl-aryl group structure.

In the DE 42 06 047 A1 also metal-free lubricant additives are described, which are attributed to corrosion-inhibiting properties. These are reaction products of epoxidized unsaturated fatty acid esters with lower or higher molecular weight sulfonic acids.

In the DE 42 31 073 A1 further lubricant additives are described which are formed by reaction of epoxidized fatty acids and fatty acid derivatives and phosphoric acid or their mono- or diesters.

disadvantage These known metal-free lubricant additives are the still weak acidity and hydrolysis and the low wear protection effect under pressure.

task The present invention is therefore metal-free lubricant additives to disposal to put, which the above-mentioned Do not have disadvantages.

These Task is achieved by polymeric Dithiophosphorsäurehydroxyfettsäureester according to claim 21 solved. These polymers are by a process according to claim 1 or claim 4 available.

The The invention also relates to a specific polymeric dithiophosphoric acid hydroxy fatty acid ester according to claim 22nd

Farther The invention relates to specific uses of the polymeric Dithiophosphorsäurehydroxyfettsäureester invention according to one the claims 29 to 31.

Further The invention relates to a lubricant according to claim 33, which is the polymeric Dithiophosphorsäurehydroxyfettsäureester contains.

preferred embodiments arise from the dependent ones Claims.

The inventive polymer Dithiophosphorsäurehydroxyfettsäureester have not been previously known in the art. Under The term "polymers" are also used here Oligomers understood that only a small number of repeat units can have.

In surprising example, it has been found that the polymers of the invention possess excellent lubricating properties. They also have one good wear protection effect under load, with the known metal-free lubricant additives is not achieved. Furthermore Improve the aging properties of a base oil and have a good acidity and hydrolysis resistance. Thus they fulfill the property profile of a modern lubricant additive without being caused by ash formation disturbing Deposits on the lubricated friction surfaces as with the metal-containing Lubricant additives occur.

The inventive polymer Dithiophosphorsäurehydroxyfettsäureester are available through two manufacturing routes, both in two steps respectively. In the first method, first epoxidized fatty acid esters reacted with substituted dithiophosphoric acids, where not all epoxide groups of the fatty acid ester to be attacked. In a further reaction step, the Polymerization with a multifunctional H-acidic compound via a intermolecular crosslinking and formation of hydroxyl groups. at the second method is epoxidized fatty acid esters with a multifunctional H-acidic compound so reacted that the epoxidized fatty acid esters intermolecular to a polymeric intermediate with free epoxide groups be networked. Subsequently the free epoxide groups with the substituted dithiophosphoric under Formation of hydroxyl groups implemented (inverse process). Both Manufacturing routes are described in detail below.

mit A = R₁O oder H,
wobei x eine Zahl von 0 bis 6 ist und R₁, R₂ und R₃ gleich oder verschieden sein können und wie nachfolgend definiert sind:

wobei R₄ H oder -CH₃ ist, m eine Zahl von 1 bis 40 ist, n eine Zahl von 1 bis 10 ist und p eine Zahl von 0 bis 8 ist,
mit einer substituierten Dithiophosphorsäure der Formel (II)

umgesetzt,
worin R₅ und R₆ gleich oder verschieden sein können und unabhängig voneinander ausgewählt sind aus H, Alkyl oder Aryl mit der Maßgabe, dass mindestens einer von R₅ und R₆ nicht H ist, wobei der Fettsäureester der Formel (I) mit der Dithiophosphorsäure der Formel (II) so umgesetzt wird, dass ein Zwischenprodukt mit nicht umgesetzten Epoxidgruppen gebildet wird.In step (a) of the first process according to the invention, an epoxidized fatty acid ester of the formula (I)

with A = R ₁ O or H,
wherein x is a number from 0 to 6 and R ₁ , R ₂ and R _{3 may be the} same or different and are as defined below:

wherein R _{4 is} H or -CH ₃ , m is a number from 1 to 40, n is a number from 1 to 10 and p is a number from 0 to 8,
with a substituted dithiophosphoric acid of the formula (II)

implemented
wherein R ₅ and R _{6 may be the} same or different and are independently selected from H, alkyl or aryl, with the proviso that at least one of R ₅ and R _{6 is} not H, wherein the fatty acid ester of formula (I) with the dithiophosphoric acid of the formula (II) is reacted so that an intermediate product is formed with unreacted epoxide groups.

In the epoxidized fatty acid ester of formula (I), x is a number from 0 to 6, preferably 1 to 4, more preferably 1 or 2 and most preferably 1. Thus, the fatty acid ester of formula (I) is in the case of x = 1 and A = R ₁ O derived from glycerol and in the case of x = 1 and A = H derived from propylene glycol.

In the radicals R ₁ , R ₂ and R _{3 of} the fatty acid ester of the formula (I) R _{4 is} H or -CH ₃ . m is a number from 1 to 40, preferably 7 to 29 and particularly preferably 10 to 16. n is a number from 1 to 10, preferably 2 to 4 and particularly preferably 2 or 3. p is a number from 0 to 8, preferably 2 to 5 and more preferably 3 or 4.

The individual methylene units (CH ₂ ) provided with the index m and the individual epoxide units (CHOCH) provided with the index n can be distributed in any order over the chain, ie in random, blockwise or alternating arrangement. However, it is preferred that at least 2 methylene units (CH ₂ ), more preferably 7 methylene units (CH ₂ ), follow the carbonyl group before one or more of the epoxide units (CHOCH) and again methylene (CH ₂ ) follows.

In a preferred embodiment are the epoxidized fatty acid esters of the formula (I) of epoxidized oils natural Derived from origin. The epoxidized oil can be natural Be selected from epoxidized soybean oil, linseed oil, rapeseed oil, sunflower oil and fish oil. This count on is only exemplary and limited the selection of epoxidized oils natural Not origin.

It is alike possible, synthetic epoxidized fatty acid esters to use, e.g. an epoxidized propylene glycol dioleate, epoxydated Glycol dioleate, epoxidized butanedioleate or epoxidized glycol dilaurylate.

preferably, is the percentage of oxirane oxygen in the fatty acid ester of the formula (I) greater than 2 wt .-% and particularly preferably greater than 3 wt .-%. The percentage Content of oxirane oxygen in an epoxy compound (e.g. the fatty acid ester of formula (I)) indicates how many grams of oxirane oxygen in 100 g of epoxy compound is contained, and is determined by Perchlorsäuretitration. These Method as described in A.J. Durbetaky, Anal. Chem. 28, 2000 (1956), R. R. Jay, Anal. Chem. 36, 667 (1964) or R. Deistra and E. Damen, Anal. Chem. Acta. 31, 38 (1964) is common to those skilled in the art known.

The substituted dithiophosphoric acid of formula (II) is preferably substituted on both O atoms, wherein R ₅ and R ₆ independently of one another are alkyl or aryl. Thus, the dialkyl, diaryl and mixed alkyl / aryl dithiophosphoric acids are preferably used. Even more preferred is when R ₅ and R _{6 are} each alkyl. The alkyl radicals preferably have 4 to 12 carbon atoms and more preferably 6 to 8 carbon atoms, and may be unbranched or branched. Examples include the compounds di-2-ethylhexyldithiophosphorsäure (R ₅ and R ₆ = 2-ethylhexyl), di-n-octyl-dithiophosphoric (R ₅ and R ₆ = n-octyl), di-iso-butyldithiophosphorsäure (R ₅ and R ₆ = iso-butyl), iso-butyl, 2-ethylhexyldithiophosphoric acid (R ₅ = isobutyl and R ₆ = 2-ethylhexyl). It is very particularly preferred if R ₅ and R _{6 are} each C ₆ - to C ₈ -alkyl, such as, for example, in the abovementioned compounds di-2-ethylhexyldithiophosphoric acid and di-n-octyl-dithiophosphoric acid. Most preferred is di-2-ethylhexyl dithiophosphoric acid.

Preferably Such amounts of the fatty acid esters of the formula (I) and the dithiophosphoric acid of the formula (II) that an intermediate with unreacted Epoxide groups is formed. Further, it is preferable that the ratio of Number of epoxide groups of the fatty acid ester to the thiol group of dithiophosphoric at least 1: 1, more preferably 3: 2, and most preferably 3: 1 lies.

The Reaction in step (a) is preferably carried out at a temperature from 20 to 40 ° C without the presence of solvents. The reaction time is preferably 0.5 to 1.5 h.

In Step (b) of the first process becomes the intermediate product unreacted epoxide groups, with a crosslinker compound to form the polymeric Dithiophosphorsäurehydroxyfettsäureesters reacted, wherein the crosslinker compound intermolecularly with two or more epoxide groups.

Suitable crosslinker compound is any molecule which has at least two functional, H-acidic groups and can react intermolecularly with the free epoxide groups. A preferred crosslinker compound has the formula (III) L- (XH) _z (III) in which L is a molecular unit, -XH is a functional, H-acidic group, wherein X is independently oxygen or sulfur and z is at least 2. In this case, L may be an inorganic or organic Be molecular unit.

In a particularly preferred embodiment the crosslinker compound of the formula (III) has two functional, H-acidic groups on (z = 2). In this case, it is a bifunctional molecule, which can react intermolecularly with two epoxide groups. Besides that is it is then preferred that both X are each oxygen or sulfur are. Preferred bifunctional crosslinker compounds are naphthalenedisulfonic acids, aliphatic and / or aromatic saturated dicarboxylic acids, Monoalkyl phosphoric acid esters, mixtures from monoalkylphosphoric acid esters and dialkylphosphoric acid esters and dimercaptothiadiazoles. Most preferred Dinonylnaphalindisulfonsäure, 2-Ethylhexylphosphorsäuremonoester, Mixtures of 2-Ethylhexylphosphorsäuremonoester and 2-Ethylhexylphosphorsäurediester and 2,5-dimercapto-1,3,4-thiadiazole.

The Reaction in step (b) is preferably carried out at a temperature from 80 to 150 ° C without the presence of solvents. The reaction time is preferably 0.5 to 1.5 h.

The first production route just described is through 1 which exemplifies the reaction of an epoxidized fatty acid glyceride with di-2-ethylhexyl dithiophosphoric acid and the subsequent polymerization with 2,5-dimercapto-1,3,4-thiadiazole.

at the second method according to the invention in step (a) an epoxidized fatty acid ester of the above Formula (I) reacted with a crosslinker compound, wherein the crosslinker compound reacts intermolecularly with two or more epoxide groups and the fatty acid ester and the crosslinker compound are reacted together such that a polymeric intermediate with unreacted epoxide groups is formed.

When Crosslinker compound, the same compounds are used as they have already been described in connection with the first production route were.

Preferably Such amounts of the fatty acid esters of the formula (I) and the crosslinker used that a polymeric intermediate is formed with unreacted epoxide groups. It is next prefers that ratio the number of epoxide groups of the fatty acid ester to functional, H-acidic groups of the crosslinker compound of the formula (III) in at least 1: 1, more preferably 10: 1, and most preferably 20: 1.

The Reaction in step (a) is preferably carried out at a temperature from 30 to 100 ° C without the presence of solvents. The reaction time is preferably 0.5 to 1.5 h.

In Step (b) of the second process then becomes the polymeric intermediate, having unreacted epoxide groups with a dithiophosphoric acid of the above-mentioned formula (II) to form the polymeric Dithiophosphorsäurehydroxyfettsäureesters implemented.

The Reaction in step (b) is preferably carried out at a temperature from 30 to 100 ° C without the presence of solvents. The reaction time is vorzugswiese 0.5 to 1.5.

The just described second production route is by 2 which exemplifies the reaction of an epoxidized fatty acid glyceride with 2,5-dimercapto-1,3,4-thiadiazole to give a polymeric intermediate and the subsequent reaction with di-2-ethylhexyl dithiophosphoric acid.

When optional measure may in both methods before or after step (b) a hydrolysis protection agent be added. A preferred hydrolysis-protecting agent is an oil-soluble one and sterically hindered aryl carbodiimide. Exemplary here Bis (2,6-diisopropylphenyl) carbodiimide listed.

Possibly it may be necessary to remove the reaction product to remove To filter fine particles.

worin R₄ unabhängig voneinander H oder -CH₃ ist,
E₁ die Formel

aufweist,
E₂ die Formel

aufweist, worin L eine Moleküleinheit ist und X unabhängig voneinander Sauerstoff oder Schwefel ist,
E₃ die Formel

aufweist, worin R₅ und R₆ gleich oder verschieden sein können und unabhängig voneinander ausgewählt sind aus H, Alkyl oder Aryl mit der Maßgabe, dass mindestens einer von R₅ und R₆ nicht H ist,
und wobei jeweils m eine Zahl von 1 bis 40 ist, n eine Zahl von 1 bis 10 ist und p eine Zahl von 0 bis 8 ist.In a further embodiment, the polymeric dithiophosphoric acid hydroxy fatty acid ester according to the invention comprises the following regularly repeating unit:

wherein R _{4 is} independently H or -CH ₃ ,
E _{1 is} the formula

having,
E _{2 is} the formula

in which L is a molecular unit and X is independently oxygen or sulfur,
E _{3 is} the formula

wherein R ₅ and R _{6 may be the} same or different and are independently selected from H, alkyl or aryl, provided that at least one of R ₅ and R _{6 is} not H,
and wherein each m is a number from 1 to 40, n is a number from 1 to 10 and p is a number from 0 to 8.

In this case, R ₅ , R ₆ , m, n, p, L and X are those preferred embodiments which have been described in connection with the inventive method. In each of the fatty acid-derived residues of the above triglyceride structure, the single methylene-substituted m can be used Units (CH ₂ ) and the individual, provided with the index n units E ₁ , E ₂ or E ₃ in any order be distributed over the chain, ie in random, blockwise or alternating arrangement. However, it is preferred that at least 2 methylene units (CH ₂ ), more preferably 7 methylene units (CH ₂ ), follow the carbonyl group before one or more of the units E ₁ , E ₂ or E ₃ and again methylene (CH ₂ ) follows ,

bedeutet.However, particularly preferred polymeric Dithiophosphorsäurehydroxyfettsäureester are those compounds in which independently R ₅ and R _{6 are} each C ₆ - to C ₈ alkyl (especially 2-ethylhexyl), m is a number from 7 to 29 (especially 10 to 16), n is a number from 2 to 4 (especially 2 or 3), p is a number from 2 to 5 (especially 3 or 4) and X is each S and L is

means.

genannt, worin R₄, R₅, R₆, m, n, p, L und X unabhängig voneinander die oben angegebenen Bedeutungen haben können.As an example of a polymeric Dithiophosphorsäurehydroxyfettsäureester invention, the following compound

wherein R ₄ , R ₅ , R ₆ , m, n, p, L and X may independently of one another have the meanings given above.

The molecular weight (weight average, M _w ) of the polymeric dithiophosphoric acid hydroxy fatty acid esters of the present invention is in the range of 1,000 to 40,000 g / mol as determined by gel permeation chromatography (GPC). The viscous to high viscosity polymers usually have a viscosity in the range of 100 to 1000 cSt (centistokes) at a temperature of 40 ° C.

The explain the following examples the invention further. All Percentages are, unless stated otherwise the weight.

example 1

• * prozentualer Gehalt an Oxiran-Sauerstoff im epoxidierten Sojaöl

A polymeric dithiophosphoric acid hydroxy fatty acid ester according to the invention is synthesized according to the first preparation route. a. quantities

• * Percent oxirane oxygen content in epoxidized soybean oil

b. manufacturing

epoxidized soybean oil is placed at room temperature in a glass jar and slowly with stirring with di-2-ethylhexyldithiophosphorsäure added. Hereby heated the reaction solution. Under countercooling becomes at 80-100 ° C the total amount on di-2-ethyl hexyl dithiophosphoric acid add. After stirring for 30 minutes at 80 ° C the reaction is complete. A pale yellow liquid is obtained. Subsequently, will at 80 ° C with stirring the hydrolysis stabilizer bis (2,6-diisopropylphenyl) carbodiimide Add and stir for a further 30 minutes until a clear, yellow liquid originated. Subsequently For crosslinking (oligomerization), the 2,5-dimercapto-1,3,4- thiadiazole with stirring at 100 ° C added. After stirring for 30 minutes at 100 ° C it dissolves Suspension on and you get a yellow clear liquid that is highly viscous at room temperature. For removal of fine particles the approach is over a filter is filtered hot and subsequently bottled.

c. Analysis of the product according to the invention

From the IR spectrum (device: Perkin Elmer Spectrum One, film between NaCl window) of the product of Example 1, the in 3 is shown, resulting in the bands listed in the following table.

A ³¹ P-NMR spectrum (200 MHz NMR spectrometer from Bruker) of the product from Example 1 in CDCl _{3 was} taken, which shows the following characteristic peaks: δ (ppm) assigned structure 98.17 (RO) ₂ P (S) SR ` 95 (RO) <sub>2</sub> P (S) SR `

Furthermore, the product of Example 1 was analyzed by gel permeation chromatography. The following devices, materials and measurement conditions were used for the GPC analysis:
Detector: refractive index, Schodex RI-71 device
Pump: Spectra Physics P100
Column oven: Yasco

The gel permeation chromatogram thus obtained is in 4 shown. This results in a weight average molecular weight M _w of 6411, a number average molecular weight M _n of 2413, and a molecular weight (centrifuge) M _z of 12230. The polydispersity M _w / M _{n of} the product of Example 1 is 2.6569.

The element contents of the product from Example 1 are:
Phosphorus: 3.51%
Sulfur: 7.96%

Example 2

• * prozentualer Gehalt an Oxiran-Sauerstoff im epoxidierten Sojaöl

A polymeric dithiophosphoric acid hydroxy fatty acid ester according to the invention is synthesized according to the second preparation route (inverse process). a. quantities

• * Percent oxirane oxygen content in epoxidized soybean oil

b. manufacturing

epoxidized soybean oil is presented at room temperature in a glass vessel, heated to 80 ° C and for oligomerization with stirring with 2,5-dimercapto-1,3,4-thiadiazole powder. After 10 minutes Stirring gives you a pale yellow viscous liquid. Subsequently you give under countercooling at 80-100 ° C within of 30 minutes the di-2-ethylhexyldithiophosphorsäure added. After stirring for 30 minutes at 80 ° C the reaction is complete. A pale yellow liquid is obtained. Subsequently becomes at 80 ° C while stirring the Hydrolysis protection stabilizer bis- (2,6-diisopropylphenyl) - added carbodiimide and stirred for another 30 minutes, until a clear, yellow liquid originated. To remove fine particles, the approach over a Filter filtered hot and subsequently bottled.

The element contents of the product are:
Phosphorus: 3.52%
Sulfur: 7.98%

Example 3

• * prozentualer Gehalt an Oxiran-Sauerstoff im epoxidierten Sojaöl

A polymeric dithiophosphoric acid hydroxy fatty acid ester according to the invention is synthesized according to the first preparation route. Instead of 2,5-dimercapto-1,3,4-thiadiazole as in Example 1, a mixture of mono- and di-2-ethylhexylphosphorsäureester (molar ratio 1: 1) is used as a crosslinker. a. quantities

• * Percent oxirane oxygen content in epoxidized soybean oil

b. manufacturing

epoxidized soybean oil is placed at room temperature in a glass jar and slowly with stirring with di-2-ethylhexyldithiophosphorsäure added. Hereby heated the reaction solution. Under countercooling becomes at 80-100 ° C the total amount on di-2-ethyl hexyl dithiophosphoric acid within 30 minutes. After stirring for 30 minutes 80 ° C is completed the reaction. A pale yellow liquid is obtained. Subsequently becomes at 80 ° C with stirring the hydrolysis stabilizer bis (2,6-diisopropylphenyl) carbodiimide Add and stir for a further 30 minutes until a clear, yellow liquid originated. Subsequently For crosslinking (oligomerization), the mixture of mono- and di-2-ethylhexyl phosphoric acid ester (molar ratio 1: 1) with stirring at 100 ° C added. After stirring for 30 minutes at 100 ° C receives a yellow clear liquid, which is highly viscous at room temperature. For removal of fine particles is the approach over a filter is filtered hot and subsequently bottled.

The element contents of the product are:
Phosphorus: 4.51%
Sulfur: 8.23%

Example 4

• * prozentualer Gehalt an Oxiran-Sauerstoff im epoxidierten Sojaöl

This example relates to the synthesis of a polymeric Dithiophosphorsäurehydroxyfettsäureesters according to the first preparation route, wherein as in Example 3, a mixture of mono- and di-2-ethylhexylphosphorsäureester (molar ratio 1: 1) used as a crosslinker compound, but no Hydroly seschutzstabilisator (bis (2, 6-diisopropylphenyl) carbodiimide) is added. a. quantities

• * Percent oxirane oxygen content in epoxidized soybean oil

b. manufacturing

epoxidized soybean oil is placed at room temperature in a glass jar and slowly with stirring with di-2-ethylhexyldithiophosphorsäure added. Hereby heated the reaction solution. Under countercooling becomes at 80-100 ° C the total amount on di-2-ethyl hexyl dithiophosphoric acid add. After stirring for 30 minutes at 80 ° C the reaction is complete. A pale yellow liquid is obtained. Then there for crosslinking (oligomerization) the mixture of mono- and Di-2-ethylhexylphosphoric acid ester (molar ratio 1: 1) with stirring at 100 ° C added. After stirring for 30 minutes at 100 ° C receives a yellow clear liquid, which is highly viscous at room temperature. For removal of fine particles the approach is over a filter is filtered hot and subsequently bottled.

The element contents of the product are:
Phosphorus: 5.0%
Sulfur: 10.1%

Example 5

• * prozentualer Gehalt an Oxiran-Sauerstoff im epoxidierten Propylenglycoldioleat

This example again relates to the synthesis of a polymeric Dithiophosphorsäurehydroxyfettsäureesters invention according to the first preparation route, being used as in Example 3, a mixture of mono- and di-2-ethylhexylphosphorsäureester (molar ratio 1: 1) as a crosslinker compound. Instead of the epoxidized soybean oil, however, a synthetic epoxidized fatty acid ester (epoxidized propylene glycol dioleate having an epoxide content of 4%) is used. a. quantities

• * Percent oxirane oxygen content in the epoxidized propylene glycol dioleate

b. manufacturing

epoxidized Propylene glycol dioleate is initially charged at room temperature in a glass jar and stirring slowly added with di-2-ethylhexyldithiophosphorsäure. Hereby heated the reaction solution. Under countercooling becomes at 80-100 ° C the total amount on di-2-ethyl hexyl dithiophosphoric acid add. After stirring for 30 minutes at 80 ° C the reaction is complete. A pale yellow liquid is obtained. Subsequently becomes at 80 ° C with stirring the hydrolysis stabilizer bis (2,6-diisopropylphenyl) carbodiimide Add and stir for a further 30 minutes until a clear, yellow liquid originated. Subsequently For crosslinking (oligomerization), the mixture of mono- and di-2-ethylhexyl phosphoric acid ester (molar ratio 1: 1) with stirring at 100 ° C added. After stirring for 30 minutes at 100 ° C receives a yellowish clear liquid, which is highly viscous at room temperature. For removal of fine particles the approach is over a filter is filtered hot and subsequently bottled.

The element contents of the product are:
Phosphorus: 3.62%
Sulfur: 7.98%

Example 6

It was first the wear characteristic value of the base oil ISO VG 46 according to DIN 51350/3. Then base oils were ISO VG 46 tested, which had different concentrations of the product of Example 1. The obtained wear characteristics (Diameter of the dome) are listed in the following table.

Example 7

It was first the welding force of the base oil ISO VG 46 according to DIN 51350/2. Then base oils were ISO VG 46 tested, which had different concentrations of the product of Example 1. The obtained welding force values are summarized in the following table.

Example 8

It became the wear index of base oils ISO VG 46 according to DIN 51350/3, those different quantities on the product of Example 1 or on zinc di-2-ethylhexyl dithiophosphate (hereinafter also called "ZDTP") added were. The obtained wear characteristics (dome diameter) are in the following table.

Example 9

It became the welding force of base oils ISO VG 46 according to DIN 51350/2, those of different quantities on the product of Example 1 or on zinc di-2-ethylhexyl dithiophosphate were added. The obtained welding force values are as follows Table compiled.

Example 10

It The antioxidant properties of zinc di-2-ethylhexyl dithiophosphate compared to the product of Example 1 in the base oil ISO VG 46 according to ASTM 2272 (Rotating bomb). The concentration ZDTP and product from Example 1 in the base oil ISO VG 46 was in each case 0.5% by weight. The results of these investigations are in the following Table compiled.

It has been found that the reaction of substituted dithiophosphoric acids with epoxidized fatty acid esters and subsequent polymerization with crosslinker compounds such as dimercapto-1,3,4-thiadiazole or dinonylnaphthalenedisulfonic acids gives oil-soluble products which are metal-free and on Because of the biodegradable components such as soybean oil have a favorable ecotoxicological profile. At the same time their production by the elimination of expensive filtrations, as is necessary in the production of Zinkdialkyldithiophosphaten, economical. In the reaction according to the invention (oligomerization or polymerization), "castor oil-like" structures (hydroxy fatty acid esters) are obtained which have excellent lubricating properties.

As can be seen from the application examples 6 to 10, leads the Use of the polymers according to the invention for significantly improving the wear of the lubricant by approx. 47% and exceeds therein the effect of the classical zinc dialkyldithiophosphates. simultaneously By the addition of the product according to the invention, the welding force value becomes of a lubricant increases and also significantly improves the aging properties of the base oil.

at Use of the polymers according to the invention the user has multifunctional additives for the formulation of lubricants by significantly improved property profiles available. Be interesting as lubricants hydraulic oils, Motor oils, Gear oils, Lubricating oils, Greases, metalworking oils and industrial oils called. In addition to the general suitability of the polymers of the invention as a lubricant additive is their specific use for improvement the wear protection effect or aging stability in lubricants.

Claims (34)

Process for the preparation of polymeric dithiophosphoric acid hydroxy fatty acid esters, characterized in that (a) an epoxidized fatty acid ester of the formula (I)

where A = R ₁ O or H, where x is a number from 0 to 6 and R ₁ , R ₂ and R _{3 may be the} same or different and are as defined below:

wherein R _{4 is} H or -CH ₃ , m is a number from 1 to 40, n is a number from 1 to 10 and p is a number from 0 to 8, with a substituted dithiophosphoric acid of the formula (II)

wherein R ₅ and R _{6 may be the} same or different and are independently selected from H, alkyl or aryl, provided that at least one of R ₅ and R _{6 is} not H, the fatty acid ester of formula (I) reacting with the dithiophosphoric acid of formula (II) to form an intermediate with unreacted epoxide groups, and (b) reacting the intermediate with a crosslinker compound to form the polymeric dithiophosphoric hydroxy fatty acid ester, wherein the crosslinker compound intermolecularly reacts with two or more epoxide groups. Method according to claim 1, characterized in that in step (a), the ratio the number of epoxide groups of the fatty acid ester of the formula (I) Thiol group of dithiophosphoric acid of formula (II) at least 1: 1, more preferably 3: 2 and most preferably 3: 1. Process according to Claim 1 or 2, characterized in that the crosslinker compound has the formula (III) L- (XH) _z (III) wherein L is a molecular moiety, -XH is a functional, H-acidic group, wherein X is independently oxygen or sulfur and z is at least 2. Process for the preparation of polymeric dithiophosphoric acid hydroxy fatty acid esters, characterized in that (a) an epoxidized fatty acid ester of formula (I) as defined in claim 1 with a crosslinker compound is reacted, wherein the crosslinker compound intermolecular with two or more epoxy groups react and the fatty acid ester and the crosslinker compound are reacted together such that a polymeric intermediate with unreacted epoxide groups is formed, and (B) the polymeric intermediate with a dithiophosphoric of formula (II) as defined in claim 1 to form the polymeric Dithiophosphorsäurehydroxyfettsäureesters is implemented. Method according to claim 4, characterized in that in step (a), a crosslinker compound of the formula (III), such as is used defined in claim 3. Method according to claim 5, characterized in that that the ratio the number of epoxide groups of the fatty acid ester of the formula (I) functional, H-acidic groups of the crosslinker compound of the formula (III) at least 1: 1, more preferably 10: 1 and most preferably 20: 1 is located. Method according to one of claims 1 to 6, characterized that x is 1. Method according to one of claims 1 to 7, characterized that the epoxidized fatty acid ester the formula (I) of epoxidized oils natural Origin is derived. Method according to claim 8, characterized in that that the epoxidized oil natural Origin is selected from epoxidized soybean oil, linseed oil, rapeseed oil, sunflower oil and fish oil. Method according to one of claims 1 to 9, characterized that in the fatty acid ester of the formula (I) A = H. Method according to claim 10, characterized in that that the fatty acid ester of formula (I) is epoxidized propylene glycol dioleate. Method according to one of claims 1 to 11, characterized the percent oxirane oxygen content in the fatty acid ester of the formula (I) greater than 2 wt .-% and preferably greater than 3 wt .-% is. Method according to one of claims 1 to 12, characterized in that R ₅ and R _{6 are} each C ₆ - to C ₈ alkyl. A method according to claim 13, characterized in that R ₅ and R _{6 are} each 2-ethylhexyl. Method according to one of claims 1 to 14, characterized that z in the crosslinker compound of the formula (III) is 2. Method according to claim 15, characterized in that the crosslinker compound of the formula (III) is selected from naphthalenedisulfonic acids, aliphatic and / or aromatic saturated dicarboxylic acids, Monoalkylphosphorsäureestern, Mixtures of monoalkylphosphoric acid esters and dialkylphosphoric acid esters and Dimercaptothiadiazolen is selected. Process according to Claim 16, characterized in that the crosslinker compound of the formula (III) is selected from dinonylnaphalindisulfonic acid, 2-ethylhexylphosphoric acid monoester, mixtures of 2-ethylhexylphosphoric monoester and 2-ethylhexylphosphoric acid diester and 2,5-dimercapto-1,3,4-thiadiazole. Method according to one of claims 1 to 17, characterized in that before or after step (b) a hydrolysis protection agent is added becomes. Method according to claim 18, characterized that the hydrolysis protection agent is an oil-soluble and sterically hindered Arylcarbodiimide is. Process according to claim 19, characterized the aryl carbodiimide is bis (2,6-diisopropylphenyl) carbodiimide is. Polymeric dithiophosphoric acid hydroxy fatty acid ester, available by a method according to the claims 1 to 20. Polymeric dithiophosphoric acid hydroxy fatty acid ester, characterized in that it contains the following regularly repeating unit:

wherein R _{4 is} independently H or -CH _3, E is _1, the formula

E _{2 has} the formula

wherein L is a molecular moiety and X is independently oxygen or sulfur, E _{3 is} the formula

E _{1 has} the formula wherein R ₅ and R _{6 may be the} same or different and are independently selected from H, alkyl or aryl, provided that at least one of R ₅ and R _{6 is} not H, and wherein each m is one Number is from 1 to 40, n is a number from 1 to 10 and p is a number from 0 to 8. Polymeric Dithiophosphorsäurehydroxyfettsäureester according to claim 22, characterized in that R ₅ and R _{6 are} each C ₆ - to C ₈ alkyl. Polymeric Dithiophosphorsäurehydroxyfettsäureester according to claim 23, characterized in that R ₅ and R _{6 are} each 2-ethylhexyl. Polymeric dithiophosphoric acid hydroxy fatty acid ester according to one of the claims 22 to 24, characterized in that m is a number from 7 to 29 and preferably from 10 to 16. Polymeric dithiophosphoric acid hydroxy fatty acid ester according to one of the claims 22 to 25, characterized in that n is a number from 2 to 4 and preferably 2 or 3. Polymeric dithiophosphoric acid hydroxy fatty acid ester according to one of the claims 22 to 26, characterized in that p is a number from 2 to 5 and preferably 3 or 4. Polymeric Dithiophosphorsäurehydroxyfettsäureester according to any one of claims 22 to 27, characterized in that X is in each case S and L

means. Use of the polymeric Dithiophosphorsäurehydroxyfettsäureesters according to one of claims 21 to 28 as a lubricant additive. Use of the polymeric Dithiophosphorsäurehydroxyfettsäureesters according to one of claims 21 to 28 for improving the wear protection effect of lubricants. Use of the polymeric Dithiophosphorsäurehydroxyfettsäureesters according to one of claims 21 to 28 for improving the aging stability of lubricants. Use according to one of claims 29 to 31, characterized that the lubricant consists of hydraulic oils, motor oils, gear oils, lubricating oils, lubricating greases, Metal working fluids and industrial oils selected is. Lubricant containing the polymeric Dithiophosphorsäurehydroxyfettsäureester according to one the claims 21 to 28 contains. Lubricant according to claim 33, characterized in that the lubricant from the lubricant fen defined in claim 32.