RU2554873C2 - Lignosulphonate-containing lubricants, method for production and use thereof - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: present invention relates to a method of producing lignosulphonate-containing lubricants, which includes: a) a step of mixing: at least one base oil, at least one calcium soap of a saturated or unsaturated monocarboxylic acid containing 10-32 carbon atoms, optionally substituted, at least one complexing agent selected from: i) an alkali metal salt, except a sodium salt, an alkali-earth metal salt or an aluminium salt of a saturated or unsaturated monocarboxylic acid or a hydroxy carboxylic acid containing 2-8 carbon atoms, a dicarboxylic acid containing 2-16 carbon atoms, wherein each of said acids can be substituted, ii) an alkali and/or alkali-earth metal salt of boric acid and/or phosphoric acid, including products of reaction thereof with LiOH and/or Ca(OH), and iii) mixtures thereof, and at least calcium lignosulphonate with weight-average molecular weight higher than 10000 g/mol, heating the mixture to temperature higher than 120°C to initiate the reaction and removing low-boiling components to obtain a lubricant base, and b) a step of cooling and adding base oil and, optionally, additives while stirring. The present invention also relates to a lubricant composition and to use of the lubricant (versions).EFFECT: use of lignosulphonates as structure-forming agents and as additives which protect from wear, reduce friction and protect from aging.29 cl, 10 ex, 3 tbl

Description

The invention relates to a method for producing lubricants (lubricants) containing calcium lignosulfonate, to lubricants of this kind and to their use.

Lignin is a complex polymer based on phenylpropane monomers, which are connected to each other using a variety of chemical compounds. Lignin is found in plant cells together with cellulose and hemicellulose. Lignin itself is a crosslinked macromolecule with an average molecular weight of, for example, greater than 10,000 g / mol.

As the main lignin monomers, essentially three types of monolignol monomers can be identified, which differ from each other in the degree of methoxylation. These are para-coumaril alcohol, coniferyl alcohol and synapyl alcohol. These lignols are embedded in the lignin structure in the form of hydroxyphenyl (H) -, guaiacil (G) - and syringal (S) monomers. Gymnosperms (Gymnospermae), for example, pines, predominantly contain G-monomers and a small fraction of H-monomers. All lignins contain small amounts of imperfect or modified monomers. The primary function of lignins in plants is to ensure their mechanical stability due to the cross-linking of plant polysaccharides. Lignin forms about 1/3 of the dry mass of the tree and, according to rough estimates, makes up 30% of the mass of inorganic organic carbon on Earth. This is the third most common organic material after cellulose and chitin, and it is a widely used reproducible raw material for industrial products.

Lignosulfonate is formed as a by-product in the manufacture of paper by the sulfite method. In this case, wood, crushed to wood chips, is heated under pressure (for example, in the range from 5 to 7 bar) for about 7-15 hours in the presence of liquor containing calcium hydrosulfite, after which lignosulfonic acid in the form of calcium lignosulfonate is removed by washing and precipitation. Instead of calcium hydrosulfite, alkalis based on magnesium, sodium or ammonium sulfites can also be used, which leads to the formation of the corresponding magnesium, sodium and ammonium salts of lignosulfonic acid. By evaporation of the washing liquor, a powdery lignosulfonate is obtained. The annual production of lignosulfonates in the world is approximately 55 million tons.

Lignosulfonates of sodium, calcium and magnesium are often used as the main active principle for plasticization and liquefaction of concrete and mortar. Lignosulfonates are also used as an auxiliary agent for granulation in the field of concentrated feed production and in other fields as dispersants and complexing agents.

Extreme pressure and anti-wear additives (EP / AW additives) used in modern lubricant compositions, which have a tribochemical effect, provide a considerable part of the cost of the compositions and therefore are often factors contributing to the increase in lubricant prices.

Many of these additives are obtained using laborious multi-stage synthesis methods, and their use is limited by toxicological side effects that arise in many cases, both due to the method of application and the concentration used in the final composition. In some applications, for example, in drive shafts with hinges of equal angular velocities or in slowly moving and heavily loaded rolling bearings, even when using fluid additives, it is not possible to avoid insufficient lubrication or contact with the second component of the friction pair. In these cases, solid lubricants based on inorganic compounds (e.g., Ca and Zn phosphate salts), polymer powders (e.g., polytetrafluoroethylene (PTFE)), or metal sulfides (e.g., MoS ₂ ) were used in previous practice. These components are often also expensive and affect the overall cost of the lubricant composition.

In previous practice, in the preparation of lubricants, additives are added in the second stage of the process, following the actual chemical reaction process with the formation of a thickener. In this case, additives, in particular, solid lubricants, to ensure their optimal effect, it is necessary to evenly distribute in a relatively high viscosity lubricant through an intensive mixing and shearing process with high costs of mechanical energy. From the modern point of view, the above is often a disadvantage and served as the basis for the present invention.

From US Pat. No. 3,249,537 A, lubricants containing sodium lignosulfonates and sodium or lithium soaps are known. However, they are not suitable for lubricating drive shafts with hinges of equal angular velocities, among other things because the grease corrodes thermoplastic elastomeric (TPE) materials of corrugated covers.

Common lubricant additives and solid lubricants are usually based on non-reproducible raw materials and are often difficult to biodegrade. In addition, most common anti-wear and lubricant additives that reduce the coefficient of friction require the use of expensive synthetic chemistry and therefore are a factor that increases costs. In particular, when using solid lubricants in friction units experiencing heavy loads, relatively expensive materials such as MoS ₂ or PTFE prevail.

Objective / Advantage of the Present Invention

Thus, the object of the present invention is to eliminate the above-described drawbacks of the prior art and to enable the use of lignosulfonates as economically more advantageous structure-forming agents and as anti-wear agents, reducing friction and anti-aging additives for lubricants, while also providing good water resistance to the lubricants.

By adding lignosulfonate, you can reduce the use of other common additives for lubricants and solid lubricants, in particular-MoS2, to a minimum or even completely abandon them.

SUMMARY OF THE INVENTION

The invention is disclosed in the independent claims. Preferred embodiments of the present invention are the subject of the dependent claims or are described below.

According to the method underlying the present invention, a precursor (lubricant base) is first prepared by mixing at least

- base oil,

fatty acids and / or esters and / or their salts, the fatty acid salt being at least partially a calcium salt used to make soaps, at least calcium soaps,

- if necessary, organic and / or inorganic complexing agents,

- alkaline earth metal hydroxides, wherein the alkaline earth metal hydroxides contain at least Ca (OH) ₂ ,

- if necessary, water (for example, as part of a hydroxide) and

- calcium lignosulfonate with a weight average molecular weight of more than 10,000 g / mol,

in order to remove low-boiling components by heating and by adding esters to ensure at least the interaction of alkaline earth metal hydroxide with fatty acids and / or their esters and lignosulfonate, including the reaction with complexing agents to the extent that complexing agents reacting with alkaline earth metal hydroxides can be used , to form a thickened structure in the base oil.

Low boiling components are those components that boil at about 100 ° C under normal pressure, for example, water or C1-C4 alcohols.

Preferably, to obtain a lubricant base, heating is carried out to a temperature above 120 ° C, preferably above 180 ° C. The conversion to the base of the lubricant is carried out in a heated reactor, which can be in the form of an autoclave or a vacuum reactor.

Then, in the second stage, the formation of a thickened structure is completed by cooling and, if necessary, other components, such as additives and / or base oil, are added to obtain the desired consistency or the desired property profile. The second stage can be carried out in the same reactor as the first, but preferably the lubricant base is transferred from the reactor to a separate reactor with a stirrer for cooling and, if necessary, adding other components.

If necessary, the lubricant thus obtained is homogenized, filtered and / or air is removed from it.

It is preferable to use thickened Ca / Li, Li / Ca, or calcium normal and complex saponifiable fats, to which calcium lignosulfonate is added even before the reaction phase of obtaining the base of the lubricant and, during the thermal process, is embedded in the structure of the lubricant so that it is present in a very homogeneous insoluble in oil form and provides very high dropping temperatures.

Due to the use of alkaline earth metal salts, preferably calcium salts, both from the side of the fatty acid salts and from the lignosulfonate side, the absence of salt conversion is ensured both when the grease base is obtained and when it is used.

The conversion of salts, in particular to sodium salts, must be impeded in order to obtain a lubricant containing lignosulfonate with good water resistance and a simultaneous high dropping point. Therefore, the use of sodium lignosulfonate and sodium hydroxide should be avoided. Under the water resistance is understood that the grease when tested according to DIN 51807-1 (Edition: 04.1979) is not emulsified by water or corresponds to a rating level of 1-90 (test at 90 ° C). In addition, water resistance is understood to mean that the lubricant when tested according to DIN 51807-2 (Edition: 03.1990) corresponds to a rating level of 1-80 (test at 80 ° C).

Due to the simultaneous use of excess alkali in the form of an excess amount of calcium hydroxide and, if necessary, additional calcium acetate or other calcium salts as complexing agents, neutralization of a small residue of free sulfonic acid groups in lignosulfonic acid and elimination of hygroscopic properties, emulsification in water and corrosion stimulation should be ensured. Due to the high operating temperature exceeding 120 ° C, in particular exceeding 180 ° C, it is additionally ensured that the residual moisture still contained in the lignosulfonate is completely evaporated from the reaction medium, and the components of the lignosulfonate not neutralized under certain conditions are neutralized by calcium hydroxide.

Conventional lubricating oils that are liquid at room temperature are suitable as base oils. The base oil preferably has a kinematic viscosity in the range from 20 to 2500 mm ² / s, in particular from 40 to 500 mm ² / s at 40 ° C.

Base oils can be classified as mineral oils or synthetic oils. As mineral oils are considered, for example, naphthenic and paraffin-based mineral oils belonging to Group I according to the classification of the American Petroleum Institute (API). Chemically modified aromatic and low sulfur mineral oils with a low content of saturated compounds and a better temperature dependence of viscosity than those of Group I oils are also suitable for API Groups II and III.

Synthetic oils include polyethers, polyesters, polyalphaolefins, polyglycols, alkyl aromatic compounds and mixtures thereof. The polyester compound may contain free hydroxyl groups, may be fully transesterified, or its end groups may be esterified to form esters and / or it may be prepared from the parent compound with one or more hydroxyl and / or carboxyl (-COOH) groups . It is also possible to use polyphenyl ethers, optionally alkylated, as single components or, more preferably, as components of a mixture. You can use esters of aromatic di-, tri- or tetracarboxylic acids with a single or C2-C22 alcohol contained in the mixture, esters of adipic acid, sebacic acid, esters of trimethylolpropane, neopentyl glycol, pentaerythritol or dipentaerythritol with branched, branched or unbranched or unbranched unsaturated C2-C22 carboxylic acids, esters of C18 dimeric acids with C2-C22 alcohols, complex esters, as single components or as any mixture.

The resulting soaps are either pure calcium soaps or mixtures containing calcium soaps, in particular containing, in addition to calcium soaps, lithium soaps and / or aluminum soaps, one or more saturated or unsaturated monocarboxylic acids containing 10-32 carbon atoms, if necessary - substituted, in particular containing 12-22 carbon atoms, the corresponding hydroxycarboxylic acids are particularly preferred. Suitable carboxylic acids are, for example, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid or behenic acid; 12-hydroxystearic acid is also preferred. Instead of free acid groups, the corresponding lower alcohol esters after saponification, for example, the corresponding triglycerides, as well as methyl, ethyl, propyl, isopropyl or sec-butyl acid / hydroxy acid esters, can also be used to provide better dispersion.

Soaps, due to the presence of a complexing agent, turn into complex soaps. The lubricant compositions according to the present invention containing complex soaps (due to the presence of complexing agents) have higher dropping temperatures, for example above 200 ° C (DIN ISO 2176). The complexing agent is used in an amount of from 0.5 to 20 wt.%, In particular from 0.5 to 10 wt.%.

Complexing agents in the context of the present invention are:

(a) alkali metal salts (preferably lithium salt), with the exception of sodium salts, alkaline earth metal salts (preferred calcium salt) or aluminum salts of saturated or unsaturated monocarboxylic acids or hydroxycarboxylic acids containing from 2 to 8 carbon atoms, preferably from 2 to 4 carbon atoms, or dicarboxylic acids containing from 2 to 16 carbon atoms, preferably from 2 to 12 carbon atoms, optionally substituted, and / or

(b) salts of alkali and / or alkaline earth metals of boric acid and / or phosphoric acid, in particular, the products of their reactions with LiOH and / or Ca (OH) ₂ .

The complexing agent (a) is preferably only a calcium salt, in particular if this salt in the form of calcium acetate is used to make a grease base. Of the monocarboxylic acids, acetic acid and propionic acid are particularly suitable. Also suitable are hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acids, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gamma-resoic acid) 4-hydroxy-4-methoxybenzoic acid. Of the dicarboxylic acids, adipic acid (C ₆ H ₁₀ O ₄ ), sebacic acid (C ₁₀ H ₁₈ O ₄ ), azelaic acid (C ₉ H ₁₆ O ₄ ) and / or 3-tert-butyl adipic acid (especially C ₁₀ H ₁₈ O ₄ ).

As borates (b), it is possible to use, for example, a metaborate, diborate, tetraborate or orthoborate, for example, lithium orthoborate or calcium orthoborate. Of the phosphates, dihydrophosphates, hydrophosphates or pyrophosphates of alkali (preferably lithium) and alkaline earth (preferably calcium) metals are considered.

Optionally, bentonites can be additionally used as co-thickeners, for example, montmorillonite (sodium ions of which can, if necessary, be replaced or partially replaced by ammonium ions), aluminosilicates, alumina, silicic acid (e.g. Aerosil), oil-soluble polymers (e.g. polyolefins, poly ( meth) acrylates, polyisobutylene, polybutene or polystyrene), as well as di- and polyurea. Bentonites, aluminosilicates, alumina, silicic acid and / or oil-soluble polymers can be added to form a lubricant base, or later, in a second step, as an additive. Di- and polyurea can be added as an additive.

The compositions of the present invention may contain other additives as adjuvants. Common adjuvants in the context of the present invention are antioxidants, antiwear additives, anticorrosion agents, detergents, colorants, lubricity improvers, viscosity regulators, friction reducing agents, and high pressure additives.

Examples include:

- antioxidants, such as amine compounds (e.g. alkylamines or 1-phenylaminonaphthalene), aromatic amines, e.g. phenylnaphthylamines or diphenylamines, phenolic compounds (e.g. 2,6-di-tert-butyl-4-methylphenol), sulfur-containing antioxidants, dithiocarbamate zinc or zinc dithiophosphate;

- high pressure additives such as organic chlorine compounds, sulfur, calcium phosphorus or borate, calcium dithiophosphate, organic bismuth compounds;

- active substances that increase the "oiliness", such as C2-C6 polyols, fatty acids, esters of fatty acids or animal or vegetable oils;

anticorrosion agents, for example, petroleum sulphonate, dinonylnaphthalene sulphonate or sorbitan ester;

- metal deactivators, for example, benzotriazole or sodium nitrite;

- viscosity regulators, for example, polymethacrylate, polyisobutylene, oligo-dec-1-ene and polystyrene;

- anti-wear additive and means for reducing friction, such as organomolibdenovye complexes (OMC), molybdenum dialkyldithiophosphates, molybdenum dialkyldithiocarbamates or molybdenum sulfide dialkyldithiocarbamates, in particular - molybdenum di-n-butyldithiocarbamate and molybdenum disulfide, dialkyldithiocarbamate (Mo ₂ O _m S _n (dialkilkarbamat) ₂ , where m is from 0 to 3, an is from 4 to 1),

- additives that reduce friction, for example, functional polymers, such as oleylamides, organic compounds based on polyethers and amides, for example, alkylpolyethylene glycol tetradecylene glycol ether.

In addition, the lubricant compositions according to the present invention contain standard additives that act against corrosion, oxidation and to protect against the effects of metals, which function as chelating compounds, free radical scavengers, UV converters, reaction layer forming agents and the like.

As solid lubricants can be used, for example, powdered polymers such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides, for example, molybdenum disulfide, tungsten disulfide and mixed sulfides based on tungsten, molybdenum, bismuth , tin and zinc, inorganic salts of alkali and alkaline earth metals, for example, calcium carbonate, sodium and calcium phosphates. Solid lubricants can be divided into the following four groups: compounds with a layered lattice structure, such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride and some metal halides; oxide and hydroxide compounds of transition and alkaline earth metals or their carbonates or phosphates; soft metals and / or polymers. The desired preferred lubricating properties can be adjusted by using lignosulfonates without the need for solid lubricants. In many cases, solid lubricants can be discarded altogether, or at least significantly reduced. In the case of solid lubricants, graphite is preferred.

As lignosulfonate, calcium lignosulfonates with a molecular weight (Mw, weight average molecular weight) of more than 10,000, in particular more than 12,000 or even more than 15,000 g / mol, for example from 10,000 to 65,000 g / mol or from 15,000 to 65,000 g, are used. / mol, which contain from 2 to 12 wt.% sulfur, preferably from 4 to 10 wt.% sulfur (in terms of elemental sulfur), and / or from 5 to 15 wt.% calcium, preferably from 8 to 15 wt.% calcium (in terms of Ca). In addition to calcium lignosulfonates, other alkaline earth metal lignosulfonates can also be used. The weight average molecular weight is determined, for example, by size exclusion chromatography. A suitable method is the SEC-MALLS method described in GEFredheim, SM Braaten and BEC Christensen's Comparison of molecular weight and molecular weight distribution of softwood and hardwood lignosulfonates, published in Journal of Wood Chemistry and Technology, Volume 23, No. 2, p .97-215, 2003, and in the article "Molecular weight determination of lignosulfonates by size exclusion chromatography and multi-angle laser scattering" of the same authors, published in the journal "Journal of Chromatography F", volume 942, issue 1 -2, January 4, 2002, p. 191-199 (mobile phase: phosphate-DMSO-SDS, stationary phase: Jordi-DVB hard gel (glucose divinylbenzene), as described in paragraph 2.5). Suitable lignosulfonates are, for example, the commercially available products Norlig 11 D and Borrement Ca 120 manufactured by Borregard Lignotech.

The lubricant according to the present invention is characterized by the following composition:

a) from 55 to 92 wt.%, in particular from 70 to 85 wt.%, base oil,

b) from 0 to 40 wt.%, in particular from 2 to 10 wt. 5, additives,

c) from 3 to 40 wt.%, in particular from 5 to 20 wt.%, soaps, and

g) from 0 to 20 wt.% or from 0.5 to 20 wt.%, in particular from 0.5 to 10 wt.%, complexing agent, and

d) an excess amount of Ca (OH) ₂ , preferably from 0.01 to 2 wt.%,

e) from 0.5 to 50 wt.%, preferably from 2 to 15 wt.%, and particularly preferably from 3 to 8 wt.%, lignosulfonate, in particular calcium lignosulfonate,

in all cases, percentages of the total weight of the composition are indicated, and the components and their preferred options are defined above.

It has been found that lignosulfonates in water-resistant lubricants act as builders with the same properties as solid lubricants or anti-wear additives and anti-aging agents. At the same time, synergistic interactions of lignosulfonates with other solid lubricants, for example, with graphite or calcium carbonate, were unexpectedly discovered.

It was also found that lignosulfonates are multifunctional components of lubricants. Due to the large number of polar groups and aromatic structures, polymer structure and poor solubility in all types of lubricating oils, lignosulfonates can be used not only as a thickening component, but also as solid lubricants in greases and greases. In addition, the presence of sulfur contributes to the effect of EP / AW additives in lubricants, and phenolic structures provide an anti-aging effect.

It is believed that the structure of lignosulfonate due to the large number of polymer and polar aromatic monomers is predominantly planar. Therefore, under the action of external friction and shear forces, these substances very easily form layered structures on the surfaces of metals, and the aromatic lignosulfonate nuclei come into associative interaction with the metal surface, and even under heavy loads or high pressure, the metal parts forming a friction pair remain effective and long separated from each other.

If lignosulfonates are added even before the start of the reaction phase in the preparation of soap thickeners, in particular complex calcium soaps, they, firstly, provide an additional thickening effect and a high dropping point, and secondly, improve the anti-wear and lubricating effects of the corresponding lubricant compositions. Therefore, it is favorable for the distribution and action of additives and solid lubricants if, during the reaction phase, they are chemically or mechanically incorporated into the thickener structure in situ as an additional structural element.

To obtain soap lubricants with high dropping temperatures in the prior art, in many cases it was necessary to use specially processed and expensive fatty acids, for example, 12-hydroxystearic acid, or special complexing agents, for example, borates or salts of acetic acid, sebacic acid and azelaic acid, which do not or only have a slight simultaneous effect as anti-wear or friction-reducing additives. Through the use of lignosulfonates, you can reduce the use of these components or even abandon them. In addition, the use of calcium lignosulfonates provides the opportunity to obtain highly effective lubricants based on reproducible raw materials and to abandon the use of additives that have a harmful effect on the environment.

If oils consisting of unchanged or slightly modified native fatty acid esters are thickened with metal soaps based on animal or vegetable fatty acids and lignosulfonates are used as the only additional thickening and additive components, then greases are obtained which, up to those used to make metal soaps calcium hydroxide is produced solely on the basis of reproducible raw materials. These lubricants protect against aging and wear, increase the maximum burden on tearing and reduce friction due to the use of lignosulfonates as thickening components.

The lubricants according to the present invention are particularly well suited for use in drive shafts with constant velocity joints, rolling bearings and gearboxes.

Since the base oils used are composed of readily biodegradable esters, for example esters containing predominantly reproducible raw materials, the lubricants of the present invention can be used in flow lubrication systems in environmentally sensitive areas (for example, mining and agriculture).

In the special case of lubrication of maintenance-free drive shafts with constant velocity joints using calcium lignosulfonate, a lubricant composition was first obtained that, in contrast to the prior art, absolutely without using MoS ₂ and other organic and inorganic molybdenum compounds provides a long service life and high efficiency.

In addition, the rejection of other additives, such as additives that reduce friction, increase the ultimate tensile load and protect against wear, provide very good compatibility with standard materials of corrugated drive shaft covers with constant velocity joints such as chloroprene rubber and thermoplastic polyesters. Since sulfur contained in lignosulfonate is bound in thermostable sulfonate groups, unlike sulfur bound in standard additives, it can be released only at very high temperatures or activation energies, which in applications related to lubricants occur only in tribocontacts at high loads. Due to this, unwanted vulcanization or cross-linking of rubber materials due to sulfur released from the aged grease is largely prevented.

By using calcium lignosulfonate in a lubricant composition that is alkaline due to excess calcium hydroxide, the hydrolytic effect of free lignosulfonic acid on corrugated case materials such as thermoplastic polyethers is prevented.

A particular aspect of the present invention is the production of cost-optimized lubricant compositions for lubrication points with high loads, in particular for constant velocity joints that are well compatible with corrugated cases consisting of thermoplastic polyethers (TPE) and chloroprene (CR), while high efficiency, low wear and long service life.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Example A (comparative example)

958 g of fatty acid, 958 g of beef tallow, 958 g of calcium acetate, 27.7 g of trisodium phosphate, 27.7 g of calcium borate and 358 g of calcium hydroxide were loaded into a reactor containing 12000 g of a base oil mixture, and 150 ml of water was added. The initial mixture was heated to 198 ° C under a given temperature program with stirring, while the added water and reaction water were evaporated. During the cooling phase, various additives were added to the mixture at certain temperatures (see table).

After adjusting the mixture to the desired consistency by adding 3700 g of the base oil mixture, the final product was homogenized using a gear colloid mill. The lubricant thus obtained can be used, for example, as a lubricant for drive shafts with constant velocity joints.

Example B

460 g of fatty acid, 445 g of beef tallow, 460 g of calcium acetate, 27.7 g of trisodium phosphate, 27.7 g of calcium borate, 168 g of calcium hydroxide and 920 g of calcium lignosulfonate (powder) were charged into a reactor containing 14000 g of a base oil mixture. Nordig 11D manufactured by Borregard Lignotech) and 150 ml of water was added. According to the set temperature program, the initial mixture was heated to 208 ° C with stirring, while the added water and reaction water were evaporated. During the cooling phase, various additives were added to the mixture at certain temperatures (see table).

After adjusting the mixture to the desired consistency by adding 3450 g of the base oil mixture, the final product was homogenized using a gear colloid mill. The lubricant thus obtained can be used, for example, as a lubricant for drive shafts with constant velocity joints.

Example C (comparative example)

800 g of 12-hydroxystearic acid, 288 g of sebacic acid, 388 g of calcium acetate and 157.3 g of calcium hydroxide were charged to a reactor containing 5000 g of a base oil mixture. 64 g of LiOH ´ H ₂ O were dissolved in 250 ml of water and added to the mixture. The initial mixture was heated to 200 ° C under a given temperature program with stirring, while the added water and reaction water were evaporated. During the cooling phase, additives were added to the mixture at certain temperatures.

After adjusting the mixture to the desired consistency by adding 3116 g of the base oil mixture, the final product was homogenized using a gear

colloid mill. The grease thus obtained can be used, for example, as a grease for rolling bearings.

Example D

600 g of 12-hydroxystearic acid, 216 g of sebacic acid, 291 g of calcium acetate, 720 g of calcium hydroxide and 300 g of calcium lignosulfonate (Nordig 11D powder manufactured by Borregard Lignotech) were charged into a reactor containing 5000 g of a base oil mixture. 48 g of LiOH ´ H ₂ O were dissolved in 250 ml of water and added to the mixture. The initial mixture was heated to 200 ° C under a given temperature program with stirring, while the added water and reaction water were evaporated. During the cooling phase, additives were added to the mixture at certain temperatures.

After adjusting the mixture to the desired consistency by adding 3116 g of the base oil mixture, the final product was homogenized using a toothed colloid mill. The grease thus obtained can be used, for example, as a grease for rolling bearings.

Example E (comparative example)

1380 g of fatty acid, 1360 g of beef tallow, 80 g of trisodium phosphate, 80 g of calcium borate, 1400 g of calcium acetate and 493 g of calcium hydroxide were loaded into a reactor containing 12000 g of a base oil mixture, and 150 ml of water was added. The initial mixture was heated to 230 ° C under a given temperature program with stirring, while the added water and reaction water were evaporated. During the cooling phase, additives were added to the mixture at certain temperatures.

After adjusting the mixture to the desired consistency by adding 3125 g of the base oil mixture, the final product was homogenized using a gear colloid mill. The grease thus obtained can be used, for example, as a grease for rolling bearings.

Example F

1260 g of a base oil mixture were charged into a reactor containing 1260 g of fatty acid, 1240 g of beef tallow, 80 g of trisodium phosphate, 80 g of calcium borate, 1278 g of calcium acetate, 493 g of calcium hydroxide and 885 g of calcium lignosulfonate (Nordig 11D powder manufactured by the company Borregard Lignotech) and 150 ml of water was added. The initial mixture was heated to 225 ° C under a given temperature program with stirring, while the added water and reaction water were evaporated. During the cooling phase, additives were added to the mixture at certain temperatures.

After adjusting the mixture to the desired consistency by adding 3125 g of the base oil mixture, the final product was homogenized using a gear colloid mill. The grease thus obtained can be used, for example, as a grease for rolling bearings.

Example G (comparative example)

In a reactor containing 3,500 g of methyl oleate ether, 975 g of calcium 12-hydrostearate, 225 g of calcium acetate and 15 g of calcium borate were charged. The initial mixture at a given temperature program was heated to 200 ° C with stirring. During the cooling phase, additives were added to the mixture at certain temperatures.

After adjusting the mixture to the desired consistency by adding 180 g of methyl oleate ether, the final product was homogenized using a 3-roller mill. Thus obtained lubricant consists mainly of reproducible raw materials.

Example H

841 g of calcium 12-hydrostearate, 219.5 g of calcium acetate, 15 g of calcium borate and 418 g of calcium lignosulfonate (Nordig 11D powder manufactured by Borregard Lignotech) were charged into a reactor containing 1965 g of methyl oleate ether. The initial mixture at a given temperature program was heated to 200 ° C with stirring. During the cooling phase, additives were added to the mixture at certain temperatures. After adjusting the mixture to the desired consistency by adding 16840 g of trimethylol propane trioleate ether, the final product was homogenized using a tri-roller mill. Thus obtained lubricant consists mainly of reproducible raw materials.

Examples I and J

The preparation of the products in the compositions of Examples I and J corresponds to the preparation of the product from Example H, but using various amounts of calcium 12-dihydroxystearate, calcium acetate and calcium linosulfonate, as well as various compositions of ester base oils. Thus obtained lubricants consist mainly of reproducible raw materials.

Claims (29)

1. The method of obtaining lubricants containing lignosulfonate, including:
a) the mixing stage:
- at least one base oil,
- at least one calcium soap of a saturated or unsaturated monocarboxylic acid containing from 10 to 32 carbon atoms, possibly substituted,
- at least one complexing agent selected from:
i) an alkali metal salt, with the exception of the sodium salt, alkaline earth metal salt or aluminum salt of saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acid containing from 2 to 8 carbon atoms, dicarboxylic acid containing from 2 to 16 carbon atoms, each of these acids may be substituted
ii) salts of an alkali and / or alkaline earth metal of boric acid and / or phosphoric acid, including products of their reactions with LiOH and / or Ca (OH) ₂ , and
iii) mixtures thereof, and
- at least calcium lignosulfonate with a weight average molecular weight of more than 10,000 g / mol,
heating the mixture to a temperature above 120 ° C to initiate a reaction and remove low boiling components to form a grease base, and
b) the stage of cooling and adding base oil and, if necessary, additives with stirring. 2. The method according to p. 1, characterized in that at the stage a) calcium hydroxide is added, if necessary, with other alkaline earth metal hydroxides. 3. The method according to p. 1, characterized in that the lubricant is alkaline due to the addition of excess calcium hydroxide. 4. The method according to p. 1, characterized in that the heating is carried out to temperatures above 180 ° C. 5. The method according to p. 1, characterized in that in addition to calcium hydroxide in stage a), lithium hydroxide, magnesium hydroxide and / or aluminum hydroxide, and / or aluminum alcoholates and / or aluminum alkoxides, and / or lithium, magnesium and / or aluminum soaps of saturated or unsaturated monocarboxylic acids containing from 10 to 32 carbon atoms, which may be substituted. 6. The method according to p. 1, characterized in that they obtain a lubricant containing independently from each other the following components:
- from 55 to 92 wt.% base oil,
- from 0 to 40 wt.% additives,
- from 3 to 40 wt.% calcium soaps, and
- from 0.5 to 10 wt.% complexing agents, and
- if necessary, an excess of Ca (OH) ₂ , and
- from 0.5 to 15 wt.% calcium lignosulfonate, if necessary, in addition to lignosulfonates of other alkaline earth metals,
in all cases, as a percentage of the total weight of the lubricant composition. 7. The method according to p. 1, characterized in that the lubricant base in stage a) can be obtained using
- from 40 to 70 wt.% base oil,
- from 10 to 60 wt.% calcium soaps, and
- from 5 to 30 wt.% complexing agents, and
- if necessary, an excess of Ca (OH) ₂ , and
- from 0.7 to 30 wt.% calcium lignosulfonate, if necessary, in addition to lignosulfonates of other alkaline earth metals,
in all cases, as a percentage of the total mass of the base lubricant. 8. The method according to p. 1, characterized in that the lubricant base contains, independently from each other, from 0.2 to 5 wt.% Graphite, and / or does not contain solid lubricant, or contains less than 1 wt.% Solid lubricant material. 9. The method according to p. 1, characterized in that the calcium soap is obtained in situ as a reaction product of calcium hydroxide with saturated or unsaturated monocarboxylic acid containing from 10 to 32 carbon atoms, which can be substituted, in the form of an ester or anhydride. 10. The method according to p. 9, characterized in that the saturated or unsaturated monocarboxylic acid may be substituted by a hydroxyl group. 11. The method according to p. 1, characterized in that in step a) a complexing agent is added in the form of a reaction product of a calcium salt with a saturated or unsaturated monocarboxylic acid containing from 2 to 8 carbon atoms or a dicarboxylic acid containing from 2 to 16 carbon atoms , each of which, if necessary, can be substituted, in the form of an ester or anhydride. 12. The method according to p. 1, characterized in that at step a) a complexing agent is added in the form of a reaction product of calcium hydroxide with saturated or unsaturated monocarboxylic acid containing from 2 to 8 carbon atoms, or a dicarboxylic acid containing from 2 to 16 carbon atoms , each of which, if necessary, can be substituted, in the form of an ester or anhydride. 13. The method according to p. 11 or 12, characterized in that the saturated or unsaturated monocarboxylic acid or dicarboxylic acid may be substituted by a hydroxyl group. 14. The method according to p. 1, characterized in that the complexing agent is a calcium salt of a carboxylic acid, and it is obtained in situ in stage a) by adding saturated or unsaturated monocarboxylic acid containing from 2 to 8 carbon atoms, or a dicarboxylic acid containing from 2 to 16 carbon atoms, each of which, if necessary, can be substituted, in the form of an ester or anhydride. 15. The method according to p. 14, characterized in that the saturated or unsaturated monocarboxylic acid or dicarboxylic acid may be substituted by a hydroxyl group. 16. The method according to p. 1, characterized in that the calcium lignosulfonate before addition is dehydrated to a water content of less than 0.5 wt.%. 17. The method according to p. 16, characterized in that the calcium lignosulfonate is dehydrated by heating in the base oil to a temperature above 95 ° C. 18. The method according to p. 1, characterized in that the composition contains a complexing agent in an amount of from 0.5 to 20 wt.%. 19. A lubricant composition containing
- from 55 to 92 wt.% base oil,
- from 0 to 40 wt.% additives,
- from 3 to 40 wt.% calcium soaps of saturated or unsaturated monocarboxylic acids containing from 10 to 32 carbon atoms, which may be substituted,
- from 0.5 to 10 wt.% complexing agents selected from:
i) an alkali metal salt, with the exception of a sodium salt, an alkaline earth metal salt or an aluminum salt of saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acids containing from 2 to 8 carbon atoms, or a dicarboxylic acid containing from 2 to 16 carbon atoms, any of which acids may be substituted,
ii) salts of an alkali and / or alkaline earth metal of boric acid and / or phosphoric acid, including products of their reaction with LiOH and / or Ca (OH) ₂ , optionally with an excess of Ca (OH) ₂ , and
iii) mixtures thereof, and
- from 0.5 to 15 wt.% calcium lignosulfonate, if necessary, in addition to lignosulfonates of other alkaline earth metals,
in all cases, as a percentage of the total weight of the lubricant composition,
moreover, the composition has a penetration value of the cone (penetration of the mixed lubricant) in the range from 265 to 385 mm / 10 (at 25 ° C), determined according to ISO 2137. 20. The composition according to p. 19, characterized in that it has a cone penetration (mixed lubricant penetration) in the range from 285 to 355 mm / 10 (at 25 ° C), determined according to ISO 2137. 21. The composition according to p. 19, characterized in that the base oil has a kinematic viscosity in the range from 20 to 2500 mm ² / s at 40 ° C. 22. The composition according to p. 19, characterized in that the complexing agent consists of:
- alkali metal salts or alkaline earth metal salts of saturated or unsaturated monocarboxylic acids containing from 2 to 8 carbon atoms, or dicarboxylic acids containing from 2 to 16 carbon atoms, each of which may be substituted. 23. The composition according to p. 19, characterized in that the additive contains one or more substances selected from the following group:
- amine compounds, phenolic compounds, sulfur-containing antioxidants, zinc dithiocarbamate or zinc dithiophosphate as antioxidants;
- organochlorine compounds, sulfur, calcium phosphorus or borate, zinc dithiophosphate, organic bismuth compounds as high pressure additives;
- C2-C6 polyols, fatty acids, fatty acid esters or animal or vegetable oils;
- petroleum sulphonate, dinonylnaphthalene sulphonate or sorbitan ester as anti-corrosion agents;
- benzotriazole or sodium nitrite as metal deactivators;
- polymethacrylate, polyisobutylene, oligo-dec-1-ene and polystyrenes as viscosity regulators;
molybdenum dialkyldithiocarbamates, or molybdenum sulfide; dialkyldithiocarbamates, or aromatic amines as anti-wear additives;
- functional polymers such as oleylamides, organic compounds based on polyethers and amides, or molybdenum dithiocarbamate as antifriction additives; and
- powdered polymers such as polyamides, polyimides or polytetrafluoroethylene, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc, inorganic alkali and alkaline earth salts metals, such as calcium carbonate, sodium phosphate and calcium, as solid lubricants. 24. The composition according to p. 19, characterized in that the lubricant is waterproof:
a) according to the test results according to DIN 51807-1 has a rating level of 1-90 and / or
b) according to the test results according to DIN 51807-2 has a rating level of 1-80. 25. The composition according to p. 19, characterized in that the calcium lignosulfonate has a weight average molecular weight (Mw) of more than 10,000 g / mol and independently contains from 2 to 12 wt.% Sulfur (in terms of elemental sulfur), and / or also independently contains from 5 to 15 wt.% calcium. 26. The composition according to p. 19, wherein the lubricant contains a base oil based on reproducible raw materials and / or a base oil, more than 95% of which is obtained from reproducible raw materials. 27. The composition according to p. 19, characterized in that it has a dropping point of more than 200 ° C according to DIN ISO 2176. 28. The use of a composition according to any one of paragraphs. 19-27 for lubricating at least the gearbox. 29. The use of the composition according to any one of paragraphs.19-27 for lubricating lubrication points in a constant velocity joint with a corrugated cover, the material of which is thermoplastic polyethers.