CZ76493A3 - Base oil - Google Patents

Abstract

Partial epoxidized vegetable oils or unsaturated esters fatty acids are suitable as base oils for the formulation of environmentally friendly lubricants, hydraulic liquids and similar pffpravkfi.

Description

BACKGROUND OF THE INVENTION.

The requirement of ecological safety is met by products r.etoxic, which in the environment of water or soil are subject to the deepest degradation effects of microorganisms.

Lubricants, hydraulic fluids and the like used in the practice are generally multi-component mixtures in which the main component is a base oil, the application properties of which are further modified by additives. The proportion of base oil is seldom less than 90% rt, so it is logical that its biodegradability is very important for the resulting degradability of the product.

The area where biodegradable and therefore environmentally harmful products are applied is gradually expanding as environmental requirements increase. As an example, oils for chain saw blade lubrication may be used when working in the spring areas of the neoc hydraulic oils for machines operating in water protection zones. However, the use of environmentally friendly oils may also be advantageous where they can come to waste water treatment plants as biological waste water treatment plants.

Petroleum oils do not meet this requirement and often pose a serious environmental risk. In contrast, it is generally known that vegetable edible oils almost ideally satisfy the requirement of non-toxicity and good biological degradability. They also have adequate tribological properties, but they are not stable to oxidation by air oxygen. In our geographical area, soybean, sunflower oil and especially rapeseed oil are the most available.

For a number of less demanding applications, rapeseed oil has been used before oil oils have been known and, to some extent, is still used for lubrication. However, the wider use of vegetable oils is hampered by their low resistance to air oxygen. In rapeseed oil, highly viscous to gums are formed, and soy or sunflower oil can produce continuous solid films which can cause malfunctions of the mechanisms lubricated by them because they are so-called. semi-drying oils. This process can be somewhat delayed by the use of antioxidants, of which substituted phenols, for example 2,6-diterobutyl-4-methyl-2-phenol, or organic phosphites, for example trifluorophosphite, can be randomly mentioned.

The carriers of the ability to polymerize under the action of oxygen are unsaturated fatty acids with multiple double bonds, in particular diene linoleic acid and linoleic triene. Therefore, the effort to solve the problem of insufficient oxygen stability is to use esters of industrial oleic acid (olein), which can be prepared in suitable quality - with a minimum content of trienoids and a low content of diene acids. The situation is well illustrated by the data in Table 1, which gives typical values for the olein composition of appropriate quality and the fatty acid composition of the three oils mentioned above together with their iodine numbers. The olein data column shows the iodine number of the glycerol ester of this olein.

Table no

Fatty acid composition in% wt. and iodine number

material olein elej řepkový soybean solar saturated acids 12.5 8 12 10 monoenoic acids 68 60 27 Mar: 30 diene acids 18 20 May 55 59 trienoic acids 1.5 12 6 1 Iodine number 93.3 117.3 133.8 130.3

The diene- and tri-enoic acid content of the oils can be greatly reduced by virtue of the known catalytic hydrogenation process. Unfortunately, none of the known catalysts is so selective that, at the same time, the monoacids do not give rise to saturated acids, whose presence in the oil undesirably increases the freezing point. Although the solids can be removed by fractional crystallization, olein esters are preferred for economic reasons. Trimethylolpropane esters are characterized by very good properties, in particular low pour point.

SUMMARY OF THE INVENTION.

However, the unsaturated acid content can also be removed by epoxidation. This process is based on the reaction of double bonds with peroxyacids, such as peroxy or peroxy form, and can be described briefly by the reaction + HCDOOH -> -CH-CH- + HOOOH (I)

IN

This process produces epoxidized oils, especially soybean oils, which are used in PVC processing as part of stabilization systems. There is no need for a more detailed description of this technology, as many of the variants in the literature are continuous, as one of the latter is a continuous variation (CXVzP et al., Fa: ChiVol. 70, 511, 19S3). Any known variation of the Frc technology can be used to prepare the products of the present invention. Frc stabilization needs The manufactured products are epoxidized as deeply as possible to give the epoxy group content, expressed as a percentage of ha. oxirane oxygen product, high cc highest and iodine product number as low as possible. Epoxidized oils are non-toxic, as evidenced by the fact that they are allowed to be used in PVC products that come into contact with food. They are also biologically very degradable. However, they do not have the necessary tribological properties.

The present invention is based on the discovery that by incomplete epoxidation of oils, in particular rapeseed oils, a product with a very orthogonal oxygen stability is obtained, which has other properties such that it can be used advantageously for a number of formulations requiring good biological degradation. it has an adequate oxidation stability as the base oil. Partial epoxidation conditions are best illustrated by the example of rapeseed oil from tank 1.

Assuming the same reactivity of all the double bonds in the triglyceride molecule at the partial epoxidation, in which the iodine value of c 52 is reduced to give a product with an oxirane oxygen content of 1.65%. virtually all of the tri-phenols (essentially linolenic) disappear and dienaonoepoxic acid is formed. In part. dienoic acids (linoleic) will form a monoenone monoepic acid and a part of the oleic acid will undergo a similar change. This is similar to that of partial hydrogenation, but no solids are formed. In fact, the reactivity of all double bonds is not the same, the first double lineage of linolenic acid reacts considerably faster, so that a technically useful effect is already achieved at an oxirane oxygen content of 2.0% and for some applications already at an epoxidation of 0.5%. Likewise, however, it does not prevent the use of oils with a higher oxygen content, for example higher than 4%, but this is no longer technically expedient.

With sunflower and soybean oil, there are different proportions due to different fatty acids. Here, the optimum result is a reduction in the iodine value by 45 to 50, which corresponds to an oxirane oxygen content of 2.7 to 5.1%.

Even in this case, of course, is it possible to apply targets? lower and higher levels of oxygen, but again this is not associated with special benefits.

The beneficial effect of partial ejoxidation on the lithium stasis is further evidenced by the results of the test, to which the materials used for comparison have also been subjected.

In this test, 50g samples at 100 ° C were bubbled with oxygen at 5 dm / h. after S hour. A strip of copper plate was inserted in the samples as an oxidation catalyst. The acid value (mg KOH / g) & kinematic viscosity (mm ² / · at 40 ° C) was compared before and after the test. The values for the following materials are given in each column of Table 2:

And partial epoxidized rapeseed oil according to example 1,

B partially epoxidized rapeseed oil according to example 2,

C in-house prepared olein ester according to table 1 and trimethylolpropane,

Refined rapeseed oil.

Samples A to E contained 0.7 wt% as an antioxidant. 2,6-di-tert-butyl-4-methylphenol.

E rapeseed oil refined without antioxidant,

P leading foreign product based on olein ester and trimethylolpropane,

G Top foreign product of unknown composition.

Table 2.

Oxygen stability test results

sample AND (B) C D E F G number before 0.88 0.56 1.81 0.47 0.12 0.60 0.77 acidity AFTER 0.87 0.56 1.98 0.49 0.53 0.78 0.99 cinema. before 43.2 61.3 47.4 37.4 34.7 50.9 33.1 viscosity AFTER 44.9 62.6 50.2 39.1 48.8 53, β 33.0

Remarkably, the acid value of the samples of Examples 1 and 2 has not changed. This can be attributed to the fact that the reactive epoxy group is able to bind the resulting acid oxidation products. The relative change in viscosity is drunk the smallest, only foreign sample G has not seen an increase in viscosity.

Samples A, C and D were subjected to four-ball machine insentience for one hour under a load of ¹⁴⁰⁰ kl · International samples were included in the test because they are known to comprise additives improving tribological properties. The results are summarized in Table 3.

Table 3.

Hourly test wear pattern, mm.

temperature, ° C on a four-ball machine A C D

1.17 2.02 2.11

60 70

-5The result confirmed the beneficial effect of partial epoxidation on the tribological properties of the oil. Plates of class 11 steel according to & ΞΜ were immersed in the sample, dripped and left in the air-conditioning chamber at 40 ° C and relative humidity 100% for 21 days · then the appearance of the platelets was weighed and weighed after washing the oil expressed in g / ia, Foreign samples were not compared because they contained corrosion inhibitors · This test again demonstrated the beneficial effect of partial epoxidation on oil behavior.

Table 4. Corrosion test sample appearance loss g / m

A C unchanged atopy kor

0,00 0,12

D corrosion apparent 2.50

PrUlftflriP ^equation * T

Example 1. Refined rapeseed oil, original iodine number 117.3, partially epoxidized to oxirane oxygen content of 1.00 wt%. Its iodine number is 93.4, the acidity face is 0.88 mg KDH / g, kinematic viscosity at 20 ° C is 95.3 mm ² / s.

Example 2. Refined rapeseed oil of the same quality, partially epoxidized to an oxirane oxygen content of 1.65% by weight. Its iodine number is 86.2, its acid value is 0.56 mg KDH / g, its kinematic viscosity at 20 ° C is 118 µm / s.

Example 3 · Refined rapeseed oil of the same quality, partially epoxidized to an oxirane oxygen content of 0,50% m / m. Its iodine number is 108, the acid number 0.42 mg KDH / g and the kineiotic viscosity 31 mm @ 2 / s at 20 ° C.

Example 4 · Refined rapeseed oil of the same quality, partially epoxidized to an oxirane oxygen content of 2,99% by mass · Its iodine value is 60,6, acid value 0,43 mg KDH / g, kinematic viscosity at 20 ° C 183 mm ² / s .

Example. 5. Refined soybean oil, original iodine No 133,8, partially epoxidised to 2,45% oxirane oxygen content. Its iodine number is 86.2 an acid number of 0.45 ms KDH / g * kinematic viscosity at 20 ° C is 165 mm ² / s.

Example 6. Refined sunflower oil, original iodine number 130.3, partially epoxidized to oxirane oxygen content 3.80%. Its iodine value is 59.4, the acid value 0.52 mg KDH / g, the kinematic viscosity at 20 ° C is 272 mm ² / a. Of course, the above examples do not exhaust all possibilities. Suitable animal fats, such as acids with aliphatic alcohols, diols or polyols of the present invention, residual epoxy and the like of unsaturated fatty acids can of course also be used as the three vegetable oils.

Industrial applicability of the invention.

partially epoxidized vegetable oils, fats or esters of unsaturated fatty acids can be advantageously used as an oil component in all preparations, where their easy biodegradability and relative environmental safety are associated with increased stability against the effects of air oxygen and ability inhibit corrosion. This is particularly true in those cases where the use of petroleum oils is a threat to a healthy environment, for example, when operating mechanisms in the spring. areas of rivers and drinking water protection zones. In the paint industry, it can serve as a non-toxic softener softener. In the area :. • The hands can be combined as hardening oils in cold beard metal forming where rapeseed oil is still in use.

Claims (2)

'FATENT REQUIREMENTS CLAIMS 1. A base oil comprising an ester of a mixture of unsaturated C12-C22 fatty acid esters and an epoxidized C12-C22 fatty acid in an amount corresponding to an oxirane oxygen content % in oil 0.5 to 5.0 wt. Base oil according to claim 1, characterized in that it is preferably a partially epoxidized rapeseed oil with an oxirane oxygen content of 0.5 to 3.0% by weight.