EP0649457A1

EP0649457A1 - Base oils with a high viscosity index and improved low-temperature behaviour.

Info

Publication number: EP0649457A1
Application number: EP93915753A
Authority: EP
Inventors: Frank Bongardt; Nicole Windges
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1992-07-08
Filing date: 1993-06-30
Publication date: 1995-04-26
Anticipated expiration: 2013-06-30
Also published as: EP0649457B1; JPH07508783A; DE59302760D1; DE4222341A1; WO1994001516A1; ATE138681T1; ES2087751T3; US5503762A

Abstract

PCT No. PCT/EP93/01686 Sec. 371 Date Jan. 9, 1995 Sec. 102(e) Date Jan. 9, 1995 PCT Filed Jun. 30, 1993 PCT Pub. No. WO94/01516 PCT Pub. Date Jan. 20, 1994.A base oil with a high viscosity index and low pour point which is a mixture of a complex ester formed from aliphatic, cycloaliphatic or aromatic dicarboxylic acids, aliphatic polyols containing 2 to 6 hydroxyl groups and aliphatic monocarboxylic acids containing 6 to 22 carbon atoms and adipic acid esters of unbranched aliphatic monohydric alcohols.

Description

"Basic oils with high viscosity index and improved cold behavior"

The present invention relates to base oils with a high viscosity index and improved low-temperature behavior, which contain complex esters and adipic acid esters of unbranched monofunctional alcohols, and to a process for the preparation of such base oils and their use as hydraulic, compressor and motor oils.

It has long been known to use synthetic esters both as a base oil and as an additive in lubricants. In comparison to the cheaper but more environmentally friendly mineral oils, the synthetic esters were mostly used as base oils when high demands were made on the viscosity-temperature behavior and a low pour point, as was the case with aircraft turbine oils. In recent times, esters based on oleochemicals have become increasingly important, since they are not only powerful, but also biodegradable. As a rule, the esters on the basis of oleochemistry are divided into 5 groups: mono-, glycerol, dicarboxylic acid, polyol and complex esters. For technological and economic reasons, the dicarboxylic acid esters are derived primarily from adipic, trimethyladipinic, sebacic, azelaic, dodecanedioic and brassylic acid, the Cβ - ^ - D'.carboxylic acid derivatives in particular being of increasing importance since they have a very good viscosity-temperature behavior. The so-called viscosity index (VI), which is determined at 40 and 100 ° C. in accordance with DIN 51562 and is calculated in accordance with DIN ISO 2909, is usually given as the index of the viscosity-temperature ratio in the lubricating oil sector. High VI values indicate that slight viscosity fluctuations are observed at different temperatures. Most of the above dicarboxylic acid esters have high VI values. In particular, linear dicarboxylic acid esters of adipic acid with VI values of 200 and higher show an extraordinarily low temperature dependence of the viscosity. A disadvantage of the dicarboxylic acid esters of adipic acid mentioned is their low viscosity, which means that they are not suitable for all fields of application.

Higher viscosities than adipic acid esters show complex esters which are composed of polyfunctional carboxylic acids and polyols and monocarboxylic acids. Unfortunately, these complex esters do not show such good viscosity-temperature behavior and thus lower Vl values than the dicarboxylic acid esters of adipic acid.

Both the adipic acid esters and the complex esters admittedly have an acceptable cold behavior insofar as the pour point, that is to say the temperature which results when 3 ° C. is added to the temperature read, at which the sample no longer cools down is flowable, is around -30 ° C. For some areas of application, however, it is advantageous if the base oil has an even lower pour point.

The object of the present invention was to provide base oils with improved cold behavior (pour point), which moreover have higher viscosities than the known adipic acid esters. Furthermore, these base oils should have very good viscosity-temperature behavior and Vl values should be over 200.

Surprisingly, base oils from certain complex esters and the dicarboxylic acid esters of adipic acid show better cold behavior with a high viscosity index.

The present invention relates to base oils which

I. complex esters of a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids with 2 to 36 carbon atoms b) aliphatic polyols with 2 to 6 hydroxyl groups c) aliphatic monocarboxylic acids with 6 to 22 carbon atoms and

II. Adipic acid esters of unbranched aliphatic monofunctional

Contain alcohols.

For the purposes of the invention, the base oils according to the invention are products which are liquid at room temperature (20 to 25 ° C.). The complex esters and adipic acid esters contained in the base oils according to the invention are so-called full esters in the sense of the invention, which means that these esters should not have any free hydroxyl or carboxyl group per molecule. Rather, complex esters and adipic acid esters are sought which have no or only small hydroxyl or acid numbers, preferably in the range below 3, because of the esterification, which is never complete in practice.

The adipic acid esters contained in the base oils according to the invention are known compounds which are formed by esterification of the adipic acid with unbranched aliphatic monofunctional alcohols. Adipic acid esters derived from saturated alcohols are preferred. Since the adipic acid esters should be as liquid as possible, those are particularly preferred which are derived from saturated alcohols having 1 to 4 carbon atoms, in particular from methanol, ethanol, propanol and / or butanol. From this group, the dibutyl adipate is of outstanding importance, especially since it also has an excellent VI.

The complex esters contained in the base oils according to the invention are also compounds known per se. For example, in the German patent DE-C-19 07 768 the use of such More complex described as a lubricant for thermoplastics. These complex esters can also be easily prepared by esterification reactions of the dicarboxylic acids, polyols and monocarboxylic acids. As aliphatic, cycloaliphatic or aromatic dicarboxylic acids are oxalic, malonic, amber, glutaric, adipic, pimeline, cork, azelaic, sebacic, undecanedicarbonic, eicosanedicarbonic, maleic, fumaric, citraconic, Mesaconic, itaconic, cyclopropane, cyclobutane, cyclopentadicarboxylic acid, camphoric acid, hexahydrophthalic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalic acid, diphenyl- o, o'-dicarboxylic acid and dimer fatty acids are suitable. Dimer fatty acids for the purposes of the invention are dicarboxylic acids which are prepared by dimerizing mono- or polyunsaturated monocarboxylic acids in the presence of catalysts. Of the dimer fatty acids, preference is given to those which have been prepared by dimerizing monounsaturated monocarboxylic acids having 12 to 22 carbon atoms, and in particular those which have been prepared by dimerizing oleic acid. Of the aliphatic dicarboxylic acids, those having 6 to 10 carbon atoms and in particular the saturated representatives thereof are particularly preferred. From the group of aromatic dicarboxylic acids, phthalic acid is particularly suitable. Instead of the dicarboxylic acids, their anhydrides can also be used to prepare the complex esters. Seen overall, aliphatic dicarboxylic acids with 6 to 10 carbon atoms, phthalic acid and / or dimer fatty acid as the basis for the complex esters are preferred from the group of the dicarboxylic acids, the dimer fatty acid being obtained by dimerizing monounsaturated monocarboxylic acids having 12 to 22 carbon atoms have been produced.

Examples of aliphatic polyols on which the complex esters are based are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Glycerin, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, xylitol, mannitol and / or sorbitol. Of these polyols are particularly preferred branched polyols which preferably have tertiary carbon atoms (that is to say those which do not bear a hydrogen atom) in the vicinity of the primary hydroxyl groups, such as trimethylolpropane, pentaerythritol, neopentylglycol, dipentaerythritol and / or mixtures thereof.

Examples of aliphatic monocarboxylic acids with 6 to 22 carbon atoms from which the complex esters are made are: caprylic, pelargon, capric, undecane, lauric, laurolein, tridecane, myristic, myristic linseed, pentadecane, palmitin, palmitolein, heptadecane, stearin, petrotselin, petroselaidin, oil, eladine, linoleic, linolaidine, linolenic, nonadecane, arachine, arachidone, Behenic, erucic and / or brassidic acid. The straight-chain representatives thereof are preferred from this group of saturated and / or unsaturated monocarboxylic acids.

The complex esters contained in the base oils according to the invention are preferably constructed such that the static average of the 2 to 6 hydroxyl groups of the polyols is 25 to 75% with dicarboxylic acids and 75 to 25% with monocarboxylic acids. When calculating the% number of esterified hydroxyl groups, it is formally assumed how many hydroxyl groups are present in the reaction mixture forming the complex ester and that 25 or 75% of this reaction mixture is esterified with dicarboxylic acids or monocarboxylic acids. In the complex esters formed in the process, it is therefore completely irrelevant on a statistical average whether the dicarboxylic acid esterifies 2 hydroxyl groups of a polyol or bridging 2 hydroxyl groups of two polyols.

The base oils according to the invention preferably contain the complex esters in amounts of 25 to 75% by weight and the adipic acid esters in amounts of 75 to 25% by weight, based on the base oil. Base oils which are present in amounts of 25 to 75% by weight of dibutyl adipate and in amounts of 25 to 75% by weight of complex esters of a) dimer fatty acids, adipic, pimeline, cork, azelaic, sebacic and / or

Phthalic acid and b) neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and / or mixtures thereof and c) caprylic, capric, lauric, myristic, palmitic, stearic and / or oleic acid.

The base oils according to the invention have a pour point which is significantly lower than the pour points of the individual complex esters or adipic acid esters. Because of the significantly lower pour point, the cold behavior of the base oils according to the invention is much better since the base oils are no longer flowable at a lower temperature. This opens up areas of application with these base oils that have so far remained closed to the individual complex esters or adipic acid esters. Furthermore, the base oils according to the invention have a significantly higher viscosity than the pure adipic acid esters, so that they are suitable for broader fields of application than the low-viscosity adipic acid esters. In addition, the base oils according to the invention have better viscosity-temperature behavior than the pure complex esters, so that the field of application also widens here. The fact that the complex esters and the adipic acid esters can be mixed with one another in wide ranges of amounts and the improved low-temperature behavior (pour point) always proves to be particularly favorable with the base oils according to the invention. Using the different viscosities of the complex esters and the adipic acid ester, any desired viscosities of the base oil can be set. It is thus possible to adjust a low-viscosity base oil by adding higher amounts of the low-viscosity adipic acid ester, which also has an extremely high viscosity index. Another object of the invention is a process for the production of base oils with a high viscosity index and improved low-temperature behavior, characterized in that complex esters of a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids having 2 to 36 carbon atoms b) aliphatic polyols having 2 to 6 Hydroxyl groups c) aliphatic monocarboxylic acids having 6 to 22 carbon atoms are mixed with adipic acid esters of unbranched aliphatic monofunctional alcohols.

If desired, the base oils according to the invention can additionally contain mono-, glycerol and / or polyol esters or also mineral oils. The amount of these additional esters or mineral oils depends on the respective area of application. Furthermore, the base oils according to the invention can be additized in order to further optimize them for their application. Suitable additives are, for example, oxidation inhibitors, such as sulfur, phosphorus, phenol derivatives or amines, detergents such as naphthenates, stearates, sulfonates, phenolates, phosphates, Phosphonates or methacrylate copolymers, extreme pressure additives such as sulfur and chlorine compounds, anti-foaming agents, demulsifiers, corrosion inhibitors or also friction coefficients. If desired, the known viscosity index improvers such as polyalkylstyrenes, polyolefins, polymethacrylic acid esters, polyisobutenes and diene polymers can also be added to the base oils according to the invention, but this makes the base oils according to the invention more sensitive to shear. On the whole, the base oils according to the invention already show such good viscosity-temperature behavior that an addition of viscosity index improvers is not necessary. Another advantage of the base oils according to the invention is that they are no longer as sensitive to shear as mineral oils to which viscosity index improvers have to be added. The base oils according to the invention can be used in a wide range of applications. However, due to their quality profile, use as hydraulic, compressor and motor oils is particularly preferred.

B e i s p i e l e

A) Preparation of the complex esters

1) Complex ester of trimethylolpropane, oleic acid, dimer fatty acid

171.84 g trimethylolpropane, corresponding to 1.42 mol,

685.2 g technical oleic acid (composition in% by weight: Ciss' 5; C17 1; Ciß

2; Ciβ '67; Cig "12; Cig" '1; > Cχ8 2 / with an acid number SZ according to DIN

53402 of 198) ₍ corresponding to 2.4 mol, and 327.77 g of Ciss di-fatty acid with an SZ of 193, corresponding to 1.1 mol, were in the presence of 0.33 g

Tin oxalate esterified with each other at increasing temperatures up to 240 ° C. The

Esterification was ended when the acid number of the complex ester obtained was below 1. The complex ester was bleached with bleaching earth at 90 ° C. and then filtered off.

Characteristic data: saponification number VZ (according to DIN 53401) 185 iodine number JZ (according to DGF-C-V 11b) 85

VI (according to DIN 51562 and calculated according to DIN ISO 2909) = 186 pour point (according to DIN ISO 3016) -31 ° C.

2) Complex esters of trimethylolpropane, oleic acid and dimer fatty acid Analogously to Example 1, 159.05 g of trimethylolpropane, corresponding to 1.325 mol, 570 g technical oleic acid having an acid number of 198, corresponding to 2 mol, and 411.0 g cis-dimer fatty acid having an acid number of 183, corresponding to 1. 3 mol converted and processed. A complex ester with the following characteristics was obtained:

VZ = 180; JZ = 85; VI = 200; Pour point -32 ° C. 3) complex esters of dipentaerythritol, isononanoic acid, Cs / io-Fe acid and

Phthalic acid 320.25 g dipentaerythritol, corresponding to 1.26 mol, 172.5 g isononanoic acid, corresponding to 1.1 mol, 646.5 g Cβ / io fatty acid (composition in% by weight: 69-75 Cs; 23-27 CIQ ; Radicals C and C12; acid number 368), corresponding to 4.2 mol, and 121.75 g phthalic anhydride, corresponding to 0.8 mol, were prepared and prepared analogously to Example 1. A complex ester was obtained with the following characteristics: VZ = 360; JZ <1, VI = 100; Pour point -15 ° C.

B) Production of base oils

The complex esters A 1) to 3) were mixed with different amounts of dibutyl adipate with the characteristics: VI =>250; Pour point = -31 ° C mixed. Table I summarizes the mixing ratios, V40 and the pour point of the base oils. The amounts of ester are given in parts by weight (T).

Table I basic values and characteristics

DBA = dibutyl adipate

From Table I it can be seen that base oils with the low-viscosity dibutyl adipate and the high-viscosity complex esters on the one hand have a higher viscosity than pure dibutyl adipate and on the other hand have much lower pour points than the pure starting materials.

Claims

Patent claims

1. Containing base oils with a high viscosity index and improved cold behavior

I. Complex esters of a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids with 2 to 36 C atoms b) aliphatic polyols with 2 to 6 hydroxyl groups c) aliphatic monocarboxylic acids with 6 to 22 C atoms and

II. Adipic acid esters of unbranched aliphatic monofunctional alcohols.

2. Base oils according to claim 1, characterized in that they contain adipic acid esters of saturated alcohols, preferably having 1 to 4 carbon atoms.

3. Base oils according to claim 1, characterized in that they contain complex esters in which 25 to 75% of the hydroxyl groups of the polyols are esterified with the dicarboxylic acids and 75 to 25% of the hydroxyl groups of the polyols with the monocarboxylic acids.

4. Base oils according to claim 1, characterized in that they contain complex esters of aliphatic dicarboxylic acids with 6 to 10 carbon atoms, phthalic acid and / or dimer fatty acid, the latter having been prepared by dimerization of monounsaturated monocarboxylic acids with 12 to 22 carbon atoms is.

5. Base oils according to claim 1, characterized in that they contain complex esters of branched polyols, which preferably have tertiary C atoms in the vicinity of the primary hydroxyl groups, such as Neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and / or mixtures thereof.

6. base oils according to claim 1, characterized in that they contain complex esters of straight-chain monocarboxylic acids.

7. Base oils according to claim 1, characterized in that they contain the complex esters in amounts of 25 to 75% by weight and the adipic acid esters in amounts of 75 to 25% by weight, based on the base oil.

8. A process for the preparation of base oils with a high viscosity index and improved low-temperature behavior, characterized in that complex esters of a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids with 2 to 36 C atoms b) aliphatic polyols with 2 to 6 hydroxyl groups c) aliphatic monocarboxylic acids with 6 to 22 carbon atoms are mixed with adipic acid ester of unbranched aliphatic monofunctional alcohols.

9. Use of base oils according to claim 1 as hydraulic, compressor and motor oils.